CN101495234A

CN101495234A - Novel molecular sieve composition, making method and use method thereof

Info

Publication number: CN101495234A
Application number: CNA2007800283649A
Authority: CN
Inventors: W·J·罗瑟; M·M·默滕斯; E·C·德克莱克; I·D·约翰逊
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2006-07-28
Filing date: 2007-07-13
Publication date: 2009-07-29
Anticipated expiration: 2027-07-13
Also published as: CN101489676B; ZA200810603B; CN101495234B; CN101489676A

Abstract

This disclosure relates to a crystalline MCM-22 family molecular sieve composition having, in its as-synthesized form, an X-ray diffraction pattern including a peak at d-spacing maximum of 12.33.fcO.23 Angstroms, a distinguishable peak at a d-spacing maximum between 12.57 to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximum between 8.8 to 11. Angstroms, wherein the peak intensity of the d-spacing maximum between 12.57 to about 14.17 Angstroms is less than 90% of the peak intensity of the d-spacing maximum at 12.33+-0.23 Angstroms. This disclosure also relates to methods of making the crystalline MCM-22 family molecular sieve composition.

Description

Novel molecular sieve composition, its manufacture method and using method

Invention field

[0001] present disclosure relates to novel molecular sieve composition, its manufacture method and using method.Specifically, present disclosure relates to novel molecular sieve composition, and it is EMM-10 or the MCM-22 section bar material with low angle feature of MCM-22-P and MCM-56.

Disclosure background

[0002] natural and synthetic molecular screen material all shows in the past various types of hydrocarbon are transformed and has catalytic performance.The molecular sieve that is applied aspect catalysis comprises any naturally occurring or synthetic crystalline molecular sieve.The example of these zeolites comprises large pore zeolite, intermediate pore size zeolite and pore zeolite.The same kind of these zeolites and they is at " Atlas of ZeoliteFramework Types ", editor W.H.Meier, and D.H.Olson and Ch.Baerlocher, Elsevier, the 5th edition, be described in 2001, the document is incorporated herein for reference.Large pore zeolite generally have the aperture of about at least 7 dusts and comprise LTL, VFI, MAZ, FAU, OFF, ^*BEA and MOR framework types zeolite (IUPAC Commission of ZeoliteNomenclature).The example of large pore zeolite comprises mazzite, offretite, zeolite L, VPI-5, zeolite Y, X zeolite, ω and β.Intermediate pore size zeolite generally has about 5 dusts to less than the aperture of about 7 dusts and comprise for example MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW and TON framework types zeolite (IUPAC Commission of ZeoliteNomenclature).The example of intermediate pore size zeolite comprises ZSM-5, ZSM-11, ZSM-22, MCM-22, siliceous zeolite (silicalite) 1 and siliceous zeolite 2.The small-bore zeolite has about 3 dusts to less than the aperture of about 5.0 dusts and comprise for example CHA, ERI, KFI, LEV, SOD and LTA framework types zeolite (IUPAC Commission of Zeolite Nomenclature).The example of pore zeolite comprises ZK-4, ZSM-2, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabasie, zeolite T, sodium chabazite, ALPO-17 and clinoptilolite.

[0003] U.S. Patent number 4,439,409 relate to molecules screen composition and its synthesizing from hydro-thermal reaction usefulness reactant mixture that the material name is called PSH-3, this hydro-thermal reaction comprises hexamethylene imine with reactant mixture, promptly serve as and be used for synthetic MCM-56 (U.S. Patent number 5, the organic compound of directed agents 362,697).Hexamethylene imine also is used for synthetic crystallization molecular sieve MCM-22 (U.S. Patent number 4,954,325) and MCM-49 (U.S. Patent number 5,236,575) by instruction.The combination of molecular sieve that is called zeolite SSZ-25 (U.S. Patent number 4,826,667) is synthetic with reactant mixture by the hydro-thermal reaction that comprises the adamantane quaternary ammonium ion.U.S. Patent number 6,077,498 relate to molecules screen composition and its synthesizing by the hydro-thermal reaction usefulness reactant mixture that comprises one or more organic additives that the material name is called ITQ-1.

[0004] Chem.Lett. the 32nd volume of S.H.Lee, C.H.Shin and S.B Hong, the 6th phase, the Microporous andMesoporous Materials of 542-543 page or leaf (2003) and S.H.Lee, C.H.Shin, D.K.Yang, S.D.Ahn, I.S.Nam and S.B Hong, the 68th volume, 97-104 page or leaf (2004) has reported that this reactant mixture is by water, dibrominated Me by the MCM-22 molecular sieve that hydro-thermal reaction is synthesized with the reactant mixture crystallization ₆-diquat-5, Ludox HS-40, aluminum nitrate non-hydrate and the preparation of 50wt% sodium hydroxide solution.The mole that this mixture has is as shown in Table I formed.Under crystallization condition (as shown in Table I) make this crystalline mixture and be characterized as being the pure phase MCM-22 that crystalline size is about 0.5 * 0.05 μ m (micron, lamellar morphology).

Table I

* the OH of this delegation ^-/ SiO ₂Under the correction in aluminium source, calculate, wherein Al (NO ₃) ₃Be used for this two pieces of articles.

The OH of this delegation of * ^-/ SiO ₂Be under the situation of not proofreading and correct the aluminium source, to calculate.

[0005] provisional application number 60/834030 discloses a kind of crystalline molecular sieve (EMM-10-P), form when synthetic has such X-ray diffraction pattern to this crystalline molecular sieve by it: being included in the d spacing maximum at 13.18 ± 0.25 and 12.33 ± 0.23 dust places, is at 90% more than of the peaked peak intensity of 12.33 ± 0.23 d of dust place spacings at the peaked peak intensity of 13.18 ± 0.25 d of dust place spacings at least wherein.

[0006] temporary patent application number 60/834,001 discloses the manufacture method of a kind of crystalline molecular sieve (EMM-10-P), and this method may further comprise the steps:

(a) provide the mixture of at least one provenance of at least one provenance of at least one provenance that comprises at least a quadrivalent element (Y), at least a alkali metal or alkali earth metal, at least a directed agents (R), water and optional at least a triad (X), described mixture has following mol ratio:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

OH ^-∶Y＝0.001-0.59

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts (Me ₆-diquat-5 salt); With

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-200 ℃ temperature and about 1 hour-400 hours crystallization time.

[0007] temporary patent application number 60/834,032 discloses a kind of crystalline molecular sieve (EMM-10) that comprises the structure cell with MWW topological structure, be the form of its ammonium exchange or the form of its calcination, the diffraction fringe by the c direction of having arranged from structure cell since the described crystalline molecular sieve is feature.This crystalline molecular sieve is a feature with the arc hk0 pattern of electron diffraction diagram further.This crystalline molecular sieve is a feature with the structure cell striped along the c direction further.

[0008] temporary patent application number 60/834,031 discloses the manufacture method of a kind of crystalline molecular sieve (EMM-10), and this method may further comprise the steps:

(a) provide the mixture of at least one provenance that comprises at least a quadrivalent element (Y), at least one provenance of at least a triad (X), at least a alkali metal or at least one provenance of alkali earth metal, at least a directed agents (R) and water, described mixture has following mole and forms:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

OH ^-∶Y＝0.001-0.59

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-200 ℃ temperature and about 1 hour-400 hours crystallization time;

(c) reclaim this crystalline molecular sieve; With

(d) make this crystalline molecular sieve and ammonium nitrate solution ion-exchange.

[0009] well-known, crystal habit, size and gathering/agglomeration or new X-ray diffraction may influence the performance of catalyst performance, particularly catalyst activity and stable aspect.Therefore, the manufacture method that still needs novel crystallization combination of molecular sieve and this kind novel crystallization combination of molecular sieve.

The summary of present disclosure

[0010] in some embodiments, present disclosure relates to crystallization MCM-22 family molecular sieve, form when synthetic has such X-ray diffraction pattern to this molecular sieve: the peak that is included in the d spacing maximum place of 12.33 ± 0.23 dusts by it, the non-discrete peak at the peak distinguished at the d spacing maximum place between about 14.17 dusts of 12.57-and the d spacing maximum place between the 8.8-11 dust, wherein the peak intensity at the d spacing maximum place between about 14.17 dusts of 12.57-is less than at 90% of the peaked peak intensity of d spacing at 12.33 ± 0.23 dust places.

[0011] in other embodiments, present disclosure relates to the manufacture method of the crystalline molecular sieve described in above-mentioned arbitrary claim, may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

Under the situation that does not have the triad source to proofread and correct, OH ^-: Y=0.001-0.59, and/or

OH ^-: Y (under the correction of triad source)=0.001-0.39

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination, wherein said OH ^-: Y calculates; With

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-250 ℃ temperature, and at least 150 RPM are to less than the mixing speed of 5000 RPM and about 1 hour-400 hours crystallization time; And

(c) reclaim this crystalline molecular sieve.

[0012] in other embodiment that also has, present disclosure relates to the manufacture method of crystalline molecular sieve, and this method may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

Under the situation that does not have the triad source to proofread and correct, OH ^-: Y=0.74-2 and/or proofread and correct in the triad source under, OH ^-: Y=0.64-2

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination, wherein said OH ^-: Y calculates under the situation that does not have the triad source to proofread and correct; With

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-200 ℃ temperature, and 150RPM is to less than the mixing speed of 5000RPM and about 1 hour-400 hours crystallization time at least; And

(c) reclaim this crystalline molecular sieve.

[0013] in other embodiment that also has, present disclosure relates to the manufacture method of crystalline molecular sieve, and this method may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝5-35

OH ^-∶Y＝0.001-2

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination, wherein said OH ^-: Y calculates under the situation that has or do not have the triad source to proofread and correct; With

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-200 ℃ temperature, and 150RPM is to less than the mixing speed of 5000 RPM and about 1 hour-400 hours crystallization time at least; And

(c) reclaim this crystalline molecular sieve.

[0014] in other embodiment that also has, present disclosure relates to the manufacture method of crystalline molecular sieve, and this method may further comprise the steps:

(a) provide the mixture of at least one provenance of at least one provenance of at least one provenance that comprises at least a quadrivalent element (Y), at least a alkali metal or alkali earth metal, at least a directed agents (R), water, at least a crystal seed and optional at least a triad (X), described mixture has following mol ratio:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

OH ^-∶Y＝0.001-2

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination, wherein said OH ^-: Y calculates under the situation that has or do not have the triad source to proofread and correct, and wherein said crystal seed has the concentration in this mixture of about 0.01-10wt%, based on the weight of quadrivalent element oxide in this mixture; With

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-200 ℃ temperature and about 1 hour-400 hours crystallization time; And

(c) reclaim this crystalline molecular sieve.

[0015] in other embodiment that also has, present disclosure relates to the manufacture method of crystalline molecular sieve, and this method may further comprise the steps:

(a) provide the mixture of at least one provenance of at least one provenance of at least one provenance that comprises at least a non-germanium quadrivalent element (Y), at least one provenance of germanium (Ge), at least a directed agents (R), water and optional at least a triad (X) and at least a alkali metal or alkali earth metal, described mixture has following mol ratio:

(Ge+Y): X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

M ⁺∶Y＝0-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R comprise at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination; With

(c) reclaim this crystalline molecular sieve.

[0016] in some embodiments, present disclosure relates to the MCM-22 family molecular sieve of making by the method for present disclosure.

[0017] in other embodiments, present disclosure relates to hydroconversion process, may further comprise the steps: allow hydrocarbon feed contact to form product with the crystalline molecular sieve of crystalline molecular sieve of making by each method among the claim 7-30 or claim 1-6 under conversion condition.

[0018] these and other aspect of the present invention will be by the following detailed description, accompanying drawing and appended claims come into focus.

The accompanying drawing summary

Product when [0019] Fig. 1 a shows embodiment 1 synthetic was at 80 hours XRD.

Product when [0020] Fig. 1 b shows embodiment 1 synthetic was at 92 hours XRD.

The XRD of the product when [0021] Fig. 2 shows embodiment 1A synthetic.

[0022] Fig. 3 shows the SEM of embodiment 1A.

The XRD of the product when [0023] Fig. 4 shows embodiment 2 synthetic.

The SEM of the product when [0024] Fig. 5 shows embodiment 2 synthetic.

The XRD of the product when [0025] Fig. 6 shows embodiment 3 synthetic.

The SEM of the product when [0026] Fig. 7 shows embodiment 3 synthetic.

The XRD of the product when [0027] Fig. 8 shows embodiment 4 synthetic.

The SEM of the product when [0028] Fig. 9 shows embodiment 4 synthetic.

The XRD of the product when [0029] Figure 10 shows embodiment 5 synthetic.

The SEM of the product when [0030] Figure 11 shows embodiment 5 synthetic.

Describe in detail

[0031] in some embodiments, present disclosure relates to crystallization MCM-22 family molecular sieve, form when this molecular sieve is synthetic by it has such X-ray diffraction pattern: the peak that is included in the d spacing maximum place of 12.33 ± 0.23 dusts, the non-discrete peak at the peak distinguished at the d spacing maximum place between about 14.17 dusts of 12.57-and the d spacing maximum place between the 8.8-11 dust, wherein the peak intensity at the d spacing maximum place between about 14.17 dusts of 12.57-is less than at 90% of the peak intensity at the d spacing maximum place at 12.33 ± 0.23 dust places. In other embodiments, present disclosure relates to manufacture method and the using method of described molecular sieve.

Introduce

[0032] all patents, patent application, test procedure, priority document, article, publication, handbook and other file of quoting of this paper is consistent with the present invention and for reference for fully introducing on the degree of all authorities that allow this introducing in these publications.

[0033] when a plurality of lower limits and a plurality of upper limit when this lists, the scope from arbitrary lower limit to arbitrary upper limit should be considered.

[0034] term that uses in this specification " framework types " is pressed the meaning of describing among " the Atlas of Zeolite Framework Types " 2001 and is used.

[0035] numbering plan of each family of the employed periodic table of elements of this paper is according to Chemical and Engineering News, and 63 (5), 27 (1985) use.

[0036] term as used herein " tabular crystalline form (tabularhabit) " form refers to have the tabular inorganic matter of " the lamellar crystal of stacked in parallel ". Term as used herein " platelet " form refers to lamellar crystal.

[0037] term as used herein " MCM-22 family material " (or " material of MCM-22 family " or " molecular sieve of MCM-22 family ") comprising:

(i) molecular sieve of being made by common the first degree crystal structure unit (building block) " structure cell with MWW matrix topology ". Structure cell is the space arrangement of atom, and this space arrangement tiles to describe crystal with three dimensions, and such as " Atlas of Zeolite Framework Types ", the 5th edition, 2001 is described, and the whole content of the document is incorporated herein by reference;

(ii) molecular sieve of being made by common the second degree structural unit (the 2-dimension tiling of this kind MWW framework types structure cell) forms " individual layer of a structure cell thickness " a preferred c-structure cell thickness;

(iii) molecular sieve of being made by common the second degree structural unit, " one or more than a structure cell thickness the layer ", wherein more than the layer of a structure cell thickness by with at least two single layer stack, the filling of a structure cell thickness of structure cell or in conjunction with making, this structure cell has the MWW matrix topology. The second degree the stacking of structural unit can be undertaken by the mode of rule, irregular mode, random fashion or its any combination this kind; Or

(iv) molecular sieve made of any rule of the structure cell by having the MWW matrix topology or 2-at random dimension or the combination of 3-dimension.

[0038] MCM-22 family material is characterised in that and has 12.4 ± 0.25, and 3.57 ± 0.07 and 3.42 ± 0.07 dust places comprise the peaked X-ray diffraction pattern of d-spacing (calcination or when synthetic). MCM-22 family material can also be characterised in that to have 12.4 ± 0.25, and 6.9 ± 0.15,3.57 ± 0.07 and 3.42 ± 0.07 dust places comprise the peaked X-ray diffraction pattern of d-spacing (calcination or when synthetic). The K-α two-wire of the X-ray diffraction data that is used for characterizing described molecular sieve by using copper as incident radiation and scintillation counter is equipped with and the computer that is connected as the standard technique acquisition of the diffractometer of gathering system. The material that belongs to MCM-22 family comprises that MCM-22 (is described in U.S. Patent number 4,954,325), PSH-3 (is described in U.S. Patent number 4,439,409), SSZ-25 (is described in U.S. Patent number 4,826,667), ERB-1 (being described in european patent number 0293032), ITQ-1 (are described in U.S. Patent number 6,077,498), ITQ-2 (being described in International Patent Publication No. WO 97/17290), ITQ-30 (being described in International Patent Publication No. WO 2005118476), MCM-36 (being described in U.S. Patent number 5,250,277), MCM-49 (are described in U.S. Patent number 5,236,575), UZM-8 (being described in U.S. Patent number 6,756,030) and MCM-56 (are described in U.S. Patent number 5,362,697). The whole content of described patent is hereby incorporated by.

[0039] self-evident, the molecular sieve of above-mentioned MCM-22 family has 12-ring surface cave (pocket) from different these MCM-22 materials that are of conventional large pore zeolite alkylation catalyst (for example modenite), and this cave is not communicated with the 10-ring internal holes system of this molecular sieve.

[0040] being called the zeolitic material with MWW topological structure by IZA-SC is multilayer material, and they are owing to the existence of 10 and 12 yuan of rings has two kinds of pore system. " Atlas of Zeolite Framework Types " with the materials classification of five kinds of different names for having this identical topological structure: MCM-22, ERB-1, ITQ-1, PSH-3 and SSZ-25.

[0041] molecular sieve of MCM-22 family has been found that and can be used for various hydrocarbon conversion process. The example of the molecular sieve of MCM-22 family is MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, UZM-8 and ERB-1. This molecular sieve analog can be used for the alkylation of aromatic compounds. For example, U.S. Patent number 6,936,744 disclose the preparation method of monoalkylation aromatic compounds (especially cumene), may further comprise the steps: but in that being contacted with alkylaromatic, many alkylaromatics prepare the monoalkylation aromatic compounds, wherein this transalkylation catalyst comprises the mixture of at least two kinds of different crystalline molecular sieves, and each in the wherein said molecular sieve is selected from zeolite beta, zeolite Y, modenite and X-ray diffraction pattern and comprises the peaked material of d-spacing at 12.4 ± 0.25,6.9 ± 0.15,3.57 ± 0.07 and 3.42 ± 0.07 dust places.

[0042] material that it will be appreciated by those skilled in the art that MCM-22 family can comprise impurity, for example amorphous materials; Structure cell (for example, MF I, MTW) with non-MWW matrix topology; And/or other impurity (for example, heavy metal and/or organic hydrocarbon). With the representative instance of the common non-MCM-22 family molecular sieve (one or more) that exists of the MCM-22 family molecular sieve (one or more) of present disclosure be kenyaite (Kenyaite), EU-1, ZSM-50, ZSM-12, ZSM-48, ZSM-5, ferrierite, modenite, sodalite and/or analcime. With other example of the common non-MCM-22 family molecular sieve (one or more) that exists of the MCM-22 family molecular sieve (one or more) of present disclosure be the molecular sieve with EUO, MTW, FER, MOR, SOD, ANA and/or MFI framework types. The MCM-22 family material of present disclosure preferably is substantially free of non-MCM-22 family's material (one or more). Term as used herein " is substantially free of non-MCM-22 family's material (one or more) " and refers to that the MCM-22 family material of present disclosure preferably comprises small scale (less than 50wt%) in this MCM-22 family material, preferably less than non-MCM-22 family's material (" impurity ") of 20wt%, this weight percent (wt%) value is based on the gross weight of impurity and pure phase MCM-22 family material.

It should be understood that in whole detailed description that [0043] characterization technique commonly used is used for describing molecular screen material. The technology that included these are commonly used is confirmed:

(a) structure of molecular screen material and degree of crystallinity are by X-ray diffraction (XRD); And/or

Form and the crystalline size of the molecular screen material of (b) measuring by SEM (SEM); And/or

(c) chemical composition is by atomic absorption spectrum and/or inductivity coupled plasma mass spectrometry (ICP-MS or ICPMS);

(d) adsorption capacity and the surface area measured by nitrogen BET method; And/or

(e) catalytic activity and the catalytic stability measured by probe reaction (probing reaction).

The X-ray powder diffraction pattern

[0044] interplanar distance d is by angstrom unit

Calculate, and the relative intensity I/I of line₀Obtain by means of curve fitting procedure (or second derivative algorithm), wherein with the strongest line strength I above the background₀Can be regarded as 100. Described intensity is not carried out Lorentz and polarization effect correction. Relative intensity provides according to following symbol: VS=is strong (greater than 60-100) very, S=strong (greater than 40-60), M=medium (greater than 20-40) and W=weak (0-20). Should be appreciated that the diffraction data that goes out as single alignment can be made of a plurality of double lines, these double lines are at the lower line that can show as decomposition or decomposed of some condition (for example difference aspect the crystallization variation). Usually, crystallization changes the variation of minor variations and/or the crystal symmetry that can comprise cell parameter, and structure does not change. These minor impact (comprising the variation of relative intensity) also can be owing to cations, skeleton composition, the nature and extent of pore filling and the difference of heat and/or hydro-thermal history occur. Other variation of diffraction pattern can be indicated the significant differences between the material, and situation was like this when relatively MCM-22 was with similar material (for example MCM-49, MCM-56 and PSH-3).

[0045] if being determined as the peak width that show about 1.5 degree from half At The Height interplanar distance d of 50% intensity level that is up to baseline, thinks that then it is wide.

[0046] term as used herein " the differentiable peak of XRD " is defined as the XRD peak with summit of knowing profile, and this summit is at least twice of average background noise level.

[0047] " non-discrete " peak (also being called " undecomposed " peak) among the term as used herein XRD refers to their middle peaks (unanimously improve (or keeping evenly) or reduce the continuity point of (or maintenance evenly) in noise) with monotonous curve.

[0048] " dispersing " peak among the term as used herein XRD (being also referred to as " decomposition " peak) refers to not be the XRD peak of non-discrete (undecomposed).

The X-ray diffraction pattern of the crystalline molecular sieve that [0049] the molecules screen composition of present disclosure can be when synthetic is as feature, and this X-ray diffraction pattern comprises three peaks: (1) is in the d spacing maximum at 12.33 ± 0.23 dust places; (2) the d spacing maximum (Table II) between 14.17 and 12.57 dusts; (3) the non-discrete d spacing maximum between 8.8 and 11.1 dusts, wherein the peak intensity at the d spacing maximum place between 14.17 and 12.57 dusts is less than at 90% of the peaked peak intensity of d spacing at 12.33 ± 0.23 dust places.

Table II

The X-ray diffraction pattern of the crystalline molecular sieve when [0050] the molecules screen composition of present disclosure can pass through to synthesize characterizes, and this X-ray diffraction pattern comprises the d spacing maximum of listing in Table III or the Table IV.

Table III

Crystal face d spacing (dust)	Relative intensity, I/I₀×100
Crystal face d spacing (dust)	Relative intensity, I/I₀×100	14.17＞d＞12.57	M-VS
12.33±0.23	M-VS	14.17＞d＞12.57	M-VS
12.33±0.23	M-VS	11.1-8.8	W-S
3.57±0.06	W-M	11.1-8.8	W-S
3.57±0.06	W-M	3.43±0.06	M-VS

Table IV

Crystal face d spacing (dust)	Relative intensity, I/I₀×100
Crystal face d spacing (dust)	Relative intensity, I/I₀×100	14.17＞d＞12.57	M-VS
12.33±0.23	M-VS	14.17＞d＞12.57	M-VS
12.33±0.23	M-VS	11.1-8.8	W-S
4.41±0.1	W-M, wide	11.1-8.8	W-S
4.41±0.1	W-M, wide	3.96±0.08	W-VS, wide
3.57±0.06	W-M	3.96±0.08	W-VS, wide
3.57±0.06	W-M	3.43±0.06	M-VS

[0051] compares with similar material (MCM-22, MCM-22-P, MCM-36, MCM-49, MCM-56, EMM-10-P and EMM-10), the composition of present disclosure has three crucial peaks that this composition and MCM-22, MCM-22-P, MCM-36, MCM-49, MCM-56 and EMM-10 are distinguished, and is as follows:

(1) have the peaked peak of d spacing at 12.33 ± 0.23 dust places:

All material, the composition of MCM-22, MCM-22-P, MCM-36, MCM-49, MCM-56, EMM-10-P, EMM-10 and present disclosure;

(2) between 14.17 and 12.57 dusts, have the peaked peak of d spacing:

(a) MCM-22, MCM-36, MCM-49, EMM-10 and MCM-56 do not have such peak,

(b) MCM-22-P, EMM-10-P and this material have such peak, yet, for EMM-10-P, such peak be have at 12.33 ± 0.23 dust places the peaked peak of d spacing at least 90% so that higher;

(3) between 8.66-11.3, have the peaked non-discrete peak of d spacing:

It is (a) similar with MCM-56, MCM-36 and EMM-10-P,

(b) for all other materials, MCM-22, MCM-22-P, MCM-49 and EMM-10, such peak is discrete peak, or in the situation of EMM-10, is decomposed.

Described difference is summarised among the following table V:

Table V

[0052] in some embodiments, the X-ray diffraction pattern of the crystalline molecular sieve of present disclosure also is included in the d spacing maximum at 28 ± 1 dust places.

SEM (SEM)

[0053] Chem.Lett of S.H.Lee, C.H.Shin and S.B Hong, the 32nd volume, the 6th phase, disclosed known MCM-22 crystalline material when synthetic is reported as particle size and the platelet form with about 0.5 * 0.05 μ m in the 542-543 page or leaf (2003).

[0054] by non-germanium with not sow the SEM image of crystalline molecular sieve of the present disclosure that preparation makes shown in Figure 5. Crystalline molecular sieve as shown in Figure 5 has the crystal habit of 5-20 micron spherical (circular, ellipse) aggregation, and this aggregation is the aggregation less than the symbiosis platelet crystal of 0.1 micron thickness. The SEM image of the crystalline molecular sieve of the present disclosure of making by germanium and/or sowing preparation is shown in Fig. 7,9 and 11. The lamellated crystal habit of crystalline molecular sieve tool shown in Fig. 7,9 and 11, this thin slice have less than the estimation crystalline size of 2 microns maximum gauge and the about estimation thickness of 100nm.

Surface area and absorption picked-up (uDtake)

[0055] Brunauer-Emmett-Teller (BET) method be can pass through and nitrogen (temperature of liquid nitrogen, the total surface area of absorption-desorption measurement molecular sieve 77K) used.The t-that can use Brunauer-Emmett-Teller (BET) to measure draws and calculates internal surface area.Calculate external surface area by deduction internal surface area from the total surface area that records by Brunauer-Emmett-Teller (BET).

[0056] crystalline molecular sieve of present disclosure (after calcining) can be with greater than 450m ²/ g is preferably greater than 475m ²/ g is more preferably greater than 500m ²The preferred total surface area of/g (outer and inner surface area sum is measured by the BET method) is a feature.

[0057] in addition, the crystalline molecular sieve of present disclosure (after calcining) can be a feature with the preferred ratio less than 0.18 external surface area (t-by the BET method draws and measures) and total surface area.

The hydro-thermal reaction preparation of reactant mixture

[0058] synthesis of molecular sieve is usually by moisture hydro-thermal reaction mixture (synthetic mixture or the synthesized gel rubber) preparation that comprises suitable oxide source.Organic directed agents also can be included in this hydro-thermal reaction with the generation that has the molecular sieve of desired structure in the reactant mixture with influence.The use of this type of directed agents people's titles such as Lok be " The Role of Organic Molecules inMolecular Sieve Synthesis " (be published in Zeolites, the 3rd the volume, October nineteen eighty-three, 282-291 page or leaf) article in discuss.

[0059] after suitably hydro-thermal reaction being mixed with each other with the component of reactant mixture, allow this hydro-thermal reaction handle with the suitable crystallization condition of reactant mixture experience.In some embodiments of present disclosure, these conditions generally include this hydro-thermal reaction are heated to the temperature of rising and stirring simultaneously with reactant mixture.This hydro-thermal reaction also is desirable with the slaking of reactant mixture under 0-120 ℃ temperature in some cases.

[0060] the crystalline molecular sieve material of present disclosure can be prepared with reactant mixture by the hydro-thermal reaction that comprises following component: the source of alkali metal or alkaline-earth metal (M), the source of sodium or potassium cationic for example, triad X is the oxide of aluminium for example, quadrivalent element Y is the oxide of silicon for example, organic directed agents (R) (more specifically describing hereinafter), and water; In some preferred embodiments, this hydro-thermal reaction has composition in the following scope in Table VI with reactant mixture, presses the molar ratio computing of oxide:

Table VI

Reactant	Useful	Preferably
Reactant	Useful	Preferably	YO ₂/X ₂O ₃	10 to infinitely great	15-120
H ₂O/YO ₂	1 to 10000	5-35	YO ₂/X ₂O ₃	10 to infinitely great	15-120
H ₂O/YO ₂	1 to 10000	5-35	OH ^-/YO ₂	0.001-0.39	0.1-0.35
OH ^-/YO ₂	0.001-0.59	0.1-0.5	OH ^-/YO ₂	0.001-0.39	0.1-0.35
OH ^-/YO ₂	0.001-0.59	0.1-0.5	M/YO ₂	0.001-2	0.1-1
R/YO ₂	0.001-2	0.01-0.5	M/YO ₂	0.001-2	0.1-1
R/YO ₂	0.001-2	0.01-0.5	Crystal seed ^***	0-25wt％	1-5wt％
R	Me ₆-diquat-5 salt	Me ₆-diquat-5 salt	Crystal seed ^***	0-25wt％	1-5wt％

* the OH of this delegation ^-/ YO ₂Be under the situation that has the triad source to proofread and correct, to calculate.

The OH of this delegation of * ^-/ YO ₂Be under the situation that does not have the triad source to proofread and correct, to calculate.

The weight percent (wt%) of * * crystal seed is based on the weight of solid tetrahedron element oxide.

[0061] for these embodiments, when hydro-thermal reaction has in the Table VI disclosed composition with reactant mixture, OH under the situation that does not have the triad source to proofread and correct ^-: YO ₂Mol ratio be about 0.001-about 0.59 and/or under the situation that has the triad source to proofread and correct OH ^-: YO ₂Be about 0.001-about 0.39.

[0062] following OH ^-: YO ₂Mol ratio (not having the triad source to proofread and correct) is the useful OH of the disclosed embodiments in the Table VI ^-: YO ₂Mol ratio (not having the triad source to proofread and correct) lower limit: 0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5 and 0.55.Following OH ^-: YO ₂Mol ratio (not having the triad source to proofread and correct) is the useful OH of the disclosed embodiments in the Table VI ^-: YO ₂Mol ratio (the not having the triad source to proofread and correct) upper limit: 0.59,0.55,0.51,0.5,0.4,0.3,0.2 and 0.1.This OH ^-: YO ₂Mol ratio (do not have triad source proofread and correct) falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This OH ^-: YO ₂Mol ratio (do not have triad source proofread and correct) can be by 0.001-0.59 in one embodiment, or 0.01-0.5, or 0.1-0.5, or the amount of 0.1-0.4 exists in another embodiment.

[0063] following OH ^-: YO ₂Mol ratio (having the triad source to proofread and correct) is the useful OH of the disclosed embodiments in the Table VI ^-: YO ₂Mol ratio (having the triad source to proofread and correct) lower limit: 0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.3 and 0.35.Following OH ^-: YO ₂Mol ratio (having the triad source to proofread and correct) is the useful OH of the disclosed embodiments in the Table VI ^-: YO ₂Mol ratio (the having the triad source to proofread and correct) upper limit: 0.39,0.35,0.31,0.3,0.2 and 0.1.This OH ^-: YO ₂Mol ratio (have triad source proofread and correct) falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This OH ^-: YO ₂Mol ratio (have triad source proofread and correct) can be by 0.001-0.39 in one embodiment, or 0.01-0.35, or 0.1-0.3, or the amount of 0.1-0.25 exists in another embodiment.

[0064] the crystalline molecular sieve material of present disclosure also can be prepared with reactant mixture by the hydro-thermal reaction that comprises following component: the source of alkali metal or alkaline-earth metal (M), the source of sodium or potassium cationic for example, triad X is the oxide of aluminium for example, quadrivalent element Y is the oxide of silicon for example, organic directed agents (R) (more specifically describing hereinafter), and water; This hydro-thermal reaction has composition in the following scope in Table VII with reactant mixture, according to the molar ratio computing of oxide:

Table VII

Reactant	Useful	Preferably
Reactant	Useful	Preferably	YO ₂/X ₂O ₃	10 to infinitely great	15-55
H ₂O/YO ₂	1 to 10000	5-35	YO ₂/X ₂O ₃	10 to infinitely great	15-55
H ₂O/YO ₂	1 to 10000	5-35	OH ^-/YO ₂	0.64-2	0.7-2
OH ^-/YO ₂	0.74-2	0.8-2	OH ^-/YO ₂	0.64-2	0.7-2
OH ^-/YO ₂	0.74-2	0.8-2	M/YO ₂	0.001-2	0.1-1
R/YO ₂	0.001-2	0.01-0.5	M/YO ₂	0.001-2	0.1-1
R/YO ₂	0.001-2	0.01-0.5	Crystal seed ^***	0-25wt％	1-5wt％
R	Me ₆-diquat-5 salt	Me ₆-diquat-5 salt	Crystal seed ^***	0-25wt％	1-5wt％

[0065] for these embodiments, when hydro-thermal reaction has in the Table VII disclosed composition with reactant mixture, OH under the situation that does not have the triad source to proofread and correct ^-/ YO ₂Mol ratio be about 0.74-about 2 and/or under the situation that has the triad source to proofread and correct OH ^-/ YO ₂Be about 0.64-about 2.

[0066] following OH ^-/ YO ₂Mol ratio (not having the triad source to proofread and correct) is the useful OH of all disclosure methods ^-/ YO ₂Mol ratio (not having the triad source to proofread and correct) lower limit: 0.74,0.77,0.78,0.80,0.90,1 and 1.5.Following OH ^-/ YO ₂Mol ratio (not having the triad source to proofread and correct) is the useful OH of all disclosure methods ^-/ YO ₂Mol ratio (the not having the triad source to proofread and correct) upper limit: 2,1.6,1.4,1.3,1.2,1,0.9 and 0.8.This OH ^-/ YO ₂Mol ratio (do not have triad source proofread and correct) falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This OH ^-/ YO ₂Mol ratio (do not have triad source proofread and correct) can be by 0.74-2 in one embodiment, or 0.8-2, or 0.8-1, or the amount of 0.8-1.1 exists in another embodiment.

[0067] following OH ^-/ YO ₂Mol ratio (having the triad source to proofread and correct) is the useful OH of all disclosure methods ^-/ YO ₂Mol ratio (having the triad source to proofread and correct) lower limit: 0.64,0.65,0.66,0.7,0.75,0.80,0.90,1 and 1.5.Following OH ^-/ YO ₂Mol ratio (having the triad source to proofread and correct) is the useful OH of all disclosure methods ^-/ YO ₂Mol ratio (the having the triad source to proofread and correct) upper limit: 2,1.6,1.4,1.3,1.2,1,0.9 and 0.8.This OH ^-/ YO ₂Mol ratio (have triad source proofread and correct) falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This OH ^-/ YO ₂Mol ratio (have triad source proofread and correct) can be by 0.74-2 in one embodiment, or 0.8-2, or 0.8-1, or the amount of 0.8-1.1 exists in another embodiment.

[0068] the crystalline molecular sieve material of present disclosure also can be prepared with reactant mixture by the hydro-thermal reaction that comprises following component: the source of alkali metal or alkaline-earth metal (M), the source of sodium or potassium cationic for example, triad X is the oxide of aluminium for example, quadrivalent element Y is the oxide of silicon for example, organic directed agents (R) (more specifically describing hereinafter), and water; This hydro-thermal reaction has composition in the following scope in Table VIII with reactant mixture, according to the molar ratio computing of oxide:

Table VIII

Reactant	Useful	Preferably
Reactant	Useful	Preferably	YO ₂/X ₂O ₃	10 to infinitely great	15-55
H ₂O/YO ₂	5-35	5-30	YO ₂/X ₂O ₃	10 to infinitely great	15-55
H ₂O/YO ₂	5-35	5-30	OH ^-/YO ₂	0.001-2	0.001-2
M/YO ₂	0.001-2	0.1-1	OH ^-/YO ₂	0.001-2	0.001-2
M/YO ₂	0.001-2	0.1-1	R/YO ₂	0.001-2	0.01-0.5
Crystal seed ^***	0-25wt％	1-5wt％	R/YO ₂	0.001-2	0.01-0.5
Crystal seed ^***	0-25wt％	1-5wt％	R	Me ₆-diquat-5 salt	Me ₆-diquat-5 salt

* the OH of this delegation ^-/ YO ₂Be under the situation that has or do not have the triad source to proofread and correct, to calculate.

The weight percent of * crystal seed (wt%) is based on the weight of solid tetrahedron element oxide.

[0069] for these embodiments, when hydro-thermal reaction has in the Table VIII disclosed composition with reactant mixture, H ₂O: YO ₂Mol ratio is about 5-about 35 or about 5-30.Following H ₂O: YO ₂Mol ratio is the useful H of the disclosed embodiments in the Table VIII ₂O: YO ₂Lower mole ratio limit: 5,10,12,15,20,22,25 and 30.Following H ₂O: YO ₂Mol ratio is the useful H of the disclosed embodiments in the Table VIII ₂O: YO ₂The mol ratio upper limit: 10,15,20,25,30 and 35.This H ₂O: YO ₂Mol ratio falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This H ₂O: YO ₂Mol ratio can be by 5-35 in one embodiment, or 5-30, or 10-35, or 10-30, or 15-35, or the amount of 15-30 exists in another embodiment.

[0070] the crystalline molecular sieve material of present disclosure also can be prepared with reactant mixture by the hydro-thermal reaction that comprises following component: the source of alkali metal or alkaline-earth metal (M), the source of sodium or potassium cationic for example, triad X is the oxide of aluminium for example, quadrivalent element Y is the oxide of silicon for example, organic directed agents (R) (more specifically describing hereinafter), and water; This hydro-thermal reaction has composition in the following scope among the Table I X with reactant mixture, according to the molar ratio computing of oxide:

Table I X

Reactant	Useful	Preferably
Reactant	Useful	Preferably	YO ₂/X ₂O ₃	10 to infinitely great	15-55
H ₂O/YO ₂	1 to 10000	5-35	YO ₂/X ₂O ₃	10 to infinitely great	15-55
H ₂O/YO ₂	1 to 10000	5-35	OH ^-/YO ₂	0.001-2	0.001-2
M/YO ₂	0.001-2	0.1-1	OH ^-/YO ₂	0.001-2	0.001-2
M/YO ₂	0.001-2	0.1-1	R/YO ₂	0.001-2	0.01-0.5
Crystal seed ^***	1wppm-25wt％	1-5wt％	R/YO ₂	0.001-2	0.01-0.5
Crystal seed ^***	1wppm-25wt％	1-5wt％	R	Me ₆-diquat-5 salt	Me ₆-diquat-5 salt

[0071] for these embodiment, when hydro-thermal reaction has among the Table I X disclosed composition with reactant mixture, synthesizing of crystalline molecular sieve because the about 25wt% of 1wppm-, the existence of the about 5wt% seeding crystals of 1-preferably approximately and being promoted, based on the gross weight of this hydro-thermal reaction with the tetrahedron element oxide (for example, silica) in the reactant mixture.Following seeding crystals wt% (based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide of reactant mixture) is the useful seeding crystals wt% lower limit of the disclosed embodiments among the Table I X: 0.01,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5,1,2,5,10 and 15.Following seeding crystals wt% (based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide of reactant mixture) is the useful seeding crystals wt% upper limit of the disclosed embodiments among the Table I X: 1,2,5,10,15,20 and 25.Described seeding crystals wt% falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.Seeding crystals wt% (based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide of reactant mixture) can be by 0.01-25 in one embodiment, or 0.01-20, or 0.1-10, or 0.5-10, or 0.5-5, or the amount of 0.1-5 exists in another embodiment.

[0072] in some embodiments, Y comprises Ge and at least a identical non-germanium tetrahedron (Y) that does not just comprise Ge with Y.The source of Ge comprises germanium oxide, nitric acid germanium and other germanium salt.Hydro-thermal reaction has the composition in the following scope in Table X with reactant mixture, according to the molar ratio computing of oxide:

Table X

Reactant	Useful	Preferably
Reactant	Useful	Preferably	(GeO ₂+YO ₂)/X ₂O ₃	10 to infinitely great	15-600
H ₂O/YO ₂	1 to 10000	1-35	(GeO ₂+YO ₂)/X ₂O ₃	10 to infinitely great	15-600
H ₂O/YO ₂	1 to 10000	1-35	OH ^-/YO ₂	0.001-2	0.001-2
M/YO ₂	0.0-2	0.0-1	OH ^-/YO ₂	0.001-2	0.001-2
M/YO ₂	0.0-2	0.0-1	R/YO ₂	0.001-2	0.01-0.5
Crystal seed ^***	0-25wt％	1-5wt％	R/YO ₂	0.001-2	0.01-0.5
Crystal seed ^***	0-25wt％	1-5wt％	R	Me ₆-diquat-5OH and/or Me ₆-diquat-6 OH	Me ₆-diquat-5OH

[0073] for these embodiments, when hydro-thermal reaction has among the Table I X disclosed composition with reactant mixture, should (GeO ₂+ YO ₂)/X ₂O ₃For about 10 to approximately infinitely great or about 15-600.Below (GeO ₂+ YO ₂)/X ₂O ₃Mol ratio is the useful (GeO of the disclosed embodiments among the Table I X ₂+ YO ₂)/X ₂O ₃Lower mole ratio limit: 10,12,15,20,22,25 and 30.Below (GeO ₂+ YO ₂)/X ₂O ₃Mol ratio is the useful (GeO of the disclosed embodiments in the Table X ₂+ YO ₂)/X ₂O ₃The mol ratio upper limit: infinity, 5000,1000,600,500 and 400.Should (GeO ₂+ YO ₂)/X ₂O ₃Mol ratio falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.Should (GeO ₂+ YO ₂)/X ₂O ₃Mol ratio can be by in one embodiment 10 to infinitely great, or 15-600, or 10-5000, or 10-600, or 15-500, or the amount of 15-300 exists in another embodiment.

[0074] source of the various elements that require in the end product can be in the commercial Application or document in describe any those, the preparation method of this synthetic mixture also can be like this.

[0075] Y is the quadrivalent element that is selected from periodic table of elements 4-14 family, for example silicon and/or germanium, preferably silicon.In some embodiments of present disclosure, YO ₂The source comprise solid YO ₂, 30wt% solid YO preferably approximately ₂To obtain the crystalline product of present disclosure.Work as YO ₂When being silica, use the silica source that preferably comprises about 30wt% solid silica, for example by the silica of Degussa with trade name Aerosil or Ultrasil (the spray-dired silica of precipitation that comprises about 90wt% silica) sale, the aqueous, colloidal suspended substance of silica, for example by the aqueous, colloidal suspended substance of Grace Davison with trade name Ludox sale, or HiSil (comprises about 87wt% silica, approximately the free H of 6wt% ₂O and approximately the 4.5wt% hydration in conjunction with H ₂O and precipitation hydration SiO with about 0.02 micron particle size ₂) help forming crystal by said mixture.Preferably, therefore, YO ₂(for example silica) source comprises about 30wt% solid YO ₂, silica for example, more preferably about 40wt% solid YO ₂, silica for example.The source of silicon can also be a silicate, for example alkali silicate or tetraalkyl original silica ester.

[0076] in the additional embodiment of present disclosure, YO ₂The source comprise the acid of quadrivalent element (Y).Work as YO ₂When being silica, silica source can be a silicic acid.

[0077] X is the triad that is selected from periodic table of elements 3-13 family, for example aluminium and/or boron, and/or iron and/or gallium, preferred aluminium.X ₂O ₃The source, for example aluminium, preferably aluminum sulfate or hydrated alumina.Other aluminium source for example comprises, other water miscible aluminium salt, and sodium aluminate or alkoxide, for example aluminium isopropoxide, or aluminum metal for example is form of chips.

[0078] advantageously lithium, sodium, potassium, calcium or magnesium of alkali metal or alkali earth metal.The source of alkali metal or alkali earth metal is metal oxide, metal chloride, metal fluoride, metal sulfate, metal nitrate or metal aluminate advantageously.The sodium source is NaOH or sodium aluminate advantageously.Alkali metal also can be by ammonium (NH ₄ ⁺) or its equivalent, for example alkyl-ammonium ion substitutes.

[0079] is used for the OH of present disclosure ^-: YO ₂Mol ratio (not having the triad source to proofread and correct) does not comprise the correction of hydro-thermal reaction with acid in the reactant mixture.It is based on adds hydro-thermal reaction to hydro-thermal reaction calculates with the total mole number in the reactant mixture divided by adding to the total mole number hydroxy in the reactant mixture.Hydroxyl (OH ^-) source advantageously alkali metal oxide, for example Li ₂O, Na ₂O, K ₂O, Rb ₂O, Cs ₂O, Fr ₂O or their any combination; Alkali metal hydroxide, for example LiOH, NaOH, KOH, RbOH, CsOH, FrOH or their any combination; Ammonium hydroxide, alkaline earth oxide, for example BeO, MgO, CaO, SrO, BaO, RaO or their any combination; Alkaline earth metal hydroxide, for example Be (OH) ₂, Mg (OH) ₂, Ca (OH) ₂, Sr (OH) ₂, Ba (OH) ₂, Ra (OH) ₂Or their any combination; Be selected from oxide (one or more) or hydroxide (one or more) and their any combination of any element of 3-17 family; And organic hydroxide, oxyammonia for example is used for the hydroxide of synthetic organic formwork (R).

[0080] is used for the OH of present disclosure ^-: YO ₂Mol ratio (having the triad source to proofread and correct) comprises the correction of hydro-thermal reaction with acid in the reactant mixture.OH after proofreading and correct ^-Molal quantity be by calculating with deduction triad molal quantity in the total mole number hydroxy the reactant mixture three times (if this triad source is with the salt form supplies except that oxide, hydroxide or metal) from adding hydro-thermal reaction to.Therefore, OH ^-: YO ₂Molal quantity hydroxy calculated divided by the total mole number that adds the Y element in the hydro-thermal reaction usefulness reactant mixture to after mol ratio (correction in triad source is arranged) was based on and proofreaies and correct.

[0081] directed agents R comprises N, N, N, N ', N ', N '-vegolysen, 5-hexane two ammonium (Me ₆-diquat-6) salt or N, N, N, N ', N ', N '-vegolysen, 5-pentane two ammonium (Me ₆-diquat-5) at least a in the salt.Me ₆The example of-diquat-5 salt is hydroxide, chloride, bromide, fluoride, nitrate, sulfate, phosphate or their any mixture.Me ₆The example of-diquat-6 salt is hydroxide, chloride, bromide, fluoride, nitrate, sulfate, phosphate or their any mixture.

[0082] in some embodiments, directed agents R comprises at least a in following: dibrominated Me ₆-diquat-5, dichloride Me ₆-diquat-5, bifluoride Me ₆-diquat-5, two iodate Me ₆-diquat-5, two hydroxide Me ₆-diquat-5, sulfuric acid Me ₆-diquat-5, dinitric acid Me ₆-diquat-5, hydroxide bromination Me ₆-diquat-5, hydroxide chlorination Me ₆-diquat-5, hydroxide are fluoridized Me ₆-diquat-5, hydroxide iodate Me ₆-diquat-5, hydroxide nitric acid Me ₆-diquat-5, fluoridize bromination Me ₆-diquat-5, fluoridize chlorination Me ₆-diquat-5, fluoridize iodate Me ₆-diquat-5, fluoridize nitric acid Me ₆-diquat-5, chlorination bromination Me ₆-diquat-5, chlorination iodate Me ₆-diquat-5, chlorination nitric acid Me ₆-diquat-5, iodate bromination Me ₆-diquat-5, bromination nitric acid Me ₆-diquat-5, dibrominated Me ₆-diquat-6, dichloride Me ₆-diquat-6, bifluoride Me ₆-diquat-6, two iodate Me ₆-diquat-6, two hydroxide Me ₆-diquat-6, sulfuric acid Me ₆-diquat-6, dinitric acid Me ₆-diquat-6, hydroxide bromination Me ₆-diquat-6, hydroxide chlorination Me ₆-diquat-6, hydroxide are fluoridized Me ₆-diquat-6, hydroxide iodate Me ₆-diquat-6, hydroxide nitric acid Me ₆-diquat-6, fluoridize bromination Me ₆-diquat-6, fluoridize chlorination Me ₆-diquat-6, fluoridize iodate Me ₆-diquat-6, fluoridize nitric acid Me ₆-diquat-6, chlorination bromination Me ₆-diquat-6, chlorination iodate Me ₆-diquat-6, chlorination nitric acid Me ₆-diquat-6, iodate bromination Me ₆-diquat-6, bromination nitric acid Me ₆-diquat-6 and their any mixture.

[0083] factor that influences synthetic cost of crystalline molecular sieve and product quality is that the amount of directed agents is (by R: YO ₂Mol ratio is represented).Directed agents is hydro-thermal reaction the most expensive reactant in the reactant mixture of many crystalline molecular sieves normally.Hydro-thermal reaction (is hanged down R: YO with the amount of directed agents in the reactant mixture is low more ₂Mol ratio), the final molecular sieve of preparation is cheap more.

[0084] for the disclosed embodiments among Table VI, VII, VIII and the X, hydro-thermal reaction can randomly comprise seeding crystals with reactant mixture.What know is, for the sowing of molecular sieve synthetic mixture has favorable influence usually, for example controls the particle size of product, avoids the needs to organic formwork, quickens synthetic and improves the ratio of the product with framework types of wanting.Usually, seeding crystals to wherein use the synthetic similar synthetic of them.In general, any type of crystalline material can be used for promoting synthesizing based on new looks.

[0085] in some embodiment of present disclosure, for the disclosed embodiments among Table VI, VII, VIII, IX and the optional X, M: YO ₂Mol ratio is about 0.001-about 2.0.Following M: YO ₂Mol ratio is the useful M of all disclosure methods: YO ₂Lower mole ratio limit: 0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5,0.55,0.76 and 1.Following M: YO ₂Mol ratio is the useful M of all disclosure methods: YO ₂The mol ratio upper limit: 2,1.5,1.2,1.1,1,0.9,0.8,0.59,0.5,0.4,0.3,0.2 and 0.1.This M: YO ₂Mol ratio falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This M: YO ₂Mol ratio can be by 0.001-0.59 in one embodiment, or 0.01-0.5, or 0.74-2, or 0.8-1, or 0.001-2, or the amount of 0.01-1 exists in another embodiment.

[0086] in some embodiment of present disclosure, for the disclosed embodiments among Table VI, VII, IX and the X, H ₂O: YO ₂Mol ratio is about 1-about 10000 or about 1-35.Following H ₂O: YO ₂Mol ratio is the useful H of all disclosure methods ₂O: YO ₂Lower mole ratio limit: 1,2,5,10,12,15,20,22,25,30,50,100,200,500,1000,2000 and 5000.Following H ₂O: YO ₂Mol ratio is the useful H of all disclosure methods ₂O: YO ₂The mol ratio upper limit: 2,5,10,15,20,25,30,35,50,100,200,500,1000,2000,5000 and 10000.This H ₂O: YO ₂Mol ratio falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This H ₂O: YO ₂Mol ratio can be by 1-35 in one embodiment, or 5-35, or 1-10000, or 1-5000, or 5-1000, or the amount of 10-100 exists in another embodiment.

[0087] in some embodiment of present disclosure, for the disclosed embodiments among Table VIII, IX and the X, OH ^-: YO ₂Mol ratio (have or do not have triad source proofread and correct) is about 0.001-about 2.0.Following OH ^-: YO ₂Mol ratio (have or do not have triad source proofread and correct) is the useful OH of all disclosure methods ^-: YO ₂Mol ratio (have or do not have triad source proofread and correct) lower limit: 0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5,0.55,0.74 and 1.Following OH ^-: YO ₂Mol ratio (have or do not have triad source proofread and correct) is the useful OH of all disclosure methods ^-: YO ₂Mol ratio (have or the do not have triad source proofread and correct) upper limit: 2,1.5,1.2,1.1,1,0.9,0.8,0.59,0.5,0.4,0.3,0.2 and 0.1.This OH ^-: YO ₂Mol ratio (have or do not have triad source proofread and correct) falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This OH ^-: YO ₂Mol ratio (have or do not have triad source proofread and correct) can be by 0.001-0.59 in one embodiment, or 0.01-0.5, or 0.74-2, or 0.8-1, or 0.001-2, or the amount of 0.01-1 exists in another embodiment.

[0088] in some embodiments of present disclosure, R: YO ₂Mol ratio is about 0.001-about 2.0.Following R: YO ₂Mol ratio is the useful R of all disclosure methods: YO ₂Lower mole ratio limit: 0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5,0.6,0.7,0.8,0.9 and 1.Following R: YO ₂Mol ratio is the useful R of all disclosure methods: YO ₂The mol ratio upper limit: 0.1,0.2,0.5,0.6,0.7,0.8,0.9,1 and 2.This R: YO ₂Mol ratio falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This R: YO ₂Mol ratio can be by 0.001-2 in one embodiment, or 0.01-1, or 0.1-2, or 0.1-1, or 0.1-0.5, or the amount of 0.1-0.35 exists in another embodiment.

[0089] in some embodiments of present disclosure, the YO of all disclosure methods ₂/ X ₂O ₃Mol ratio is about 10 to approximately infinitely great or about 15-600.Following YO ₂/ X ₂O ₃Mol ratio is the useful YO of all disclosure methods ₂/ X ₂O ₃Lower mole ratio limit: 10,12,15,20,22,25 and 30.Following YO ₂/ X ₂O ₃Mol ratio is the useful YO of all disclosure methods ₂/ X ₂O ₃The mol ratio upper limit: infinity, 5000,1000,600,500,400,300,200,100,90,80,70,60,50,55,40 and 30.This YO ₂/ X ₂O ₃Mol ratio falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.This YO ₂/ X ₂O ₃Mol ratio can be by in one embodiment 10 to infinitely great, or 15-600, or 10-5000, or 10-600, or 15-500, or the amount of 15-55 exists in another embodiment.

[0090] in some embodiment of present disclosure, for the disclosed embodiments among Table VI, VII, VIII and the X, synthesizing of crystalline molecular sieve because the about 25wt% of 0-, the existence of the about 5wt% seeding crystals of 1-preferably approximately and being promoted, based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide (for example, silica) of reactant mixture.Following seeding crystals wt% (based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide of reactant mixture) is the useful seeding crystals wt% lower limit of all disclosure methods: 0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5,1,2,5,10 and 15.Following seeding crystals wt% (based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide of reactant mixture) is the useful seeding crystals wt% upper limit of all disclosure methods: 1,2,5,10,15,20 and 25.Described seeding crystals wt% falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.Seeding crystals wt% (based on the gross weight of hydro-thermal reaction with the tetrahedron element oxide of reactant mixture) can be by 0.001-25 in one embodiment, or 0.01-20, or 0.1-10, or 0.5-10, or 0.5-5, or the amount of 0.1-5 exists in another embodiment.

[0091] after hydro-thermal reaction is finished with the crystallization of reactant mixture, can be from this hydro-thermal reaction with reclaiming crystallized product the remainder (particularly its liquid contents) of reactant mixture.This kind recovery can comprise filters crystal and washes these crystal with water.Yet,, make this crystal experience high-temperature calcination (for example under 500 ℃, possibly in the presence of oxygen) handle necessity normally in order from crystal, to remove hydro-thermal reaction with whole undesirable residue of reactant mixture.This kind calcination processing is not only removed from crystal and is anhydrated, and this processing also is used for making the residue of organic directed agents to decompose and/or oxidation, and the residue of this organic directed agents may be enclosed in the hole of crystal, and may occupy ion exchange sites wherein.

Should be realized that [0092] reactant mixture of hydro-thermal reaction component can pass through more than a provenance supply.Hydro-thermal reaction can prepare off and on or continuously with reactant mixture.The crystalline size of the crystalline molecular sieve of present disclosure and crystallization time can become with character and the crystallization condition of the hydro-thermal reaction that is adopted with reactant mixture.

[0093] those skilled in the art are to be understood that, synthetic mixture with the composition in above-mentioned molar range be meant this synthetic mixture be mix, add, the product of reaction or any means by this kind mixture is provided, wherein this kind product has the composition in above-mentioned molar range.When preparation during this synthetic mixture, mix, add, the product of reaction or any means by this kind mixture is provided can comprise or can not comprise each composition.When synthetic mixture by mix, add, reaction or when preparing by any means that this kind mixture is provided, mix, add, the product of reaction or any means by this kind mixture is provided even can comprise the product of each composition.

Crystallization condition

[0094] in some embodiments, when hydro-thermal reaction neither comprises Ge and does not comprise crystal seed again with reactant mixture, the crystallization of the crystalline molecular sieve of present disclosure can be carried out under following crystallization condition, this crystallization condition comprises temperature, crystallization time and at least 150 rev/mins (RPM), preferred 200RPM, the more preferably stirring of 250RPM at least at least.neither comprise hydro-thermal reaction that Ge do not comprise crystal seed again aspect some of reactant mixture in, crystallization can be carried out having under the stirring of any kind (for example allowing container stir or rotation around trunnion axis) (rolling).When carrying out under crystallization is being stirred, stirring speed is the about 10000RPM of 150-, the preferred about 5000RPM of 200-.Neither comprising hydro-thermal reaction that Ge do not comprise crystal seed again with in the others of reactant mixture, it is useful stirring speed lower limit that crystallization condition has following stirring speed: 110,120,150,200,250,300,500,1000 and 5000 and to have following stirring speed be useful stirring rate-limit: 10000,5000,1000,500 and 400.For neither comprising the hydro-thermal reaction reactant mixture that Ge does not comprise crystal seed again, the stirring speed of crystallization condition falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.The stirring speed of crystallization condition can be by 150-10000 in one embodiment, or 200-5000, or 200-1000, or 240-500, or 250-1000, or the amount of 150-500 exists in another embodiment.

[0095] in some embodiments, when hydro-thermal reaction comprised Ge or crystal seed with reactant mixture, the crystallization of the crystalline molecular sieve of present disclosure can be carried out under following crystallization condition, and this crystallization condition comprises temperature, crystallization time and optional stirring.In the hydro-thermal reaction that comprises Ge or crystal seed was aspect some of reactant mixture, crystallization can carried out in reactor vessel (for example autoclave) under static or the stirring condition.Randomly, adopt the stirring of any kind, for example carry out hydro-thermal reaction around trunnion axis stirring or rotary container (rolling).When carrying out under crystallization is being stirred, for the hydro-thermal reaction reactant mixture that comprises Ge or crystal seed, stirring speed is the about 1000RPM of 1-, the preferred about 400RPM of 10-.In some embodiments, crystallization condition has the useful stirring speed lower limit that following stirring speed is all disclosure methods: 1,10,20,50,100,200 and 500 and have a useful stirring rate-limit that following stirring speed is all disclosure methods: 100,200,500 and 1000.The stirring speed of crystallization condition falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.The stirring speed of crystallization condition can be by 1-500 in one embodiment, or 10-200, or 50-500, or 20-500, or 50-1000, or the amount of 10-500 exists in another embodiment.

[0096] in some embodiments, crystallization condition has about 100 ℃-about 250 ℃ temperature and the time that keeps crystallization to be enough to take place, for example about 1 hour-about 400 hours under employed temperature.Preferably, crystallization condition has about 140 ℃-about 180 ℃ temperature and the time that keeps crystallization to be enough to take place, for example about 1 hour-about 200 hours under employed temperature.

[0097] in some embodiments of present disclosure, crystallization condition has the useful lowest temperature that following temperature is all disclosure methods: 100,110,120,130,140,150,160,170,180,190 and 200 and have a useful temperature upper limit that following temperature is all disclosure methods: 150,160,170,180,190,200,210,220,230,240 and 250.The temperature of crystallization condition falls in above-mentioned lower limit any and the above-mentioned upper limit scope between any, as long as this lower limit is less than or equal to this upper limit ideally.The temperature of crystallization condition can be by 100-250 in one embodiment, or 100-200, or 140-200, or 140-190, or 140-180, or the amount of 150-180 exists in another embodiment.

[0098] after this, with crystal and fluid separation applications and recovery.This program can comprise the maturation period, at room temperature (～25 ℃) or, preferably, under medium high temperature (less than 120 ℃), hydrothermal treatment consists (" hydro-thermal reaction ") under higher temperature then.The latter can comprise that one section of the temperature aspect gradually changes or the staged changing period.

[0099] can further filter from synthetic molecular sieve product, wash with water and/or drying.Can reclaim the crystalline molecular sieve that forms by crystallization and make it to experience further processing, for example with ammonium salt (one or more) (for example ammonium hydroxide, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium carbonate or their any combination) ion-exchange and/or at oxidizing atmosphere (air for example, have gas greater than the partial pressure of oxygen of 0kPa-a) in greater than 200 ℃, preferably at least 300 ℃, more preferably at least 400 ℃, at least 500 ℃ temperature lower calcination most preferably.

Catalysis and absorption

[00100] molecular sieve and/or zeolite about the summary of production, modification and the sign of molecular sieve at books " Molecular Sieves-Principles of Synthesis andIdentification "; (R.Szostak, Blackie Academic ﹠amp; Professional, London, 1998, second edition) in be described.Except molecular sieve, amorphous materials mainly is that silica, alumina silicate and aluminium oxide are also as adsorbent and catalyst carrier.Many forming techniques of knowing, as spray-drying, balling-up, granulation with extrude and and be used to prepare macrostructure, this macrostructure for example is, and is used for the micropore of catalysis, absorption and ion-exchange and spherical particle, extrudate, pellet and the tablet form of other type porous material.The summary of these technology is at " Catalyst Manufacture ", A.B.Stiles and T.A.Koch, and Marcel Dekker, New York is described in 1995.

[00101] to the degree of wishing, the original metal cation of the material when synthetic can be substituted by other cation by ion-exchange at least in part according to the technology of knowing in this area.Preferred substituting cation comprises metal ion, hydrogen ion, hydrogen precursor (for example ammonium ion) and their mixture.Especially preferred cation is to regulate those of catalytic activity for some hydrocarbon conversion reactions.They comprise hydrogen, rare earth metal and periodic table of elements 1-17 family, the metal of preferred 2-12 family.

[00102] when being used as adsorbent or catalyst in the organic compound conversion process, the crystalline molecular sieve of present disclosure, the molecular sieve of preferred MCM-22 family should be partial dehydration at least usually.This can followingly carry out: in the atmosphere of for example air or nitrogen and at atmospheric pressure, be lower than atmospheric pressure or be higher than and be heated to for example 200 ℃-595 ℃ temperature under the atmospheric pressure, kept for example 30 minutes to 48 hours.Degree of dehydration down keeps the percentage of 48 hour total weight loss to measure at the drying nitrogen (less than the 0.001kPa dividing potential drop of water vapour) that flows with respect to sieve sample by the loss in weight under 595 ℃.Dehydration also at room temperature (～25 ℃) only carry out in a vacuum by this silicate is placed, but require the longer time in order to obtain enough dehydrating amounts.

[00103] the crystallization MCM-22 family molecular sieve of present disclosure particularly is its metal, hydrogen and ammonium form, can advantageously be transformed into another kind of form by heat treatment.This heat treatment is following carrying out usually: under at least 370 ℃ temperature in these forms of heating a kind of at least 1 minute and usually no longer than 1000 hours.Though pressure below atmospheric pressure can be used for heat treatment, atmospheric pressure is wished for convenience's sake.Heat treatment can be carried out under up to about 925 ℃ temperature.Heat treated product especially can be used for the catalysis of some hydrocarbon conversion reaction.Heat treated product particularly is its metal, hydrogen and ammonium form, especially can be used for the catalysis of some organic matter (for example hydrocarbon) conversion reaction.The limiting examples of described reaction comprises those that describe in the following patent: U.S. Patent number 4,954,325; 4,973,784; 4,992,611; 4,956,514; 4,962,250; 4,982,033; 4,962,257; 4,962,256; 4,992,606; 4,954,663; 4,992,615; 4,983,276; 4,982,040; 4,962,239; 4,968,402; 5,000,839; 5,001,296; 4,986,894; 5,001,295; 5,001,283; 5,012,033; 5,019,670; 5,019,665; 5,019,664 and 5,013,422, each piece is hereby incorporated by about the description of catalytic reaction.

[00104] crystalline molecular sieve of present disclosure can be shaped to various particle sizes.Generally speaking, particle can be for example extrudate form of powder, particulate or molding product.When molding catalyst (for example by extruding), can before drying, extrude crystal, or partly dry and extrude crystal then.

[00105] crystalline molecular sieve of present disclosure can be used as adsorbent, for example be used for from the mixture separating at least one component of the component that is gas phase or liquid phase, described component has the difference characterization of adsorption with respect to the crystalline molecular sieve (one or more) of present disclosure.Therefore, contact with the crystalline molecular sieve (one or more) of present disclosure optionally to adsorb a kind of component by the mixture that allows crystalline molecular sieve (one or more) with respect to present disclosure have the component of difference characterization of adsorption, partially or substantially completely separating at least one component from this mixture.

[00106] crystalline molecular sieve of present disclosure useful as catalysts in large-scale technical process (comprising separation process and hydrocarbon conversion process).By the crystalline molecular sieve (one or more) of present disclosure (individually or with one or more other catalytic active substances, comprise that other crystalline catalysts is in combination) effectively the instantiation of the hydrocarbon conversion process of catalysis comprise following:

(i) with long-chain olefin C for example ₁₄Alkene is aromatic hydrocarbon benzene alkylation for example, and the chain alkyl aromatic compounds is provided, and wherein reaction condition comprises about 340 ℃-about 500 ℃ temperature individually or by any in combination, the about pressure of the about 20200kPa-a of 101-(definitely), about 2hr ^-1-about 2000hr ^-1Weight (hourly) space velocity (WHSV) and about aromatic hydrocarbon/olefin molar ratio of 1/1-about 20/1, this Alkylaromatics can be sulfonated subsequently and synthectic detergents is provided;

(ii) provide the short-chain alkyl aromatic compounds with the aromatic hydrocarbon alkylation with gaseous olefin, for example, provide cumene with propylene with benzene alkylation, wherein reaction condition comprises about 10 ℃-about 125 ℃ temperature individually or by any in combination, approximately pressure and the 5hr of the about 3030kPa-a of 101- ^-1-about 50hr ^-1Aromatic hydrocarbon weight (hourly) space velocity (WHSV) (WHSV);

(iii) with containing C ₅The fuel gas of alkene will contain the reformate alkylation of a large amount of benzene and toluene and single-and two-alkylates especially will be provided, wherein reaction condition comprises about 315 ℃-about 455 ℃ temperature individually or by any in combination, the pressure of about about 6000kPa-a of 3000-, approximately 0.4hr ^-1-about 0.8hr ^-1WHSV-alkene, about 1hr ^-1-about 2hr ^-1The WHSV-reformate and the about gas circulation of 1.5-2.5vol/vol fuel gas raw material;

(iv) with long-chain olefin C for example ₁₄Alkene is aromatic hydrocarbon for example benzene,toluene,xylene and decalin base and alkylating aromatics lube base stock is provided, and wherein reaction condition is individually or by any about 160 ℃-about 260 ℃ temperature and about pressure of 2600-3500kPa-a of comprising in combination;

(v) the alcohol with alkene or equivalence provides long chain alkylphenol with the phenols alkylation, and wherein reaction condition comprises about 200 ℃-about 250 ℃ temperature individually or by any in combination, the approximately pressure of 1500-2300kPa-a and approximately 2hr ^-1About 10hr ^-1Total WHSV;

(vi) light paraffins is changed into alkene and aromatic compounds, wherein reaction condition is individually or by any about 425 ℃-about 760 ℃ temperature and about pressure of the about 15000kPa-a of 170-of comprising in combination;

(vii) light olefin is changed into the hydrocarbon of gasoline, distillate and lube range, wherein reaction condition is individually or by any about 175 ℃-about 375 ℃ temperature and about pressure of the about 15000kPa-a of 800-of comprising in combination;

(viii) two-stage reforming, in the phase I, use the MCM-22 family molecular sieve of present disclosure as catalyst initial boiling point to be become senior distillate and gasoline boiling range product greater than about 260 ℃ hydrocarbon flow upgrading in conjunction with 8-10 family metal, in second stage, use the zeolite beta that also combines 8-10 family metal as the effluent reaction of catalyst by the phase I, reaction condition comprises about 340 ℃-about 455 ℃ temperature individually or by any in combination, the pressure of about about 18000kPa-a of 3000-, approximately about 1760 liters/liter hydrogen circulation and the about 0.1-10h of 176- ^-1Liquid hourly space velocity (LHSV) (LHSV);

(ix) in MCM-22 family molecular sieve and hydrogenation component as the present disclosure of catalyst, or the combined hydrocracking/dewaxing process under the existence of the mixture of this kind catalyst and zeolite beta, wherein reaction condition comprises about 350 ℃-about 400 ℃ temperature individually or by any in combination, the approximately pressure of the about 11000kPa-a of 10000-, the approximately LHSV of 0.4-about 0.6 and approximately about 880 liters/liter hydrogen circulation of 528-;

(x) reaction of alcohol and alkene is to provide compound ether, for example the reaction of methyl alcohol and isobutene and/or iso-amylene is to provide methyl-tertbutyl ether (MTBE) and/or tert pentyl methyl ether (TAM), wherein conversion condition comprises about 20 ℃-about 200 ℃ temperature individually or by any in combination, the pressure of the about 20000kPa-a of 200-, approximately 0.1hr ^-1-about 200hr ^-1WHSV (gram alkene/hour gram zeolite) and alcohol and the alkene molar feed ratio of about 0.1/1-about 5/1;

(xi) use C ₉+ aromatic compounds is as co-fed toluene disproportionation, wherein reaction condition comprises about 315 ℃-about 595 ℃ temperature individually or by any in combination, the pressure of about about 7200kPa-a of 101-, the hydrogen of about 0 (not adding hydrogen)-about 10/hydrocarbon mol ratio and about 0.1hr ^-1-about 30hr ^-1WHSV;

(xii) be prepared as follows pharmaceutical active compounds 2-(4-isobutyl phenenyl) propionic acid, i.e. brufen: make the reaction of isobutyl-benzene and propylene oxide so that intermediate 2-(4-isobutyl phenenyl) to be provided propyl alcohol, then this alcohol is oxidized to corresponding carboxylic acid;

(xiii) be used as acid-binding agent in the reaction of amine in the dyestuff preparation and heterocycle fiber reactivity component with the in fact salt-free solution that contains chemically-reactive dyes of preparation, as such among the German patent DE 3,625,693, this full patent texts is incorporated herein for reference;

(xiv) be used for 2 as absorbent, and the 6-toluene di-isocyanate(TDI) (2,6-TDI) with the TDI isomer separation, as U.S. Patent number 4, like that, this full patent texts is incorporated herein for reference in 721,807, wherein allow and comprise 2,6-TD I and 2, the raw mix of 4-TDI with contact to absorb 2,6-TDI with the MCM-22 family molecular sieve of the present invention that the K ion has carried out cation exchange, then by reclaim with the desorb material desorb that comprises toluene this 2,6-TDI;

(xv) be used for 2 as absorbent, 4-TDI and its isomer separation are as U.S. Patent number 4,721, such in 806, this full patent texts is incorporated herein for reference, wherein allows comprise 2 4-TDI and 2, the raw mix of 6-TDI with contact to absorb 2 with the MCM-22 family molecular sieve of the present invention that Na, Ca, Li and/or Mg ion have carried out cation exchange, 4-TDI, then by reclaim with the desorb material desorb that comprises toluene this 2,4-TDI;

(xvi) reduce in the fraction at the bottom of the 90-200 that obtains the catalyzed conversion from methyl alcohol to gasoline ℃+tower in the method for durene content, this method comprises that allowing this contain fraction and hydrogen at the bottom of the tower of durene is contacting on the catalyst of MCM-22 family molecular sieve of the present invention and metal hydride individually or by any comprising in combination under about 230 ℃-about 425 ℃ temperature and the condition of the pressure of about about 22000kPa-a of 457-;

(xvii) in the method for co-production phenol and ketone, this method is via benzene alkylation, then forms alkylbenzene hydroperoxide and this alkylbenzene hydroperoxide is cracked into phenol and ketone carries out, and for example benzene and propylene is transformed into phenol and acetone, with benzene and C ₄Alkene is transformed into phenol and methyl ethyl ketone, those that describe among International Application PCT/EP2005/008557 for example, in this case can be then with phenol and acetone conversion Cheng Shuan-phenol-A, as described in International Application PCT/EP2005/008554, benzene is transformed into phenol and cyclohexanone, or benzene and ethene is transformed into phenol and methyl ethyl ketone, as describing among the PCT/EP 2005/008551;

(xviii) require therein in the optionally benzene alkylation reaction method to an alkylbenzene, for example by benzene be rich in the C of linear butylene ₄Olefin feedstock optionally prepares sec-butylbenzene, as described in International Application PCT/EP2005/008557, preferably, this conversion is following to be carried out: at about 60 ℃-about 260 ℃, for example about 100 ℃-200 ℃ temperature, 7000kPa-a or littler pressure and about 0.1-50h ^-1Based on C ₄Benzene and the C of the raw material weight (hourly) space velocity (WHSV) (WHSV) of alkylating agent and about 1-about 50 ₄Under the mol ratio of alkylating agent with benzene and C ₄Olefin feedstock and the common charging of catalyst of the present invention; With

(xix) at transalkylation, for example in the method for polyalkylbenzene transalkylation.

[00107] under the situation of many catalyst, hope with this novel crystal with temperature and indefatigable other material of other condition that adopts in the organic transformation process combined.This type of material comprises active and non-active material and synthesizing or naturally occurring zeolite and inorganic material clay, silica and/or metal oxide aluminium oxide for example for example.The latter can be naturally occurring or be the gelatinous precipitate or the gel form of the mixture that comprises silica and metal oxide.Material is used in combination with this novel crystal, promptly combines with it or exist between the synthesis phase of the crystal of this novel active often to change conversion ratio and/or the selectivity of this catalyst in some organic transformation process.Inactive material serves as compatibly that diluent is controlled the amount of the conversion in the given process so that product can obtain economically and in an orderly manner, and needn't adopt other means of control reaction rate.These materials can be incorporated into naturally occurring clay, for example in bentonite and the kaolin, to improve the crushing strength of catalyst under the commercial operation condition.This material, promptly clay, oxide etc. are as the binding agent of catalyst.It is desirable that catalyst with good crushing strength is provided, because prevent that in commercial Application it is desirable that catalyst is broken into dusty material.These clay bonds once only were used to improve the crushing strength of catalyst usually.

[00108] can comprise imvite and kaolin families with the compound naturally occurring clay of this novel crystal, described family comprise the change bentonite and often be called the kaolin of Dixie, McNamee, Georgia and Florida clay or wherein main inorganic composition be other of galapectite, kaolinite, dictite, narcite or anauxite.This type of clay can use or originally experiences calcining, acid treatment or chemical modification and handle by the reset condition of initial recovery.Can be used for also comprising inorganic oxide, particularly aluminium oxide with the compound binding agent of crystal of the present invention.

[00109] except above-mentioned material, all right and the porous matrix material of this novel crystal, for example for example silica-alumina-thorium oxide, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia are compound for silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllia, silica-titania and ternary composition.

[00110] the finely divided crystalline molecular sieve and the relative scale of inorganic oxide matrix change widely, wherein crystalline content is the about 99wt% of about 1-of this composite, especially when this composite prepares with bead form, be more typically the about 80wt% of about 20-.

[00111] the following example reflection embodiment of the present invention but do not think limit the scope of the invention.

Embodiment

Embodiment 1,1A (contrast) and 2:

[00112] by water, dibrominated Me ₆-diquat-5 (" R ") (SACHEM, Inc.), silica (Ultrasil ^TM, Degussa Corp.), aluminum sulfate solution (8.1%Al ₂O ₃) solution and 50wt% sodium hydroxide solution prepare the hydro-thermal reaction reactant mixture.This mixture has following mole as shown in Table IX and forms:

Table I X

	Embodiment 1	Embodiment 1A	Embodiment 2
	Embodiment 1	Embodiment 1A	Embodiment 2	SiO ₂/Al ₂O ₃	23.6	23.6	25.5
H ₂O/SiO ₂	21	21	20	SiO ₂/Al ₂O ₃	23.6	23.6	25.5
H ₂O/SiO ₂	21	21	20	OH ^-/SiO ₂ ^*	0.22	0.26	0.24
OH ^-/SiO ₂ ^**	0.47	0.51	0.48	OH ^-/SiO ₂ ^*	0.22	0.26	0.24
OH ^-/SiO ₂ ^**	0.47	0.51	0.48	Na ⁺/SiO ₂	0.47	0.51	0.48
R/SiO ₂	0.15	0.15	0.14	Na ⁺/SiO ₂	0.47	0.51	0.48
R/SiO ₂	0.15	0.15	0.14	Temperature (℃)	170	170	170
Mixing speed (RPM)	250	100	250	Temperature (℃)	170	170	170
Mixing speed (RPM)	250	100	250	Crystal seed (wt%)	0	0	0
Time (hr)	80，92	72	80	Crystal seed (wt%)	0	0	0
Time (hr)	80，92	72	80	XRD result	The present invention (80 hours) (referring to Fig. 1 a); The present invention and＜15%EUO zeolite (92 hours) (referring to Fig. 1 b)	EMM-10-P and＜15% analcime (referring to Fig. 2)	The present invention (referring to Fig. 4)
SiO ₂/Al ₂O ₃(mol ratio)	21	19.5	21	XRD result		EMM-10-P and＜15% analcime (referring to Fig. 2)	The present invention (referring to Fig. 4)
SiO ₂/Al ₂O ₃(mol ratio)	21	19.5	21	BET area (m ²/g)	522 (87 is outer)		506 (109 is outer)
Hexane cracking (ALPHA)	260			BET area (m ²/g)	522 (87 is outer)		506 (109 is outer)
Hexane cracking (ALPHA)	260			Form		5-20 micron sphere (circle, ellipse) aggregation (referring to Fig. 3) less than the symbiosis platelet of 0.1 micron thickness	5-20 micron sphere (circle, ellipse) aggregation (referring to Fig. 5) less than the symbiosis platelet of 0.1 micron thickness
Crystalline size (SEM)	NA	5-20 micron (referring to Fig. 3)	5-20 micron (referring to Fig. 5)	Form
Crystalline size (SEM)	NA	5-20 micron (referring to Fig. 3)	5-20 micron (referring to Fig. 5)	Thickness (SEM)	NA	Less than 0.1 micron (referring to Fig. 3)	Less than 0.1 micron (referring to Fig. 5)

* the OH of this delegation ^-/ SiO ₂Be under the correction that the triad source is arranged, to calculate.

The OH of this delegation of * ^-/ SiO ₂Be under the situation of the correction that does not have the triad source, to calculate.

[00113] at the crystalline mixture that in the Parr autoclave, under agitation makes the foregoing description under 170 ℃.After crystallization, filter this hydro-thermal reaction reaction mixture slurry, wash with water and under 120 ℃ at air drying.

[00114] embodiment 1 80 hours XRD (Fig. 1 a) shows following feature:

(1) in the d spacing maximum at 12.33 ± 0.23 dust places;

(2) the d spacing maximum between 14.17 and 12.57 dusts; With

(3) the non-discrete d spacing maximum between 8.8 and 11.1 dusts, wherein the peak intensity at the d spacing maximum place between 14.17 and 12.57 dusts is less than at 90% of the peak intensity at the d spacing maximum place at 12.33 ± 0.23 dust places.

[00115] embodiment 1 80 hours XRD (Fig. 1 a) also demonstrates to list in and is the following peak of MCM-22 molecular sieve common trait in the Table X:

Table X

Crystal face d spacing (dust)	Relative intensity, I/I ₀×100
Crystal face d spacing (dust)	Relative intensity, I/I ₀×100	4.41±0.1	W-M, wide
3.96±0.08	W-VS, wide	4.41±0.1	W-M, wide
3.96±0.08	W-VS, wide	3.57±0.06	W-M
3.43±0.06	M-VS	3.57±0.06	W-M

[00116] together with the same characteristic features that approximately shows Fig. 1 a at 92 hours XRD (Fig. 1 b) less than the embodiment 1 of 5%EUO zeolite.Contain the same characteristic features that shows Fig. 1 less than the XRD (Fig. 5) of the embodiment 2 of 5% analcime.

[00117] XRD of embodiment 1A shows the same characteristic features of EMM-10-P.

Embodiment 3 (crystal seed of embodiment 4):

[00118] makes reactant mixture according to following program.In reactor, add 376.2g water and 75.9g Al ₂(SO ₄) ₃18H ₂O (Riedel-de Haen).Add the 50wt% solution of 62.1g NaOH in this solution, used NaOH derives from Baker.In this solution, add 91.1g Ultrasil VN35P (Ultrasil Corporation) and mixing then, then add the 50wt% solution of 145.8g dibrominated five first ammoniums (SACHEM Inc.).Stir this mixture up to evenly.The mole of this reactant mixture is formed and can be expressed as:

0.275Na ₂O/0.033 Al ₂O ₃/SiO ₂/0.15R/22 H ₂O

[00119] closes this reactor, stir and adopt the speed of 25 ℃/hr to be heated to 170 ℃.Under stirring condition, continue heating 72 hours.Behind cool to room temperature, reclaim crystal and wash with water 3 times from mother liquor by centrifugation.120 ℃ of dry down crystal a whole nights of being somebody's turn to do through washing.With respect to the total amount of initial synthetic mixture, the productive rate of this crystal is 8.8wt%.XRD and SEM provide (Fig. 6 and 7) in the accompanying drawings.

	Embodiment 3
	Embodiment 3	SiO ₂/Al ₂O ₃	33
H ₂O/SiO ₂	22	SiO ₂/Al ₂O ₃	33
H ₂O/SiO ₂	22	OH ^-/SiO ₂ ^*	0.35
OH ^-/SiO ₂ ^**	0.55	OH ^-/SiO ₂ ^*	0.35
OH ^-/SiO ₂ ^**	0.55	Na ⁺/SiO ₂	0.55
R/SiO ₂	0.15	Na ⁺/SiO ₂	0.55
R/SiO ₂	0.15	Temperature (℃)	170
Mixing speed (RPM)	100	Temperature (℃)	170
Mixing speed (RPM)	100	Crystal seed (wt%)	Do not have
Crystallization time (hr)	72	Crystal seed (wt%)	Do not have
Crystallization time (hr)	72	The XRD figure case	(referring to Fig. 6)
SiO ₂/Al ₂O ₃(mol ratio)	n.a.	The XRD figure case	(referring to Fig. 6)
SiO ₂/Al ₂O ₃(mol ratio)	n.a.	BET area (m ²/g)	n.a.
Hexane cracking (ALPHA)	n.a.	BET area (m ²/g)	n.a.
Hexane cracking (ALPHA)	n.a.	Form	Thin slice (referring to Fig. 7)
Crystalline size (SEM)	The maximum gauge of estimation is less than 2 μ m (referring to Fig. 7)	Form	Thin slice (referring to Fig. 7)
Crystalline size (SEM)		Thickness (SEM)	～100nm (referring to Fig. 7)

[00120] XRD of embodiment 3 (Fig. 6) shows the following feature identical with Fig. 1:

(1) in the d spacing maximum at 12.33 ± 0.23 dust places;

(2) the d spacing maximum between 14.17 and 12.57 dusts; With

(3) the non-discrete d spacing maximum between 8.8 and 11.1 dusts, wherein the peaked peak intensity of d spacing between 14.17 and 12.57 dusts is less than at 90% of the peaked peak intensity of d spacing at 12.33 ± 0.23 dust places.

[00121] XRD of embodiment 3 (Fig. 6) also shows to list in and is the following peak of MCM-22 molecular sieve common trait in the Table X.

Embodiment 4:

[00122] makes reactant mixture according to following program.The group water solution that adds sodium aluminate in Teflon reactor bushing pipe (comprises 10wt%NaOH and 7.8wt%Al ₂O ₃, employed NaOH derives from Baker, and aluminium hydroxide derives from Alcoa).In this solution, add 40wt% sodium hydroxide solution (NaOH derives from Baker).In this solution, add Ultrasil VN35P (Ultrasil Corporation) and mixing when stirring.Add the 50wt% solution of dibrominated five first ammoniums (SACHEM Inc.) then.After with this mixture homogenization, add the crystal of embodiment 3 and reach concentration with respect to the gross weight 0.5wt% of this synthetic mixture.The amount of using in the said mixture satisfies the mole of this reactant mixture to be formed, and can be expressed as:

0.23Na ₂O/0.04 Al ₂O ₃/SiO ₂/0.15R/18 H ₂O

[00123] then this bushing pipe is put into stirred reactor, this reactor is closed and adopt the speed of 25 ℃/hr to be heated to 170 ℃.Under stirring condition, continue heating 60 hours.Behind cool to room temperature, reclaim crystal and wash with water 4 times from mother liquor by centrifugation.120 ℃ of dry down crystal a whole nights of being somebody's turn to do through washing.With respect to the total amount of initial synthetic mixture, the productive rate of this crystal is 13.9wt%.XRD and SEM provide (Fig. 8 and 9) in the accompanying drawings.

	Embodiment 4
	Embodiment 4	SiO ₂/Al ₂O ₃	25
H ₂O/SiO ₂	18	SiO ₂/Al ₂O ₃	25
H ₂O/SiO ₂	18	OH ^-/SiO ₂	0.76
Na ⁺/SiO ₂	0.46	OH ^-/SiO ₂	0.76
Na ⁺/SiO ₂	0.46	R/SiO ₂	0.15
Temperature (℃)	170	R/SiO ₂	0.15
Temperature (℃)	170	Mixing speed (RPM)	60
Crystal seed (wt%)	0.5	Mixing speed (RPM)	60
Crystal seed (wt%)	0.5	Crystallization time (hr)	60
The XRD figure case	Referring to Fig. 8	Crystallization time (hr)	60
The XRD figure case	Referring to Fig. 8	SiO ₂/Al ₂O ₃(mol ratio)	n.a.
BET area (m ²/g)	n.a.	SiO ₂/Al ₂O ₃(mol ratio)	n.a.
BET area (m ²/g)	n.a.	Hexane cracking (ALPHA)	n.a.
Form	Thin slice (referring to Fig. 9)	Hexane cracking (ALPHA)	n.a.
Form	Thin slice (referring to Fig. 9)	Crystalline size (SEM)	The maximum gauge of estimation is less than 2 μ m (referring to Fig. 9)
Thickness (SEM)	～100nm (referring to Fig. 9)	Crystalline size (SEM)

* the OH of this delegation ^-/ SiO ₂Be under the situation that has the triad source to proofread and correct, to calculate, because aluminium is as Al ₂O ₃Provide.

[00124] XRD of embodiment 3 (Fig. 8) shows the following feature identical with Fig. 1:

(1) in the d spacing maximum at 12.33 ± 0.23 dust places;

(2) the d spacing maximum between 14.17 and 12.57 dusts; With

[00125] XRD of embodiment 4 (Fig. 8) also shows to list in and is the following peak of MCM-22 molecular sieve common trait in the Table X.

Embodiment 5:

[00126] makes reactant mixture according to following program.In stainless steel autoclave, add 28.7g hydroxide hexamethylamine [R] (SACHEM, 22% group water solution Inc.).When stirring this solution, add the 1.8g germanium oxide (99.99wt%, Aldrich) and this mixture of homogenizing, add then the 18.5g tetraethyl orthosilicate (98wt%, Aldrich).Interpolation 1.1g aluminium isopropoxide in this mixture (98wt%, Aldrich).When stirring this homogeneous mixture is heated to 60 ℃.After heating 1 hour, stop to stir and under static conditions, continue again heating 1.5 hours.Behind cool to room temperature, during reaction evaporate the 9.5g original mixture.Total mole of composition of this synthetic mixture can be expressed as before heating:

0.2GeO ₂/0.03 Al ₂O ₃/SiO ₂/0.3R/4 EtOH/0.045 iPA/14H ₂O

[00127] after this preliminary treatment, closes this autoclave and do not having to adopt the speed of 20 ℃/hr to be heated to 190 ℃ under the condition of stirring.Under static conditions, continue heating 144 hours.Behind cool to room temperature, reclaim crystal and use 150ml water washing 4 times from mother liquor by centrifugation.120 ℃ of dry down crystal a whole nights of being somebody's turn to do through washing.With respect to the total amount of initial synthetic mixture, the productive rate of this crystal is 14wt%.XRD and SEM provide (Figure 10 and 11) in the accompanying drawings.

	Embodiment 5
	Embodiment 5	SiO ₂/Al ₂O ₃	33
(GeO ₂+SiO ₂)/Al ₂O ₃	40	SiO ₂/Al ₂O ₃	33
(GeO ₂+SiO ₂)/Al ₂O ₃	40	H ₂O/SiO ₂	14
H ₂O/(GeO ₂+SiO ₂)	11.7	H ₂O/SiO ₂	14
H ₂O/(GeO ₂+SiO ₂)	11.7	OH ^-/SiO ₂ ^*	0.3
OH ^-/(GeO ₂+SiO ₂) ^*	0.25	OH ^-/SiO ₂ ^*	0.3
OH ^-/(GeO ₂+SiO ₂) ^*	0.25	R/SiO ₂	0.3
Temperature (℃)	190	R/SiO ₂	0.3
Temperature (℃)	190	Mixing speed (RPM)	0
Crystal seed (wt%)	Do not have	Mixing speed (RPM)	0
Crystal seed (wt%)	Do not have	Crystallization time (hr)	144
The XRD figure case	Referring to Figure 10	Crystallization time (hr)	144
The XRD figure case	Referring to Figure 10	SiO ₂/Al ₂O ₃(mol ratio)	n.a.
BET area (m ²/g)	n.a.	SiO ₂/Al ₂O ₃(mol ratio)	n.a.
BET area (m ²/g)	n.a.	Hexane cracking (ALPHA)	n.a.
Form	Thin slice (referring to Figure 11)	Hexane cracking (ALPHA)	n.a.
Form	Thin slice (referring to Figure 11)	Crystalline size (SEM)	The maximum gauge of estimation is less than 2 μ m (referring to Figure 11)
Thickness (SEM)	～100nm (referring to Figure 11)	Crystalline size (SEM)

* these the row OH ^-/ SiO ₂And OH ^-/ (GeO ₂+ SiO ₂) be under the situation that does not have the triad source to proofread and correct, to calculate, because aluminium provides as aluminium isopropoxide.

[00128] XRD of embodiment 5 (Figure 10) shows the following feature as Fig. 1:

(1) in the d spacing maximum at 12.33 ± 0.23 dust places;

(2) the d spacing maximum between 14.17 and 12.57 dusts; With

[00129] XRD of embodiment 5 (Figure 10) also shows to list in and is the following peak of MCM-22 molecular sieve common trait in the Table X.

[00130] whole patents and the patent application here listed, test method (as the ASTM method) and other document will be introduced for reference on this type of publication degree consistent with the present invention and for all authorities that allow these introducings fully.

[00131] when a plurality of lower limits and a plurality of upper limit when this lists, the scope from arbitrary lower limit to arbitrary upper limit should be considered.

[00132] meaning of term as used herein should adopt their common meanings in the art; Specifically, should be with reference to " Handbook of Petroleum RefiningProceses ", the third edition, editor Robert A.Meyers, McGraw-Hill (2004).In addition, all patents of quoting of this paper are consistent with the present invention and for reference at fully introducing on the degree of all authorities that allow this introducing in this publication with patent application, test procedure (as the ASTM method) and other file.In addition, when a plurality of lower limits and a plurality of upper limit when this lists, the scope from arbitrary lower limit to arbitrary upper limit should be considered.Further point out, the employed trade name of this paper by ^TMSymbol or

Symbolic representation shows that these titles may be protected by some trade mark right, and for example they may be the registration marks in the various judicial powers.

[00133], but is to be understood that revising at various other that does not break away from spirit and scope of the invention is apparent and easy to reach for a person skilled in the art although described exemplary embodiment especially.Therefore, do not think that the scope of appended claim is limited to embodiment given here and narration, but claim is believed to comprise all features of the novelty that can patent that exists in the present invention, comprising all further features of the equivalent of being thought these features by the technical staff in the technical field of the invention.

Claims

1. crystallization MCM-22 family molecular sieve, form when synthetic has such X-ray diffraction pattern to this molecular sieve: the peak that is included in the d spacing maximum place of 12.33 ± 0.23 dusts by it, the non-discrete peak at the peak distinguished at the d spacing maximum place between about 14.17 dusts of 12.57-and the d spacing maximum place between the 8.8-11 dust, wherein the peak intensity at the d spacing maximum place between about 14.17 dusts of 12.57-is less than at 90% of the peak intensity at the d spacing maximum place at 12.33 ± 0.23 dust places.

2. the crystallization MCM-22 family molecular sieve of claim 1 also is included in the XRD peak at the d spacing maximum place of 3.57 ± 0.06 and 3.43 ± 0.06 dusts.

3. each crystalline molecular sieve during aforesaid right requires, wherein said X-ray diffraction pattern also is included in the d spacing maximum at 28 ± 1 dust places.

4. the crystalline molecular sieve of claim 2, wherein said X-ray diffraction pattern comprises value as shown in the table basically and relative intensity:

Crystal face d spacing (dust) Relative intensity, I/I ₀×100 14.17＞d＞12.57 M-VS 12.33±0.23 M-VS 11.1-8.8 W-S 3.57±0.06 W-M 3.43±0.06 M-VS

5. the crystalline molecular sieve of claim 2 also is included in the XRD peak at the d spacing maximum place of 4.41 ± 0.1 dusts.

6. the crystalline molecular sieve of claim 5, wherein said X-ray diffraction pattern comprises value as shown in the table basically and relative intensity:

Table IV

Crystal face d spacing (dust) Relative intensity, I/I ₀×100 14.17＞d＞12.57 M-VS 12.33±0.23 M-VS 11.1-8.8 W-S 4.41±0.1 W-M, wide 3.96±0.08 W-VS, wide 3.57±0.06 W-M 3.43±0.06 M-VS

7. the manufacture method of each crystalline molecular sieve during aforesaid right requires may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

OH ^-∶Y＝0.001-0.59

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

(b) allow this mixture experience crystallization condition comprise the product of required crystalline molecular sieve with formation, wherein this crystallization condition comprises 100 ℃-250 ℃ temperature, and 150RPM is to less than the mixing speed of 5000RPM and about 1 hour-400 hours crystallization time at least; And

(c) reclaim this crystalline molecular sieve.

8. the method for claim 7 also is included in the triad correction and is the OH of 0.01-0.39 down ^-: Y.

9. the manufacture method of crystalline molecular sieve, this method may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

OH ^-∶Y＝0.74-2

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

(c) reclaim this crystalline molecular sieve.

10. the method for claim 9 also is included in the triad correction and is the OH of 0.64-2 down ^-: Y.

11. each method among the claim 7-10, wherein said H ₂O: the Y mol ratio is 5-35.

12. the manufacture method of crystalline molecular sieve, this method may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝5-35

OH ^-∶Y＝0.001-2

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

(c) reclaim this crystalline molecular sieve.

13. the method for claim 12, wherein said OH ^-: Y is 0.01-0.5.

14. each method among the claim 7-12, wherein said Y: X ₂Be 10-55.

15. each method among the claim 7-14, wherein said crystallization condition further comprises stirring, and described stirring has the speed of 200-1000RPM.

16. each method among the claim 7-15, wherein said R: Y is 0.01-0.5.

17. the manufacture method of crystalline molecular sieve, this method may further comprise the steps:

Y: X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

OH ^-∶Y＝0.001-2

M ⁺∶Y＝0.001-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination, wherein said OH ^-: Y calculates under the situation that has or do not have the triad source to proofread and correct, and wherein said crystal seed has the concentration in described mixture of about 0.01-10wt%, based on the weight of quadrivalent element oxide described in the described mixture; With

(c) reclaim this crystalline molecular sieve.

18. the method for claim 17, wherein said OH ^-: Y is 0.01-1.

19. the method for claim 17, wherein said OH ^-: Y is 0.1-0.5.

20. each method among the claim 17-19, wherein said Y: X ₂Be 10-55.

21. each method among the claim 17-20, described crystal seed have the concentration in described mixture of about 0.1-5wt%, based on the weight of quadrivalent element oxide described in the described mixture.

22. the manufacture method of crystalline molecular sieve, this method may further comprise the steps:

(Ge+Y): X ₂=10 to infinitely great

H ₂O∶Y＝1-10000

M ⁺∶Y＝0-2

R∶Y＝0.001-2

Wherein M is that alkali metal and R are at least a N, N, N, N ', N ', N '-vegolysen, 5-pentane di-ammonium salts, N, N, N, N ', N ', N '-vegolysen, 6-hexane di-ammonium salts, or their any combination; With

(c) reclaim this crystalline molecular sieve.

23. the method for claim 22, wherein said (Ge+Y): X ₂Be 15-600.

24. each method among the claim 22-23, wherein said H ₂O: Y is 5-35.

25. each method among the claim 22-24, wherein said M ⁺: Y is 0-1.

26. each method among the claim 17-25, wherein said crystallization condition further comprises stirring, and described stirring has the speed of 50-1000RPM.

27. each method among the claim 7-26, wherein said quadrivalent element (Y) is a silicon.

28. each method among the claim 7-27, wherein said triad (X) is an aluminium.

29. each method among claim 7-16 and the 22-28 also comprises crystal seed, described crystal seed has the concentration in described mixture of about 0.01-10wt%, based on the weight of quadrivalent element oxide described in the described mixture.

30. each method among the claim 7-29, wherein said crystalline molecular sieve has by N ₂The BET method measure greater than 450m ²The total surface area of/g.

31. MCM-22 family molecular sieve by each manufacturing among the claim 7-30.

32. hydroconversion process may further comprise the steps:

(a) under conversion condition, allow hydrocarbon feed contact to form product with the crystalline molecular sieve of crystalline molecular sieve of making by each method among the claim 7-30 or claim 1-6.