CN104854064B

CN104854064B - The aromatics using UZM-39 aluminosilicate zeolite turns alkylation

Info

Publication number: CN104854064B
Application number: CN201380064584.2A
Authority: CN
Inventors: C·P·尼古拉斯; E·P·博尔丁格; M·R·施赖埃尔
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 2012-12-12
Filing date: 2013-05-01
Publication date: 2016-11-30
Anticipated expiration: 2033-05-01

Abstract

The present invention has synthesized TUN and the IMF zeolite type complex New raxa of coherent growth and has shown that it is the effective catalyst that aromatics turns alkylated reaction.These zeolites are by empirical formula: Na_nM_m ^k+T_tAl_1‑xE_xSi_yO_zRepresent, wherein M represents from following metal: the 1st race (IUPAC 1), the 2nd race (IUPAC 2), the 3rd race (IUPAC 3) or the lanthanide series of zinc or periodic chart, T is the organic directing agent being derived from reactant R and Q, wherein R is through Α, the substituted alkane of Ω dihalo (such as Isosorbide-5-Nitrae dibromobutane) and Q are that at least one has 6 or the neutral amine (such as 1 crassitude) of less carbon atom.E is backbone element such as gallium.The method relates to making to comprise C₇、C₉、C₁₀And C₁₁The charging circulation alkylation of one or more in+aromatic compounds is to obtain C₈Aromatic compounds substrate concentration turns alkylate stream relative to what this feed stream increased.

Description

The aromatics using UZM-39 aluminosilicate zeolite turns alkylation

Prioity claim

This application claims the priority of the U. S. application 61/736,382 submitted to for 12nd in December in 2012, by this application Being incorporated by reference in its entirety herein of content.

Invention field

The present invention relates to use the new aluminosilicate zeolite kind being referred to as UZM-39 to turn urging of alkylated reaction as aromatics Change complex.This zeolite type is represented by following empirical formula:

Na_nM_m ^k+T_tAl_1-xE_xSi_yO_z

Wherein M represents from following metal: the 1st race (IUPAC 1) of zinc or periodic chart, the 2nd race (IUPAC 2), the 3rd Race (IUPAC 3) or lanthanide series, T is the organic directing agent being derived from reactant R and Q, and wherein R is to replace through Α, Ω-dihalo Alkane (such as 1,4-dibromobutane) and Q be that at least one has 6 or neutral amine (the such as 1-methyl pyrrole of less carbon atom Cough up alkane).E is backbone element such as gallium.

Background of invention

Zeolite is by corner-sharing AlO₂And SiO₂The microporous crystalline silico aluminate compositions that tetrahedron is formed.Numerous naturally occur With synthetically prepared zeolite in multiple commercial runs.Synthetic zeolite uses suitable source and the structure directing agent of Si, Al As alkali metal, alkaline-earth metal, amine or organoammonium cations are prepared via Hydrothermal Synthesis.These structure directing agents reside at zeolite Hole in and be largely fixed the concrete structure ultimately formed.Skeleton electric charge that these material balances are relevant to aluminum and also may be used As space implant.Zeolite is characterized by the hole opening of uniform-dimension, has notable ion-exchange capacity, and can The absorption being scattered in the whole internal pore of crystal the most reversibly desorbing is made significantly to replace any composition permanent zeolite crystalline substance The atom of body structure.Zeolite can be used as the catalyst of hydrocarbon conversion reaction, and these reactions can interior table on the outer surface and in hole Occur on face.

A kind of concrete zeolite (referred to as TNU-9) initially open in 2004 by Hong etc. (J.Am.Chem.Soc.2004, 126,5817-26) and then disclosed in Korean Patent KR480229 authorized for 2005.Report at this and after patent, Within 2007, report this synthesis (J.Am.Chem.Soc.2007,129,10870-85) comprehensively.These papers describe and exist at sodium Under by double (the N-crassitude of flexible dication structure directing agent 1,4-) dibromobutane synthesis TNU-9.Resolving TNU- After the structure (Nature, 2006,444,79-81) of 9, structure committee of International Zeolite Association (International Zeolite Association Structure Commission) give this zeolite structure type code TUN, see zeolite framework type figure Collection (Atlas of Zeolite Framework Types), this atlas by structure committee of International Zeolite Association at http: // Www.iza-structure.org/databases/ is upper to be safeguarded.Find that TUN structure type contains 3 groups of mutually orthogonal passages, The most each passage is limited by 10 Yuans rings of tetrahedral coordination atom.Additionally, this structure there is also 2 10 varied in size Member's ring passage.

Another concrete zeolite IM-5 was initially disclosed (FR96/12873 by Benazzi etc. in 1996；WO98/17581), its Describe in the presence of sodium by double (the N-crassitude of flexible dication structure directing agent 1,5-) dibromo pentane or 1,6- Double (N-crassitudes) dibromo-hexane synthesis IM-5.Baerlocher etc. resolve IM-5 structure (Science, 2007,315,113-6), after, international zeolite structure committee gives this zeolite structure type code IMF, sees zeolitic frameworks class Type atlas.Also finding that IMF structure type contains three groups of mutually orthogonal passages, the most each passage is by tetrahedral coordination atom 10 Yuans rings limit, but, the connective every 2.5nm in the third dimension interrupts, and the most slightly limits diffusion.Additionally, in the structure shown here There are multiple different size of 10 Yuans ring passages.

The applicant the most successfully prepares the new material kind of referred to as UZM-39.The topology of these materials with to TNU-9 and IM-5 is viewed similar.These materials are via using and Na⁺Synergistic simple commercially available structure directing agent (such as 1,4- Dibromobutane and 1-crassitude) mixture use zeolite synthesis layered material transform mode (being described below) come Preparation.These materials (referred to as UZM-39) can be used as the catalyst that aromatics turns in alkylated reaction.

Summary of the invention

As it has been described above, the present invention relates to TUN and the IMF zeolite type that use includes coherent growth (coherently grown) The new catalytic composite (referred to as UZM-39) of complex turns the catalytic composite in alkylation as aromatics.The most former Sample (as synthesized) and anhydrous on the basis of, microporous crystalline zeolite has at least AlO₂And SiO₂The three-dimensional of tetrahedron element Skeleton and the experience represented by following empirical formula form:

Na_nM_m ^k+T_tAl_1-xE_xSi_yO_z

Wherein " n " be Na with the mol ratio of (Al+E) and have 0.05 to 0.5 value, it is as follows that M represents that at least one is selected from Metal: zinc, the 1st race (IUPAC 1), the 2nd race (IUPAC 2), the 3rd race (IUPAC 3) and the lanthanide series of periodic chart and Any combination, " m " be M with the mol ratio of (Al+E) and have 0 to 0.5 value, " k " is the mean charge of metal M, and T is for being derived from The Organic structure directing agent of reactant R and Q, wherein R is the Α with 3 to 6 carbon atoms, the substituted alkane of Ω-two halogen, and Q is that at least one has 6 or the neutral monoamine of less carbon atom, and " t " is the N from Organic structure directing agent and (Al+E) Mol ratio and have 0.5 to 1.5 value, E is the element of group that choosing free gallium, ferrum, boron and combinations thereof form, and " x " is rubbing of E Your mark and have 0 to 1.0 value, " y " is Si and the mol ratio of (Al+E) and by more than 9 to 25 changes, and " z " is O and (Al + E) mol ratio and be there is the value determined by below equation:

Z=(n+k m+3+4 y)/2

And it is characterized in that its there is the coherence arrangement TUN region of (coherently aligned) and IMF region so that Obtain [010]_TUNCrystal zone axis and [001]_IMFCrystal zone axis is parallel to each other and makes (002)_TUNType and (060)_IMFType crystal face has seriality, Wherein indexing (indexing) relates separately to monocline C of TUN and IMF_2/mWith tiltedly side C_mcmStructure cell.

In post synthesis former state and anhydrous on the basis of, this microporous crystalline zeolite further may be described as having at least AlO₂And SiO₂Four Three-dimensional framework and the experience represented by following empirical formula of face body unit form:

Na_nM_m ^k+T_tAl_1-xE_xSi_yO_z

Wherein " n " be Na with the mol ratio of (Al+E) and have 0.05 to 0.5 value, M represents from following metal: week 1st race (IUPAC 1), the 2nd race (IUPAC 2), the 3rd race (IUPAC3), lanthanide series or the zinc of phase table, " m " is M and (Al+E) Mol ratio and have 0 to 0.5 value, " k " is the mean charge of metal M, T be derived from reactant R and Q organic structure guide Agent, wherein R is the Α with 3-6 carbon atom, the substituted alkane of Ω-two halogen, and Q is that at least one has 6 or less The neutral monoamine of carbon atom, " t " is the mol ratio of N and (Al+E) from Organic structure directing agent and has 0.5 to 1.5 Value, E is the element of group that choosing free gallium, ferrum, boron and combinations thereof form, " x " be the molar fraction of E and have 0 to 1.0 value, " y " is Si and the mol ratio of (Al+E) and by more than 9 to 25 changes, and " z " be O with the mol ratio of (Al+E) and have by with The value that lower equation determines:

Z=(n+k m+3+4 y)/2

And zeolite is characterised by that it has x-ray diffraction pattern, this x-ray diffraction pattern at least has in Table A 1 listed D-spacing and intensity.

Table A 1

* the complex spike being made up of multiple overlapping reflections

This zeolite in one embodiment more than up to 600 DEG C at a temperature of thermally-stabilised and in another embodiment At a temperature of up at least 800 DEG C thermally-stabilised.

Layered material transform mode can be used to prepare crystalline microporous zeolite as described above.The method includes that formation contains Have the reactive source of Na, R, Q, Al, Si, the crystal seed of layered material L and optionally E and/or M reactant mixture and 150 DEG C to be enough to reactant mixture heating at a temperature of 200 DEG C, 155 DEG C to 190 DEG C or 160 DEG C to 180 DEG C to be formed zeolite time Between.L does not have the zeolite type same with UZM-39 coherent growth composite bulk phase.Reactant mixture has with the molar ratio computing of oxide By being expressed as forming of following formula:

a-b Na₂O:bM_n/2O:cRO:dQ:1-eAl₂O₃:eE₂O₃:fSiO₂:gH₂O

Wherein " a " has the value of 10 to 30, and " b " has the value of 0 to 30, and " c " has the value of 1 to 10, and " d " has 2 to 30 Value, " e " has the value of 0 to 1.0, and " f " has the value of 30 to 100, and " g " has the value of 100 to 4000.Additionally, reaction mixing Thing comprises based on the SiO in reactant mixture₂The crystal seed zeolite L of amount 1wt.% to 10wt.%, if in such as reactant mixture There is 100g SiO₂, then 1g to 10g crystal seed zeolite L can be added to reactant mixture.In view of reactive reagent source so Many, multiple order of addition can be designed.Generally, before adding silica agents, aluminon is dissolved in sodium hydroxide.As The most visible, reagent R from Q can together with or individually add with multiple different orders of addition.

The present invention uses UZM-39 as the catalyst turning in alkylation of alkylaromatic hydrocarbons or catalytic component.Cause This, the broad practice of the present invention is for making to comprise C₇、C₉、C₁₀And C₁₁The feed stream of one or more in+aromatic compounds Turn alkylation to obtain C₈The method turning alkylate stream that aromatic compounds substrate concentration increases relative to feed stream, the method Contact with the catalyst comprising UZM-39 under turning alkylation conditions including making feed stream.

Accompanying drawing is sketched

Fig. 1 is the XRD figure case of the UZM-39 zeolite formed in embodiment 1.This pattern displaying is in intact form after synthesis UZM-39 zeolite.

Fig. 2 is also the XRD figure case of the UZM-39 zeolite formed in embodiment 1.UZM-39 after the calcining of this pattern displaying Zeolite.

Fig. 3 is the XRD figure case of the UZM-39 zeolite formed in embodiment 16.This pattern displaying is in intact form after synthesis UZM-39 zeolite.

Fig. 4 is also the XRD figure case of the UZM-39 zeolite formed in embodiment 16.This pattern displaying is H⁺The UZM-of form 39 zeolites.

Fig. 5 is the XRD figure case of the UZM-39 zeolite formed in embodiment 28.This pattern displaying is in intact form after synthesis UZM-39 zeolite.

Fig. 6 is also the XRD figure case of the UZM-39 zeolite formed in embodiment 28.This pattern displaying is H⁺The UZM-of form 39 zeolites.

Fig. 7 shows the result that the high resolution scanning electron microscopy of the UZM-39 product of embodiment 1 characterizes.This electronic display Micro-photo display UZM-39 forms the lath (lathes) being assembled into rectangular bars granule, and is generally of the arrangement of sudden and violent bunch of star.? Sudden and violent bunch of rod of star of visible UZM-39 in the scanning electron microscopy result of Fig. 7.

Fig. 8 shows the result that the high resolution scanning electron microscopy of the different UZM-39 products of embodiment 18 characterizes.Electricity Sub-microphotograph also shows the lath being assembled into rectangular bars granule with the arrangement of sudden and violent bunch of numerous star.

Fig. 9 shows the line frame graph (left figure) of the TUN skeleton in AC face.Each summit is T site and in each bar Between be oxygen atom.The line frame graph of the IMF skeleton in AB face is shown in right figure.Project along these, both TUN and IMF skeletons Containing the almost identical projection by channel attached 5 loop chains of 6 rings and 10 rings.

Figure 10 shows that the UZM-39 product of embodiment 17 is carried out by use high-resolution imaging and computer optics diffraction pattern The result that transmission electron microscopy characterizes.These results display UZM-39 includes TUN and the IMF zeolite type composite junction of coherent growth Structure.

Figure 11 is electron diffraction analysis and the display of the rod-shpaed particle section of Figure 10, is sent out by seeming to be single crystals zeolite granular Existing index turns to [010] crystal zone axis of TUN and the region of [001] crystal zone axis of IMF.TUN region and the arrangement of IMF region coherence.

Figure 12 is the curve in the low angle region in the XRD analysis of material, and its display is in the sample being mainly made up of TUN The IMF of small percentage can be measured to.

Figure 13 is the curve in the low angle region in the XRD analysis of material, and its display is in the sample being mainly made up of IMF The TUN of small percentage can be measured to.

Figure 14 is the catalyst for containing in catalyst composite and without UZM-39, and benzene purity becomes with toluene conversion The curve changed.

Detailed Description Of The Invention

The applicant has prepared and is applicable to be catalyzed aromatics and turns the catalyst component of alkylated reaction, and wherein this catalyst component is silicon Aluminosilicate zeolitic (referred to as UZM-39), its topological structure with as by structure committee of International Zeolite Association at http: // TUN described in the zeolite framework type atlas of the upper maintenance of www.iza-structure.org/databases/ is correlated with, its The most named TNU-9 of member.As hereafter displayed the details of, numerous features (including its x-ray diffraction pattern (XRD)) of UZM-39 Different from TNU-9.UZM-39 is also relevant to the IMF as described in zeolite framework type atlas, the most named IM-5 of its member. As hereafter displayed the details of, numerous features (including its x-ray diffraction pattern) of UZM-39 are different from TNU-9 and IM-5.Closing After one-tenth former state and anhydrous on the basis of, the microporous crystalline zeolite (UZM-39) of the present invention has the experience group represented by following empirical formula Become:

Na_nM_m ^k+T_tAl_1-xE_xSi_yO_z

Wherein " n " be Na with the mol ratio of (Al+E) and have 0.05 to 0.5 value, M represents selected from following metal: Zinc, the 1st race (IUPAC 1), the 2nd race (IUPAC 2), the 3rd race (IUPAC 3), lanthanide series and any combination thereof of periodic chart, " m " be M with the mol ratio of (Al+E) and have 0 to 0.5 value, " k " is the mean charge of metal M, and T is for being derived from reactant R and Q Organic structure directing agent, wherein R is the Α with 3-6 carbon atom, the substituted alkane of Ω-two halogen, and Q is at least one There is 6 or the neutral monoamine of less carbon atom, " t " be from the N of Organic structure directing agent and the mol ratio of (Al+E) and Having the value of 0.5 to 1.5, E is the element of the group of choosing free gallium, ferrum, boron and combinations thereof composition, and " x " is molar fraction and the tool of E Having the value of 0 to 1.0, " y " is Si and the mol ratio of (Al+E) and by more than 9 to 25 changes, and " z " be O with (Al+E) mole Than and be there is the value determined by below equation:

Z=(n+k m+3+4 y)/2

If M is only a kind of metal, then weighted average valence is the quantivalence of this kind of metal, i.e.+1 or+2.But, When there is more than one M metal, total amount is:

M_m ^k+=M_m1 ^(k1)++M_m2 ^(k2)++M_m3 ^(k3)++M_m4 ^(k4)++……

And weighted average valence " k " is given by below equation:

In one embodiment, microporous crystalline zeolite UZM-39 is synthesized by the hydrothermal crystallization of reactant mixture, should Reactant mixture is prepared by combining following material: reactive source, Organic structure directing agent T, aluminum, silicon, the layering material of sodium Material L crystal seed and optionally E, M or the two.The source of aluminum include, but is not limited to aluminum alkoxide, precipitated alumina, aluminum metal, Aluminium hydroxide, sodium aluminate, aluminium salt and alumina sol.The particular instance of aluminum alkoxide includes, but is not limited to aluminium secondary butylate and just Aluminum isopropylate..The source of silicon dioxide include, but is not limited to tetraethyl orthosilicate, colloidal silica, precipitated silica and Alkaline silicate.The source of sodium includes, but is not limited to sodium hydroxide, sodium aluminate, sodium bromide and sodium silicate.

T is the Organic structure directing agent being derived from reactant R and Q, and wherein R is the Α with 3-6 carbon atom, Ω-dihalo- The substituted alkane of element, and Q includes that at least one has 6 or the neutral monoamine of less carbon atom.R can be selected from following tool Have the Α of 3-6 carbon atom, the substituted alkane of Ω-two halogen: 1,3-dichloropropane, 1,4-dichloroetane, 1,5-dichloropentane, 1,6-dichloro hexane, 1,3-dibromopropane, 1,4-dibromobutane, pentamethylene bromide, 1,6-dibromo-hexane, 1,3-diiodo-third Alkane, 1,4-bis-iodobutane, 1,5-bis-iodopentane, 1,6-bis-iodohexane and combinations thereof.Q includes that at least one has 6 or less The neutral monoamine of carbon atom, such as 1-ethyl pyrrolidine, 1-crassitude, 1-ethyl azetidine, 1-methyl azepine Tetramethylene., triethylamine, diethylmethyl amine, dimethylethyl amine, trimethylamine, dimethylbutyl amine, dimethyl propyl amine, diformazan Base isopropylamine, Methylethyl propyl group amine, Methylethyl isopropylamine, di-n-propylamine, diisopropylamine, Aminocyclopentane, methylcyclohexylamine, Hexamethylene imine.Q can include the combination of the multiple neutral monoamine with 6 or less carbon atom.

L includes the crystal seed of at least one layering zeolite.Suitable crystal seed zeolite is the layered material for micro-pore zeolite, and this is slightly The crystal thickness of hole zeolite is less than 30nm to 50nm at least one dimension.These poromerics have the hole less than 2nm Footpath.This crystal seed layering zeolite has the zeolite type different from synthesized UZM-39 coherent growth complex.Suitable layered material Example include, but is not limited to UZM-4M (US6776975), UZM-5 (US6613302), UZM-8 (US6756030), UZM- 8HS (US7713513), UZM-26 (US-2010-0152023-A1), UZM-27 (US7575737), BPH, FAU/EMT material, * BEA or zeolite beta, member (such as MCM-22P and MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-of MWW kind 2, ITQ-30, ERB-1, EMM-10P and EMM-10, SSZ-25 and SSZ-70) and less poromerics, such as PREFER (front Ferrierite (pre ferrierite)), NU-6 etc..

M represents that at least one is from the 1st race (IUPAC 1) of periodic chart, the 2nd race (IUPAC 2), the 3rd race (IUPAC 3) Or lanthanide series and or the exchangeable cations of metal of zinc.The particular instance of M include, but is not limited to lithium, potassium, rubidium, caesium, magnesium, Calcium, strontium, barium, zinc, yttrium, lanthanum, gadolinium and mixture thereof.The reactive group including, but is not limited to consist of of originating of M: halogenation Thing, nitrate, sulfate, hydroxide or acetate.E is the element of the group of choosing free gallium, ferrum, boron and combinations thereof composition, and Suitable reactivity source includes, but is not limited to boric acid, gallium oxide hydroxide, gallium sulfate, Ganite (Fujisawa)., iron sulfate, ferric nitrate, chlorination Ferrum and mixture thereof.

The reactant mixture in the reactive source containing required component can be described as following formula with the molar ratio computing of oxide:

a-b Na₂O:bM_n/2O:cRO:dQ:1-eAl₂O₃:eE₂O₃:fSiO₂:gH₂O

Wherein " a " has the value of 10 to 30, and " b " has the value of 0 to 30, and " c " has the value of 1 to 10, and " d " has 2 to 30 Value, " e " has the value of 0 to 1.0, and " f " has the value of 30 to 100, and " g " has the value of 100 to 4000.Additionally, it is mixed in reaction In compound, crystal seed zeolite L is based on the SiO in reaction₂Amount be 1wt.% to 10wt.%, if in such as reactant mixture exist 100g SiO₂, then by interpolation 1g to 10g crystal seed zeolite L.The display of this example produces the numerous specific of the reactant mixture of UZM-39 Order of addition.But, owing to there are at least 6 kinds of parent materials, therefore can there is multiple order of addition.Such as, crystal seed L can be as Rear composition adds to reactant mixture, or adds to reactive Si source, or adds at other suitable time points.And, If use alcoxylates, then can comprise distillation or evaporation step to remove alcohol hydrolyzate.Although can crowd in the method Organic structure directing agent R and Q is added to reactant mixture by many time points individually or together, but the most at room temperature by R and Q Mix and the mixture of merging is added the cooling originated to reactive Si, Al and the Na maintaining at 0 DEG C-10 DEG C and mix In compound.Another is chosen as, and can cool down and by the reactive source of Si, Al and Na after at room temperature being mixed by the mixture of R with Q Add to Organic structure directing agent mixture, maintain the temperature of 0 DEG C-10 DEG C simultaneously.In replacing embodiment, can be in room temperature Lower reagent R and Q is added individually or together to reactant mixture.

Then at autogenous pressures at 150 DEG C to 200 DEG C, 155 DEG C to 190 DEG C or 160 in sealing stirring reaction vessel DEG C to making at a temperature of 180 DEG C reactant mixture react 1 day to 3 weeks, and react 3 days to 12 days in another embodiment.Complete After becoming crystallization, filter by (such as) or centrifugal by non-homogeneous mixture separation solid product, and be then washed with deionized And be dried in atmosphere under the ambient temperature of at most 100 DEG C.

After the synthesis of TUN and IMF zeolite type, former state coherent growth complex UZM-39 is characterised by least having following table D-spacing listed in A1-A3 and the x-ray diffraction pattern of relative intensity.Diffraction pattern herein uses typical laboratory powder Diffractometer utilizes the K of copper_αLine (Cu K α) obtains.Bragg equation can be used by the position of the diffraction maximum represented by 2 θ angles Calculate characteristic interplanar spacing d of sample_hkl.Intensity calculates based on relative intensity scale, and it is specified on X-ray diffraction pattern The value of the line of expression highest peak is 100, and then: the most weak (vw) means less than 5；Weak (w) means less than 15；Medium (m) means In the range of 15 to 50；(s) means in the range of 50 to 80 by force；Extremely strong (vs) means more than 80.Intensity is also shown as Above-mentioned inclusive scope.The X-ray diffraction pattern being obtained data (d spacing and intensity) by it is characterised by reflecting in a large number, this Some in a little reflections are broad peak or the peak forming shoulder on higher-strength peak.These shoulders some or all of can not be resolved.This Situation occurs in that degree of crystallinity is low, there is the sample of concrete coherent growth composite construction in or crystal is little causes notable widthization to being enough to In the sample of X-ray.This situation can also occur in the equipment for producing diffraction pattern or operating condition and for the present invention When those in situation are dramatically different.

The X-ray diffraction pattern of UZM-39 contains multiple peak.The x-ray diffraction of the UZM-39 product of former state after multiple synthesis The example of pattern is shown in Fig. 1, Fig. 3 and Fig. 5.For various coherent growth composite constructions, those characteristic peaks of UZM-39 show It is shown in Table A 1-A3.Also can there are the most weak those in other peaks, especially intensity.It is present in coherent growth composite construction All medium or higher-strength the peak of UZM-39 kind apoplexy due to endogenous wind is shown at least in Table A 3.

Table A 1 contains selected d-spacing and the relative intensity of UZM-39X ray diffraction pattern.Relative intensity is shown as containing The scope of the UZM-39 material that the relative quantity of TUN with IMF zeolite type is different.

Table A 1

* the complex spike being made up of multiple overlapping reflections

The feature of zeolite can be furthermore that at least have d-spacing listed in Table A 2 and the X-ray diffraction pattern of intensity Case, wherein d-spacing and intensity provide under the different relative concentrations of the component of coherent growth composite construction.

Table A 2

The feature of zeolite can be furthermore that at least have d-spacing listed in Table A 3 and the X-ray diffraction pattern of intensity Case, wherein d-spacing and intensity provide under the different relative concentrations of the component of coherent growth composite construction.

Table A 3

In Table A 2 and Table A 3, term " high " refers to that the specified ingredients of 60 mass % to 95 mass %, term " medium " are Refer to the specified ingredients of 25 mass % to 70 mass %, and term " low " refers to the specified ingredients of 5 mass % to 40 mass %.Some Peak can be the shoulder on higher peak, and the complex spike that some peaks can be made up of multiple overlapping reflections.

As displayed the details of in an embodiment, UZM-39 material is thermally-stabilised and separately at a temperature of up at least 600 DEG C In one embodiment thermally-stabilised at a temperature of up at least 800 DEG C.Also as shown in embodiment, UZM-39 material can have and accounts for The percentage ratio of the total pore volume micro pore volume more than 60%.

By high resolution scanning electron microscopy, the sign of UZM-39 product is shown that UZM-39 is formed and be assembled into rectangle The lath of rod-shpaed particle, these laths are generally of the arrangement of sudden and violent bunch of star.Two kinds of concrete UZM-39 products in figures 7 and 8 Sudden and violent bunch of rod of star of visible UZM-39 in scanning electron microscopy result.

UZM-39 is TUN and the IMF zeolite type composite construction of coherent growth.Coherent growth composite construction means two kinds of structures It is present in most of crystal of given sample.This coherent growth composite construction at two kinds of zeolite type structure along its crystal structure The projection of at least one crystal face be possible when there is almost identical steric arrangement and there is similar holes topological structure.Figure The line frame graph (left figure) of the TUN skeleton in 9 display AC faces.Each summit is tetrahedral site (or T site) and at each bar Centre be corner-sharing oxygen atom.The line frame graph of the IMF skeleton in AB face is shown in the right figure of Fig. 9.Project along these, TUN 5 loop chains that 6 rings containing the almost identical passage vertical with this face by formation with both IMF zeolite types and 10 rings are connected Projection.

Owing to TUN and IMF zeolite type both at 3-dimensional 10 ring zeolite and has almost identical projection in a face, Therefore these two kinds of structures can depart from the crystal coherent growth of another structure at compatible with interface, to form coherent growth Composite construction.

The physical mixture of coherent growth composite construction not two kinds of molecular sieves.Use electronic diffraction, transmission electron microscopy Art and x-ray diffraction analysis carry out display material and are coherent growth composite construction rather than physical mixture.Generally electronic diffraction and TEM The combination of imaging has produced in coherent growth composite construction most definitiveness, this is because it provides the most measuring a kind of material The positive evidence of two kinds of structures is there is in a crystal.

Owing to the coherent growth composite construction zeolite of the present invention can have different amounts of two kinds of structure types, therefore should manage Solving, the relative intensity of some diffracted rays and line width will depend upon which that the amount of each structure present in coherent growth composite construction becomes Change.Although the diversity factor of the x-ray powder diffraction pattern of the most measurable ad hoc structure, but coherent growth composite construction In nature, most probable pattern is random, and is therefore difficult to pre-when not using large-scale hypothesized model as calculating basis Survey.

Different from the physical mixture of TNU-9 with IM-5, use high-resolution imaging and computer optics diffraction pattern to carry out Transmission electron microscopy (TEM) analyze display, UZM-39 includes TUN and the IMF zeolite type composite construction of coherent growth.

In Fig. 10, the tem analysis from the rod-shpaed particle section of embodiment 17 product shows have TUN and IMF structure Region occur in effective single crystals zeolite granular as coherence subregion.In the left side of Figure 11, it is shown in Figure 10 Electron diffraction analysis on the left of granule shows and index can turn to the electron diffraction pattern of 002 of TUN.The right side of Figure 11 shows Show the electron diffraction pattern on the right side of granule shown in Figure 10.This pattern index can turn to 060 of IMF.TUN region It is arranged so as to [010] with IMF region coherence_TUNCrystal zone axis and [001]_IMFCrystal zone axis is parallel to each other, and makes (002)_TUNType and (060)_IMFThe crystal face of type has seriality, and wherein indexing relates separately to monocline C of TUN and IMF_2/mWith tiltedly side C_mcmStructure cell (knot The details of structure sees IZA website).Although two kinds of zeolite types are present in the different piece of granule, but image does not show any Describe the obvious border of the independent crystal of TUN and IMF, thus show that this granule is coherent growth complex.

Additionally, (Rietveld is analyzed in the Li Te Wald that the feature of UZM-39 zeolite may be in XRD figure case analysis).Least square mode (the Journal of Applied researched and developed by Li Te Wald is analyzed in Li Te Wald Crystallography 1969,2:65-71), which refine Molded Line XRD spectral line is until it mates institute as closely as possible The XRD figure case measured, and be by the method for optimizing of sample (such as UZM-39) the derivation structural information containing strong overlapping reflection.Its It is generally used for quantifying two kinds of out of phase amounts in XRD diffraction pattern.The precision of Li Te Wald method is big by parameter such as crystallite Little (peak broadening), peak-shaped function, Lattice cell constant and Background fitting determine.For sample shown in embodiment, this The error that applicants have determined that in report value under the conditions of being used is ± 5%.The applicant has also determined that, special in being used Wald model cannot the quantized value amount of minority composite construction phase component less than 10%, but it practice, content lacking more than 5% The amount that array is divided can be by being compared to observation to model pattern.Table 1 shows the multiple UZM-39 sample from embodiment Li Te Wald refine result and display UZM-39 contain more than 0wt.% and less than the IMF zeolite type of 100wt.% be less than 100wt.% and the TUN zeolite type more than 0wt.%.In another embodiment, UZM-39 contains more than 5wt.% and is less than The IMF zeolite type of 95wt.% and less than 95wt.% and the TUN zeolite type more than 5wt.%, and in yet another embodiment, UZM-39 contains the IMF zeolite type more than 10wt.% and being less than 90wt.% and is less than 90wt.% and the TUN more than 10wt.% Zeolite type.As visible in table 1 and embodiment, wide scope coherent growth composite construction can be formed by changing synthesis condition.

After synthesis the UZM-39 material of former state in its hole will containing some commutative or charge balance cation.These can Exchange cation can exchange with other cationes, or in the case of organic cation, it can be by heating under controlled conditions Remove.Some organic cations are directly removed by UZM-39 zeolite also by ion exchange.UZM-39 zeolite can be with multiple side Formula is modified so that it is be applicable to specifically applying.Modification includes calcining, ion exchange, steam process, multiple acid extraction, hexafluoro silicon Acid ammonium process or its any combination, such as US 6, in 776,975B1, the situation to UZM-4M is summarized, by the full text of this patent with Way of reference is incorporated to.Harsher shown than in US 6,776,975 of condition.The characteristic being modified includes porosity, suction Attached, Si/Al ratio rate, acidity, heat stability etc..

Calcining, ion exchange and calcining after and on the anhydrous basis, microporous crystalline zeolite UZM-39 has at least AlO₂ And SiO₂Three-dimensional framework and the experience in hydrogen form represented by following empirical formula of tetrahedron element form:

M1_a ^N+Al_(l-x)E_xSi_y’O_z”

Wherein M1 is that at least one is selected from following exchangeable cations: alkali metal, alkaline-earth metal, rare earth metal, ammonium from Son, hydrion and combinations thereof, " a " is M1 and the mol ratio of (Al+E) and by 0.05 to 50 change, and " N " is the weighted average of M1 Conjunction valency and have+1 to+3 value, E is the element of group that choosing free gallium, ferrum, boron and combinations thereof form, x be E molar fraction and By 0 to 1.0 change, y ' be Si with the mol ratio of (Al+E) and by more than 9 to the purest silicon dioxide change, and z " be O With the mol ratio of (Al+E) and be there is the value determined by below equation:

Z "=(a N+3+4 y ')/2.

In hydrogen form, in calcining, ion exchange and calcining to remove NH₃After, UZM-39 demonstrates in table B1-B3 and is shown The XRD figure case shown.For various coherent growth composite constructions, those characteristic peaks of UZM-39 are shown in table B1-B3.Also can deposit The most weak those at other peaks, especially intensity.It is present in UZM-39 kind apoplexy due to endogenous wind all medium of coherent growth composite construction Or the peak of higher-strength is at least shown in table B3.

Table B1 contains selected d-spacing and the relative intensity of the UZM-39X ray diffraction pattern of hydrogen form.Relative intensity shows It is shown as the scope containing the different UZM-39 material of the relative quantity of TUN with IMF zeolite type.

Table B1

* the complex spike being made up of multiple overlapping reflections

The feature of zeolite can be furthermore that at least have d-spacing listed in table B2 and the X-ray diffraction pattern of intensity Case, wherein d-spacing and intensity provide under the different relative concentrations of the component of coherent growth composite construction.

Table B2

The feature of zeolite also can be furthermore that at least have d-spacing listed in table B3 and the X-ray diffraction pattern of intensity Case, wherein d-spacing and intensity provide under the different relative concentrations of the component of coherent growth composite construction.

Table B3

In table B2 and table B3, term " high " refers to that the specified ingredients of 60 mass % to 95 mass %, term " medium " are Refer to the specified ingredients of 25 mass % to 70 mass %, and term " low " refers to the specified ingredients of 5 mass % to 40 mass %.Some Peak can be the shoulder on higher peak, and the complex spike that some peaks can be made up of multiple overlapping reflections.

(HNO such as it is exposed in acid treatment₃Or H₂SiF₆) afterwards and on the anhydrous basis, microporous crystalline zeolite UZM-39 has There is at least AlO₂And SiO₂The three-dimensional framework of tetrahedron element and the experience group in acid treatment form represented by following empirical formula Become:

M1_a ^N+Al_(l-x)E_xSi_y’O_z”

Z "=(a N+3+4 y ')/2

Similar to the material of former state after synthesis, it is modified UZM-39 material thermally-stabilised at a temperature of up at least 600 DEG C And thermally-stabilised at a temperature of up at least 800 DEG C in another embodiment, and can have that to account for the percentage ratio of total pore volume big In the micro pore volume of 60%.

The purest silicon dioxide means the most to be removed all aluminum and/or E metal by skeleton.It is known that it is real All aluminum and/or E metal can not be removed on border.Numerically, have at least 3 at y ', 000, preferably 10,000, most preferably 20,000 value time, zeolite is the purest silicon dioxide.Therefore, y ' in the range of 9 to 3,000, more than 20 to 3,000,9 To 10,000, more than 20 to 10,000,9 to 20,000 and more than 20 to 20,000.

Unless otherwise stated, describe the ratio of zeolite parent material or the absorption spy of zeolite product in this article in detail During property etc., zeolite will be intended to be in " anhydrous state ".Term as used herein " anhydrous state " refers to that zeolite is the most not Containing physical absorption and both the water of chemisorbed.

UZM-39 zeolite and modified form thereof also act as urging in the catalytic composite turning alkylation for aromatics Agent or catalytic component.As used herein, term " turns alkylation " to be contained between Alkylaromatics, at benzene and alkane Turn alkylation between base aromatic compounds, and it includes that dealkylation and disproportionation, such as toluene are to benzene and dimethylbenzene.These virtues Race's hydrocarbon may also include naphthalene and other C₁₀And C₁₁Aromatic compounds.In this article, hydrocarbon molecule can be abbreviated as C₁、C₂、C₃……C_n, its In " n " represent the carbon number in hydrocarbon molecule.After these abbreviations "+" for representing the carbon number of each molecule or more, And "-" is for representing the carbon number of each molecule or less.UZM-39 catalyst composite can further include refractory inorganic Oxide adhesive and metal component.This catalyst also can stand pre-sulfiding step to mix sulfur.

As it has been described above, zeolite as outlined above or its modified form can be in having the compound of commonly known binding agent Bodily form formula.Use UZM-39 as the catalyst in multiple reaction or catalyst carrier.Can be with 5 mass % to 100 mass % UZM-39 is mixed so that forming catalyst by the ratio of UZM-39 zeolite and 0 mass % to 95 mass % binding agents with binding agent Granule.In one embodiment, binding agent is porous, and surface area is 5m²/ g to 800m²/ g, and relatively can be to institute in method Refractory for the condition utilized.The limiting examples of binding agent is silicon dioxide, aluminium oxide, titanium dioxide, zirconium oxide, oxidation Zinc, magnesium oxide, boron oxide, thorium oxide, chromium oxide, stannum oxide with and combinations thereof and complex, such as silica-alumina, Silica-magnesia, silica-zirconium oxide, chrominaalumina, alumina-boron oxide, aluminium oxide-titanium dioxide, Aluminum phosphate, silica-zirconium oxide, silica gel and clay.In one embodiment, binding agent is armorphous silicon dioxide and oxygen Change one or more in aluminum, including gama-alumina, η-aluminium oxide and θ-aluminium oxide.In another embodiment, binding agent is Gama-alumina and or η-aluminium oxide.Aluminium oxide can be used as refractory inorganic oxide used herein, and aluminium oxide can be multiple The monohydrate Alpha-alumina of any one in hydrated alumina or alumina gel, such as boehmite structure, gibbsite structure Three hydration Alpha-aluminas, three hydration beta-aluminas etc. of bayerite structure.

Binding agent and zeolite can in any usual manner or other convenient manner combine to form spheroid, pill, agglomerate, grain Material, extrudate or other suitable particle shapes.Such as, zeolite in small, broken bits and metal salt particle are dispersed among in alumina sol, and Mixture is scattered in hot oil bath with drops again, gelling thus occurs and forms spherical gel particle.The method is more detailed It is described in US 2,620,314.A kind of method includes the form in small, broken bits of selected zeolite, refractory inorganic oxide and slaine With binding agent and/or mix lubricant and mixture is compressed into the uniform pill of size and shape or agglomerate.Another is chosen as And still more preferably, zeolite, refractory inorganic oxide and slaine are merged with peptizer in mixing and grinding machine and mixes, dilute Nitric acid is an example of suitable peptizing agent.Gained dough can pressurize via the mould of predefined size or aperture to form extrusion Composition granule, these extrudate granules can drying and calcining be used with former state.May there be numerous kinds of different extrudates Shape, includes, but is not limited to cylinder, quatrefoil, dumb-bell shape and symmetrical and asymmetric many slivers shape, wherein trilobe shape Formula is favourable.Extrudate also can be shaped to spheroid by rotating disk or drum and is then dried and calcines.

In one embodiment, extrudate and or spheroid it are shaped as.Extrudate is prepared by conventional methods, and it relates to With formation, there is appropriate moisture contain adding compositions to be mixed with binding agent and suitable peptizing agent before or after metal component The homogeneous dough of amount or thick paste thing, so that the extrusion having acceptable full to tolerate dinectly bruning can be formed Thing.Then via mould extrusion dough to obtain shaped extrudate.May there be numerous kinds of different extrudate shapes, including (but not limited to) cylinder, quatrefoil, dumb-bell shape and symmetrical and asymmetric many slivers shape.In scope of the invention, also may be used Extrudate is made to be shaped to any desired form (such as spheroid) further by any mode known in the art.

Spheroid can pass through US 2, and prepared by the drop method of knowing described in 620,314, this patent is with way of reference also Enter.The method relates to the mixture of zeolite and (such as) alumina sol and gellant is instilled the oil maintained at elevated temperature In bath.Mixture droplets is maintained in oil bath until it solidifies and forms hydrogel spheroid.Then spheroid is continuous by oil bath Take out and generally make it stand specific burin-in process in oil and ammonia solution to improve its physical features further.It is washed out institute The aging and granule of gelling being dried under the relative low temperature of 50 DEG C to 200 DEG C, and make its temperature at 450 DEG C to 700 DEG C Under stand calcination procedure 1 hour to 20 hours.This process makes hydrogel change into corresponding alumina host.

The catalyst of the present invention optionally can comprise other zeolite component.Other zeolite component are preferably selected from one or more There is the zeolite of following framing structure: MFI, MEL, EUO, FER, MFS, MOR, MTT, MTW, MWW, MAZ, TON and FAU (zeolite Framework types atlas) and such as the UZM-8 in US 6,756,030.In one embodiment, MOR zeolite can be such as US 7, UZM-14 in 687,423.In one embodiment, other zeolite component are substantially made up of UZM-14.In catalyst Suitable zeolite total amount is 1wt% to 100wt%, preferably 10wt% to 95wt%, more preferably 60wt% to 90wt%.

Catalyst can further include the metal component containing one or more elements, and these elements are selected from periodic chart VIB (6) race, VIIB (7) race, VIII (8-10) race, IB (11) race, IIB (12) race, IIIA (13) race and IVA (14) race.When inciting somebody to action When catalyst is used for turning in alkylation, one or more in following of metal component: rhenium, nickel, cobalt, molybdenum and tungsten.Urge Agent can contain phosphorus.Turning the suitable metal amount in alkylation catalyst is 0.01wt% to 15wt% based on element, preferably 0.1wt% to 12wt%, in fact it is highly preferred that 0.1wt% to 10wt%.Catalyst has the most been made to stand pre-sulfiding step to mix It is the sulfur of 0.05wt.% to 2wt.% based on element.This pre-sulfiding step can fill during catalyst manufactures or by catalyst Carry out after being loaded onto in technical process unit.

Can be in air atmosphere at a temperature of 425 DEG C to 750 DEG C or in another embodiment at 475 DEG C to 600 DEG C At a temperature of by finished product complex calcine 0.5 hour to 10 hours.

Entrance turns the feed stream rich in aromatic compounds of alkylation or disproportionation process and may originate from multiple source, including (but It is not limited to) catalytic reforming；Pyrolysis naphtha, distillation or other hydrocarbon are to produce light olefin and the heavier pair rich in aromatic compounds Product；With catalytic pyrolysis or thermal cracking heavy oil to produce the product in gasoline-range.From pyrolysis or the product of other cracking operations Thing generally will can affect product quality according to the hydrogenated process of well-known process in industry to remove before being loaded to complex Sulfur, alkene and other compounds.Also can hydrocracking light cycle oil is to produce lighter component valuably, these lighter components can be through Catalytic reforming is to produce the feed stream rich in aromatic compounds.If feed stream is catalytic reformate, then can be under high stringency Operation reformer is to realize high aromatics yield and low non-aromatic compound concentration in the product.Reformate is the most favourable Ground stand alkene saturated with remove potential product pollution thing and weight can be aggregated in turning alkylation can not conversion product Material.These process step and are described in US 6, and in 740,788B1, this patent is incorporated by reference.

Enter turn the purest alkylaromatic hydrocarbons that the feed stream of alkylation or disproportionation process can be 6 to 15 carbon atoms, The mixture of these alkylaromatic hydrocarbons or the hydrocarbon part rich in described alkylaromatic hydrocarbons.Feed stream includes formula C₆H_(6-n)R_nAlkane Base aromatic hydrocarbon, wherein n be 1 to 5 integer and R be following in any combination of one or more: CH₃、C₂H₅、C₃H₇、C₄H₉ Or C₅H₁₁.Feed stream may also include benzene and has the aromatic compounds of 2 to 4 rings.Therefore, the suitable ingredients of feed stream is generally wrapped Containing (such as, but be not intended to the present invention) benzene, toluene, ethylo benzene, meta-xylene, ortho-xylene, p-xylene, ethyl-first Benzene, trimethylbenzene, diethyl-benzene, triethylbenzene, propylbenzene, methyl-propyl benzene, ethyl propyl benzene, diisopropyl benzene, butyl Benzene, dihydroindene, naphthalene, tetrahydronaphthalene, decahydronaphthalenes, biphenyl, hexichol and fluorenes.Feed stream also can be containing relatively low non-aromatic of concentration Compound, such as pentane, hexane, heptane and compared with heavy paraffin and methyl cyclopentane, hexamethylene and heavier cycloalkane；At aromatics Pentane and relatively light chain alkane in compound complex are generally removed by before process.Merge to turn alkylation feed preferred Non-aromatic compound containing no more than 10wt%；Preferably the bromine index of alkene is limited to no more than 1000, is preferably no greater than 500。

In one embodiment, the component of raw material is attached most importance to aromatic stream (comprising C9 aromatic compounds), thus Realize toluene and C9 aromatic compounds turns alkylation to produce other dimethylbenzene.Benzene also can be through turning alkylation to produce other first Benzene.Dihydroindene may be present in weight aromatic stream, but it not realizes the high yield of C8 compound product Required component.In one embodiment, C10+ aromatic compounds can also feed 30% or less amount exist.Weight aromatics The aromatic compounds of compound stream preferably containing at least 90 mass %, and may originate from identical or different with benzene and methylbenzene raw material Known refine and petrochemistry method and/or can be by the separation recirculation turning alkylate.

In one embodiment, raw material is turned in the gas phase and in the presence of hydrogen alkylation.If turning alkyl in the liquid phase Change, then hydrogen exist for optional.If exist, then free hydrogen with 0.1 moles/mole Alkylaromatics to 10 moles/rub You are combined with raw material and recirculation hydrocarbon the amount of Alkylaromatics.This ratio of hydrogen and Alkylaromatics be also known as hydrogen with The ratio of hydrocarbon.Turn alkylated reaction and produce the product that C8 aromatic content increases relative to feed stream.Another embodiment party In case, turn alkylated reaction and also produce toluene.

Enter and turn the indirect heat exchange that the charging of alkylation reaction zone generally first passes through with reaction zone effluent and heat, And then by being heated to reaction temperature with the exchange of the stream more warmed, steam or stove.Then making charging by reaction zone, this is anti- Answer district can comprise one or more independent reactor.The charging making merging makes to produce by reaction zone and comprises entering of unconverted Material and the outflow stream of product hydrocarbon.This effluent generally by with enter reaction zone stream carry out indirect heat exchange cool down and Then via using air or cooling water to cool down further.Effluent can be passed through in stripper, the most all existence C5 and relatively lighter hydrocarbons in effluent are all condensed into overhead and are removed by the method.Reclaim the stream rich in aromatic compounds As clean stripper bottom stream, it is referred to herein as turning alkylation effluent.

Turn alkylation or dismutation reaction can contact with the catalytic composite of the present invention with any routine or other convenient manner Realize and type operation in batches or continuously can be included, the most preferably operating continuously.In the reaction zone of vertical type tubular reactor Catalyst can use with fixed bed form, and the Alkylaromatics raw material of load passes through this bed with upper or downward stream mode. The condition employed in alkylation zone that turns generally includes 200 DEG C to 540 DEG C, the temperature of preferably 200 DEG C to 480 DEG C.Turn alkylation Operate under the pressure that district's appropriateness in the range of the width of 100kPa to 6Mpa absolute pressure raises.Turning alkylated reaction can be at wide model The space velocity enclosed (i.e. load volume/volume of catalyst/hour) realizes, and liquid hourly space velocity (LHSV) is generally at 0.1hr-1 to 20hr-1 model In enclosing.

Alkylation effluent will be turned and be divided into light recirculation flow, mixing C8 compound product and weight aromatic compounds material Stream.Mixing C8 compound product can carry for reclaiming p-xylene and other valuable isomers.Light recirculation flow Other purposes (such as benzene and toluene recovery) can be turned to, but another is chosen as partial recirculation to turning alkylation zone.For reclaiming The purposes of benzene, benzene purity is important.Benzene separates generally to be implemented by boiling point in (such as) fractionating column, is the most preferably turning Alkylation effluent is substantially not present boiling point compound (the such as C close to benzene₆And C₇Non-aromatic compound).Benzene purity is with weight Amount % counts by calculating of such as getting off: benzene/(benzene+C₆And C₇Non-aromatic compound).In one embodiment, benzene purity is more than 99%, It is typically larger than 99.3%, preferably greater than 99.5%.Weight aromatic stream contains the most all C9 and heavier aromatic compounds And can partly or entirely be recycled to turn alkylation reaction zone.Generally, can be divided into turning alkylation effluent rich in benzene Stream and one or more remaining mass flow, wherein should comprise at least 99.3wt.% benzene rich in the stream of benzene.

Provide following instance with the explaination present invention and to be not intended as the present invention wide described in claims The excessive restriction of general category.The structure of the UZM-39 zeolite of the present invention is analyzed by x-ray and is measured.Go out given in following instance X-ray pattern use Standard x-ray powder diffraction techniques obtain.Source radiation is the high intensity of operation under 45kV and 35ma X-ray tube.Obtained from the alpha-emitting diffraction pattern of copper K-by computer based proper technology.Compressed flat powder Sample scans under 2 ° to 56 ° (2 θ) continuously.By angstrom in units of interplanar distance (d) obtained by the position (representing with θ) of diffraction maximum , wherein θ is the Bragg angle as observed by digitalized data.Intensity is by true after integrated diffraction peak area subtracting background Fixed, " I_o" it is the intensity at the strongest line or peak, and " I " is the intensity in other peaks each.

As appreciated by one of skill in the art, the mensuration of parameter 2 θ is easily generated artificially and both machine error, this group Conjunction can apply the uncertainty of ± 0.4 ° to each 2 θ values reported.Certainly, this uncertainty is also manifested by by 2 θ values calculating In the report value of d-spacing.This inaccuracy generally exist in this area and be not sufficient to get rid of crystalline material of the present invention each other it Between and with the difference of prior art compositions.In some the x-ray patterns reported, the relative intensity of d-spacing is by respectively Mark vs, s, m and w of representing extremely strong, strong, medium and weak indicate.About 100 × I/I_o, above tag definitions is:

Vw=< 5；W=6-15；M=16-50；S=51-80；And vs=80-100

In some cases, the purity of synthetic product refers to its x-ray powder diffraction pattern and evaluates.It is therefoie, for example, If describing sample is pure sample product, the x-ray pattern of sample to be referred to is without the line produced because of crystalline impurities, rather than does not exist non- Crystal formation material.

Following example are described more fully to explain the present invention.Should be understood that these embodiments only have illustrative and also It is not intended as the excessive restriction to the width category of the present invention described in claims.

Embodiment 1

The sample of UZM-39 is prepared as follows.6.02g NaOH (97%) is dissolved in 125.49g water.By 0.62g Al(OH)₃(29.32wt.%Al) add to NaOH solution to form the first solution.Individually, by 0.24g layered material UZM-8 stirs to 30.0g Ludox AS-40 to form the second solution.Second solution is added to the first solution.Will be mixed Compound is cooled to 0 DEG C-4 DEG C.Individually, by 6.54g Isosorbide-5-Nitrae-dibromobutane (99wt.%) and 7.65g 1-crassitude (97wt.%) mixing is to form the 3rd solution.3rd solution is added to the cooling mixture of the first and second solution with shape Become final reacting mixture.Final reacting mixture it is transferred in 300cc agitated autoclave and stirs at 160 DEG C and 100rpm Lower digestion (digest) 144 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39, as shown in fig. 1. It is 12.64 that analysis result shows that this material has following mol ratio: Si/Al, and Na/Al is 0.116, and N/Al is 0.92, and C/N is 7.23。

Scanning electron microscopy (SEM) display crystal is alternate, and the sudden and violent type square rod form in star, along square face length of side 250nm To 700nm, and aspect ratio is 2:1 to 5:1.Microphotograph is shown in Fig. 7.At 550 DEG C, product is calcined under air 3hr.The XRD figure case of calcined materials is shown in Fig. 2.

Comparative example 2

Follow the preparation of embodiment 1, except for the difference that without layered material UZM-8 in the second solution.At 160 DEG C After stirring 144 hours under 100rpm, it is isolated by filtration product.By XRD, product is identified as analcime.

Comparative example 3

6.68g NaOH (97%) is dissolved in 145.44g water.By 2.86g Al (NO₃)₃·9H₂O (97%) adds extremely Sodium hydroxide solution.13.33g Aerosil 200 is stirred to mixture.Add 13.1g H₂O.Add 7.26g 1,4- Dibromobutane (99%) and 5.84g 1-crassitude (97%) and mixture is stirred vigorously 1 day.By mixture decile and Load to 8 45cc Parr containers and be placed in 160 ° of rotary dryings (rotisserie oven).At one Mixture in Parr container is identified as the material with TUN structure 256 little generations constantly by XRD.Analysis result shows It is 15.51 that this material has following mol ratio: Si/Al, and Na/Al is 0.12, and N/Al is 1.29 and C/N to be 6.89.Sem analysis shows Showing that form is square bar bunch, a length of 300-800nm and aspect ratio are 1.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH under 500 °₄ ⁺Change into H⁺。

To through calcining, through ion exchange sample analysis display 39.2wt.%Si, 2.34wt.%Al, < 0.005wt.%Na and 378m²The BET surface area of/g, 0.220cm³The pore volume of/g and 0.190cm³The micro pore volume of/g.

By the XRD refine of Li Te Wald, the analysis of the H+ form of this material is shown that this material is all by TUN structure class Type forms.Tem analysis confirms not occur the coherent growth of IMF crystal.

Embodiment 4

6.40g NaOH (97%) is dissolved in 111.88g water.By 1.16g Al (OH)₃(29.32wt.%Al) add To produce the first solution to sodium hydroxide solution.Individually, by 0.30g layered material (UZM-8) stirring to 37.5g Ludox To form the second solution in AS-40.Second solution is added to the first solution and is stirred vigorously 1-2 hour.Mixture is cold But to 0 DEG C-4 DEG C.Individually, by 8.18g Isosorbide-5-Nitrae-dibromobutane (99wt.%) and 9.56g 1-crassitude (97wt.%) Mixing is to form the 3rd solution.3rd solution is added to cooling mixture to produce final reacting mixture.It is stirred vigorously Final reacting mixture and being transferred in 300cc agitated autoclave.Under final reacting mixture is stirred at 160 DEG C and 100rpm Digestion 144 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result shows that this material has Following mol ratio: Si/Al is 12.07, and Na/Al is 0.124, and N/Al is 0.90, and C/N is 6.85.

Embodiment 5

7.19g NaOH (99wt.%) is dissolved in 90.1g water.By 1.56g Al (OH)₃(29.32wt.%Al) add Add in sodium hydroxide solution to produce the first solution.Individually, by 0.405g layered material (UZM-8) stirring to 50.62g To form the second solution in Ludox AS-40.Second solution is added to the first solution and is stirred vigorously 1-2 hour.Will be mixed Compound is cooled to 0 DEG C-4 DEG C.Individually, by 11.04g Isosorbide-5-Nitrae-dibromobutane (99wt.%) and 12.90g 1-crassitude (97wt.%) mixing is to form the 3rd solution.3rd solution is added to cooling mixture to produce final reacting mixture. Final reacting mixture is stirred vigorously 5 minutes and is transferred in 300cc agitated autoclave.By final reacting mixture 160 DEG C and the lower digestion of 100rpm stirring 144 hours.It is isolated by filtration 16.5g product.By XRD, product is identified as containing few The UZM-39 of amount MOR impurity.It is 14.14 that analysis result shows that this material has following mol ratio: Si/Al, and Na/Al is 0.16, N/Al is 1.02, and C/N is 7.33.

Embodiment 6

It is dissolved in 600g water to produce sodium hydroxide solution by 37.62g NaOH (97wt.%).By 6.96g Al (OH)₃(29.32 mass %Al) adds to sodium hydroxide solution to produce the first solution.Individually, by 1.80g layered material (UZM-8) stir to 225g Ludox AS-40 to form the second solution.Second solution is added to the first solution and acute Strong stirring 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 49.08g Isosorbide-5-Nitrae-dibromobutane (99wt.%) with 57.36g 1-crassitude (97wt.%) mixes 1-5 minute to form the 3rd solution.3rd solution is added to cooling mixed To produce final reacting mixture in compound.Final reacting mixture it is stirred vigorously 5 minutes and is transferred to 2 liters of agitated autoclave In.Digestion 144 hours under final reacting mixture is stirred at 160 DEG C and 250rpm.It is isolated by filtration product.Pass through XRD Product is identified as UZM-39.It is 11.62 that analysis result shows that this material has following mol ratio: Si/Al, and Na/Al is 0.12, N/Al is 0.88, and C/N is 7.36.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Borrow Help the Li Te Wald XRD refine H to this material⁺The analysis of form provides the result being shown in table 1.

Embodiment 7

505.68g NaOH (99wt.%) is dissolved in 10542g water.By 52.08g Al (OH)₃(29.3wt.%Al) Add to sodium hydroxide solution to produce the first solution.Individually, by 20.16g layered material (UZM-8) stirring to 2520g To form the second solution in Ludox AS-40.Second solution is added to the first solution and is stirred vigorously 1-2 hour.Will be mixed Compound is cooled to 0 DEG C-4 DEG C.Individually, by 549.36g Isosorbide-5-Nitrae-dibromobutane (99wt.%) and 642.6g 1-crassitude (97wt.%) 3-5 minute is mixed to form the 3rd solution.3rd solution is added to cooling mixture to produce end reaction Mixture.Final reacting mixture is stirred vigorously 5 minutes and is pumped in 5 gallons of agitated autoclave.End reaction is mixed Thing is digestion 150 hours under 160 DEG C and 100rpm stirrings.It is isolated by filtration product.By XRD, product is identified as UZM- 39.Analysis result shows that this material has a following mol ratio: Si/Al=13.35, Na/Al=0.087, N/Al=0.96, C/N =7.12.

Embodiment 8

Follow the preparation of embodiment 4, except for the difference that substitute UZM-8 with 0.30g UZM-26.By XRD, product is identified as UZM-39.Analysis result shows that this material has a following mol ratio: Si/Al=12.88, Na/Al=0.25, N/Al=0.88, C/N=7.31.

Embodiment 9

It is dissolved in 111.88g water to produce sodium hydroxide solution by 6.27g NaOH (99%).By 1.16g Al (OH)₃ (29.32 mass %Al) adds to sodium hydroxide solution to produce the first solution.37.5g Ludox AS-40 is added to the In one solution, and then add 0.22g layered material UZM-5.First solution is stirred vigorously 1-2 hour.By cold for the first solution But to 0 DEG C-4 DEG C.Individually, 8.18g Isosorbide-5-Nitrae-dibromobutane (99%) is mixed 1-with 9.56g 1-crassitude (97%) 5 minutes to form the second solution.Second solution is added to the first solution of cooling to produce final reacting mixture.Will be End reaction mixture is stirred vigorously 5 minutes and is transferred in 300cc agitated autoclave.By final reacting mixture at 160 DEG C and The lower digestion of 100rpm stirring 144 hours.It is isolated by filtration product.By XRD, product is identified as containing few EUO or NES The UZM-39 of pollutant.

Comparative example 10

This embodiment is the same as in Example 4, except for the difference that substitutes UZM-8 with 0.30g UZM-39.Product is identified as comprising The compositions of MTW, UZM-39, ANA and MOR.

Embodiment 11

6.27g NaOH (97wt.%) is dissolved in 111.88g water.By 1.16g Al (OH)₃(29.32wt.%Al) Add to sodium hydroxide solution to produce the first solution.Individually, by 0.30g layered material (UZM-8) stirring to 37.5g To form the second solution in Ludox AS-40.Second solution is added to the first solution and is stirred vigorously 1-2 hour.Will be mixed Compound is cooled to 0 DEG C-4 DEG C.Individually, by 12.27g Isosorbide-5-Nitrae-dibromobutane (99wt.%) and 14.34g 1-crassitude (97wt.%) mixing is to form the 3rd solution.3rd solution is added to cooling mixture to produce final reacting mixture. It is stirred vigorously final reacting mixture and is transferred in 300cc agitated autoclave.By final reacting mixture at 160 DEG C and The lower digestion of 100rpm stirring 144 hours.It is isolated by filtration product.By XRD, product is identified as the UZM-containing ESV impurity 39.Analysis result shows that this material has a following mol ratio: Si/Al=13.17, Na/Al=0.126, N/Al=1.03, C/N =7.22.

Embodiment 12

Follow the program of embodiment 4, except for the difference that substitute 9.56g 1-first by 8.05g dimethylethyl amine (97wt.%) Base pyrrolidine (97wt.%).Product is identified as comprising the compositions of modenite and UZM-39.

Embodiment 13

6.27g NaOH (99wt.%) is dissolved in 111.88g water.By 1.16g Al (OH)₃(29.32wt.%Al) Add to sodium hydroxide solution to produce the first solution.0.30g layered material UZM-8 and 37.5g Ludox AS-40 is added Add in the first solution.First solution is stirred vigorously 1-2 hour.First solution is cooled to 0 DEG C-4 DEG C.Individually, will 4.02g dimethylethyl amine (97wt%) mixes 1-2 minute to form amine aqueous solution with 4.78g 1-crassitude (97wt%). 8.18g 1,4-dibromobutane (99wt.%) is added to amine aqueous solution and then mixes 1-2 minute to form the second solution.Will Second solution adds to the first solution of cooling to produce final reacting mixture.Final reacting mixture is stirred vigorously 5 Minute and be transferred in 300cc agitated autoclave.Under being stirred at 160 DEG C and 100rpm by final reacting mixture, digestion 192 is little Time.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result shows that this material has following mole Ratio: Si/Al=12.42, Na/Al=0.175, N/Al=0.91, C/N=6.92.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Analysis display 38.7%Si, 2.97%Al, 0.0089%Na and the 375m of the sample exchanged through calcining, through ion²The BET of/g Surface area, 0.238cm³The pore volume of/g and 0.184cm³The micro pore volume of/g.By the XRD refine of Li Te Wald to this material H⁺The analysis of form provides the result being shown in table 1.

Embodiment 14

It is dissolved in 111.88g water to produce sodium hydroxide solution by 6.21g NaOH (99%).By 1.16g Al (OH)₃ (29.32wt.%Al) add to sodium hydroxide solution to produce the first solution.By 0.30g layered material (UZM-8) and 37.5g Ludox AS-40 adds to the first solution.First solution is stirred vigorously 1-2 hour.First solution is cooled to 0 ℃-4℃.Individually, 8.18g Isosorbide-5-Nitrae-dibromobutane (99wt.%) is mixed with 9.56g 1-crassitude (97wt.%) 1-5 minute to form the second solution.Second solution is added to the first solution of cooling to produce final reacting mixture.Will Final reacting mixture is stirred vigorously 5 minutes and is transferred in 300cc agitated autoclave.By final reacting mixture at 170 DEG C Digestion lower with 100rpm stirring 96 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result Show this material have following mol ratio: Si/Al be 12.76, Na/Al be 0.116, N/Al be 0.94, C/N is 6.98.

Embodiment 15

It is dissolved in 111.88g water to produce sodium hydroxide solution by 6.21g NaOH (99%).By 1.16g Al (OH)₃ (29.32wt.%Al) add to sodium hydroxide solution to produce the first solution.By 0.30g layered material (UZM-8) and 37.5g Ludox AS-40 adds to the first solution.First solution is stirred vigorously 1-2 hour.First solution is cooled to 0 ℃-4℃.Individually, 8.18g Isosorbide-5-Nitrae-dibromobutane (99wt.%) is mixed with 9.56g 1-crassitude (97wt.%) 1-5 minute to form the second solution.Second solution is added to the first solution of cooling to produce final reacting mixture.Will Final reacting mixture is stirred vigorously 5 minutes and is transferred in 300cc agitated autoclave.By final reacting mixture at 175 DEG C Digestion lower with 100rpm stirring 44 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result Show this material have following mol ratio: Si/Al be 12.97, Na/Al be 0.20, N/Al be 0.95, C/N is 6.98.

Embodiment 16

5.96g NaOH (97%) and 0.25g KOH (86%) is dissolved in 111.88g water.By 1.22g Al (OH)₃ (27.9wt.%Al) add to sodium hydroxide solution.37.5g Ludox AS-40 is added to the first solution, and then Add 0.30g layered material UZM-8 and be stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 8.18g 1,4-dibromobutane (99%) mixes with 9.56g 1-crassitude (97%) to form the 3rd mixture.By the 3rd mixture Add to cooling mixture to produce final reacting mixture.It is stirred vigorously final reacting mixture and is transferred to 300cc and stirs Mix in autoclave.Digestion 144 hours under final reacting mixture is stirred at 160 DEG C and 100rpm.It is isolated by filtration product. By XRD, product is identified as UZM-39.X-ray diffraction pattern is shown in Fig. 3.It is following that analysis result shows that this material has Mol ratio: Si/Al is 11.69, and Na/Al is 0.137, and K/Al is 0.024, and N/Al is 0.848, and C/N is 7.16.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Through calcining, through ion exchange sample analysis display 39.4%Si, 3.23%Al, 0.011%Na, 0.005%K and 362m²The BET surface area of/g, 0.231cm³The pore volume of/g and 0.176cm³The micro pore volume of/g.X-ray diffraction pattern shows In Fig. 4.

Embodiment 17

5.96g NaOH (99%) and 0.50g KOH (86%) is dissolved in 111.88g water.By 1.16g Al (OH)₃ (29.32wt.%Al) add to sodium hydroxide solution.37.5g Ludox AS-40 is added to the first solution, and then Add 0.30g layered material UZM-8 and be stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 4.09g 1,4-dibromobutane (99%) mixes with 11.15g 1-crassitude (97%) to form the 3rd mixture.Mix the 3rd Thing adds to cooling mixture to produce final reacting mixture.It is stirred vigorously final reacting mixture and is transferred to 300cc In agitated autoclave.Digestion 144 hours under final reacting mixture is stirred at 160 DEG C and 100rpm.It is isolated by filtration product Thing.By XRD, product is identified as UZM-39.It is 11.98 that analysis result shows that this material has following mol ratio: Si/Al, Na/Al is 0.114, and K/Al is 0.0375, and N/Al is 0.84, and C/N is 7.50.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Analysis display 37.7%Si, 3.01%Al, 0.012%Na, the 0.006%K of the sample exchanged through calcining, through ion.By inner The special Wald XRD refine H to this material⁺The analysis of form provides the result being shown in table 1.Tem analysis display UZM-39 For TUN and the IMF zeolite type composite construction of coherent growth, the result of this analysis is shown in Figure 10 and Figure 11.

Embodiment 18

5.64g NaOH (97%) and 1.00g KOH (86%) is dissolved in 111.88g water.By 1.22g Al (OH)₃ (27.9wt.%Al) add to sodium hydroxide solution.37.5g Ludox AS-40 is added to the first solution, and then Add 0.30g layered material UZM-8 and be stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 8.18g 1,4-dibromobutane (99%) mixes with 9.56g 1-crassitude (97%) to form the 3rd mixture.By the 3rd mixture Add to cooling mixture to produce final reacting mixture.It is stirred vigorously final reacting mixture and is transferred to 300cc and stirs Mix in autoclave.Digestion 144 hours under final reacting mixture is stirred at 160 DEG C and 100rpm.It is isolated by filtration product. By XRD, product is identified as UZM-39.It is 11.29, Na/Al that analysis result shows that this material has following mol ratio: Si/Al Being 0.078, K/Al is 0.053, and N/Al is 0.88, and C/N is 6.92.The SEM image display of product is in Fig. 8.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Through calcining, through ion exchange sample analysis display 42.6%Si, 3.65%Al, 0.0018%Na, 0.02%K and 351m²The BET surface area of/g, 0.218cm³The pore volume of/g and 0.170cm³The micro pore volume of/g.By Li Te Wald XRD The refine H to this material⁺The analysis of form provides the result being shown in table 1.

Embodiment 19

5.02g NaOH (97%) and 2.00g KOH (86%) is dissolved in 111.88g water.By 1.22g Al (OH)₃ (27.9wt.%Al) add to sodium hydroxide solution.37.5g Ludox AS-40 is added to the first solution, and then Add 0.30g layered material UZM-8 and be stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 8.18g 1,4-dibromobutane (99%) mixes with 9.56g 1-crassitude (97%) to form the 3rd mixture.By the 3rd mixture Add to cooling mixture to produce final reacting mixture.It is stirred vigorously final reacting mixture and is transferred to 300cc and stirs Mix in autoclave.Digestion 136 hours under final reacting mixture is stirred at 160 DEG C and 100rpm.It is isolated by filtration product. Being identified as by product by XRD may be containing the UZM-39 of a small amount of NES pollutant.Analysis result shows that this material has following rubbing You compare: Si/Al is 10.99, and Na/Al is 0.088, and K/Al is 0.11, and N/Al is 0.84, and C/N is 7.36.

Embodiment 20

5.96g NaOH (99%) is dissolved in 111.88g water.By 1.22g Al (OH)₃(27.9wt.%Al) add To sodium hydroxide solution.The most in the listed order by 0.24g Mg (OH)₂(95%), 37.5g Ludox AS-40 and 0.30g layered material UZM-8 adds to the first solution and is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Single Solely, 8.18g Isosorbide-5-Nitrae-dibromobutane (99%) mixed with 9.56g 1-crassitude (97%) and add to cooling down mixing To produce final reacting mixture in thing.It is stirred vigorously final reacting mixture and is transferred in 300cc agitated autoclave.Will be End reaction mixture is digestion 144 hours under 160 DEG C and 100rpm stirrings.It is isolated by filtration product.By XRD, product is known Wei UZM-39.It is 12.12 that analysis result shows that this material has following mol ratio: Si/Al, and Na/Al is 0.148, and Mg/Al is 0.38, N/Al is 0.91, and C/N is 6.96.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Through calcining, through ion exchange sample analysis display 39.6%Si, 2.99%Al, 83ppm Na, 0.14%Mg and 351m²The BET surface area of/g, 0.218cm³The pore volume of/g and 0.170cm³The micro pore volume of/g.

Embodiment 21

By 5.96g NaOH (99%) and 0.51g La (OH)₃(99.9%) it is dissolved in 111.88g water.By 1.16g Al (OH)₃(29.32wt.%Al) add to sodium hydroxide solution.37.5g Ludox AS-40 is added to the first solution, And then add 0.30g layered material UZM-8 and be stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, will 8.18g 1,4-dibromobutane (99%) and 9.56g 1-crassitude (97%) mix and add to cooling mixture in Produce final reacting mixture.It is stirred vigorously final reacting mixture and is transferred in 300cc agitated autoclave.By end reaction Mixture is digestion 168 hours under 160 DEG C and 100rpm stirrings.It is isolated by filtration product.By XRD, product is identified as UZM-39.It is 12.22 that analysis result shows that this material has following mol ratio: Si/Al, and Na/Al is 0.20, and La/Al is 0.18, N/Al is 0.89, and C/N is 7.13.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 4 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Through calcining, through ion exchange sample analysis display 39.1%Si, 3.06%Al, 60ppm Na, 0.25%La and 335m²The BET surface area of/g, 0.226cm³The pore volume of/g and 0.163cm³The micro pore volume of/g.

Embodiment 22

3.14g NaOH (97%) is dissolved in 106.41g water.By 1.16g Al (OH)₃(29.32wt.%Al) add To sodium hydroxide solution.37.5g Ludox AS-40 is added to the first solution, and then adds 0.30g layered material UZM-8.Subsequently by 26.7g sodium silicate solution (13.2wt.%Si；6.76wt.%Na) add in thing mixed above and acutely Stir 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 8.18g Isosorbide-5-Nitrae-dibromobutane (99%) and 9.56g 1- Crassitude (97%) mixes to form the 3rd mixture.3rd mixture is added to cooling mixture final to produce Reactant mixture.It is stirred vigorously final reacting mixture and is transferred in 300cc agitated autoclave.Final reacting mixture is existed Digestion 224 hours under 160 DEG C and 100rpm stirrings.It is isolated by filtration product.By XRD, product is identified as UZM-39.Point Analysis result show this material have following mol ratio: Si/Al be 11.75, Na/Al be 0.11, N/Al be 0.90, C/N is 6.99.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 3 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Right Analysis display 38.8%Si, 3.05%Al, 0.011%Na and the 364m of the sample exchanged through calcining, through ion²The BET of/g Surface area, 0.273cm³The pore volume of/g and 0.174cm³The micro pore volume of/g.By the XRD refine of Li Te Wald to this material H⁺The analysis of form provides the result being shown in table 1.

Embodiment 23

5.33g NaOH (99%) is dissolved in 111.88g water.By 1.16g Al (OH)₃(29.32wt.%Al) add To sodium hydroxide solution.Individually, will 0.30g β zeolite stirring to 37.5g Ludox AS-40 mix with manufacture second Thing.This second mixture is added to the first solution and is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually Ground, mixes with 9.56g 1-crassitude (97%) to form the 3rd mixture by 8.89g pentamethylene bromide (97%). 3rd mixture is added to cooling mixture to produce final reacting mixture.It is stirred vigorously final reacting mixture and turns Move in 300cc agitated autoclave.Digestion 256 hours under final reacting mixture is stirred at 160 DEG C and 100rpm.By mistake Filter separates product.By XRD, product is identified as UZM-39.Analysis result shows that this material has following mol ratio: Si/Al and is 13.24, Na/Al be 0.13, N/Al be 0.91, C/N is 7.21.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 3 secondary ion exchanges, calcines 2 hours subsequently under air with by NH at 500 DEG C₄ ⁺Change into H⁺.Borrow Help the Li Te Wald XRD refine H to this material⁺The analysis of form provides the result being shown in table 1.

Comparative example 24

While stirring, 10.8g Aerosil 200 is added to double (the N-crassitude of 12.24g 1,5-) two Bromo pentane silane is in 114g H₂Solution in O.Form the thickest gel.Individually, by 60g H₂O, 3.69g NaOH (99%), 0.95g Sodium aluminate (by analyzing as 26.1%Al) and 1.86g NaBr (99%) manufacture solution.This second solution is added to above mixed In compound, this mixture is the most thinning.Final mixture is aliquoted between 7 45cc Parr containers.One container is existed At 170 DEG C in 15rpm rotary drying digestion 12 days, produce the product by XRD determining with IMF structure.By filtering Separate product.Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then by it under 75 ° Carry out 4 secondary ion exchanges with 1M ammonium nitrate solution, under 500 °, calcine 2 hours subsequently under air with by NH₄ ⁺Change into H⁺.Borrow Help the Li Te Wald XRD refine H to this material⁺The analysis of form shows that this material is all made up of IMF structure type.TEM It is analyzed to identify the coherent growth that TUN crystal does not occurs.

Embodiment 25

31.98g NaOH (99%) is dissolved in 671.3g water.By 6.96g Al (OH)₃(29.32wt.%Al) add To sodium hydroxide solution.Individually, stir to 225.0g Ludox AS-40 to manufacture by 1.80g layered material UZM-8 Second mixture.This second mixture is added to the first solution and is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C- 4℃.Individually, mix 53.34g pentamethylene bromide (97%) with 57.36g 1-crassitude (97%) to form Three mixture.3rd mixture is added to cooling mixture to produce final reacting mixture.It is stirred vigorously end reaction Mixture and being transferred in 2L agitated autoclave.Under being stirred at 160 DEG C and 250rpm by final reacting mixture, digestion 256 is little Time.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result shows that this material has following mole Ratio: Si/Al is 12.30, Na/Al is 0.13, N/Al is 0.92, and C/N is 7.51.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then under 75 ° by its with 1M ammonium nitrate solution carries out 3 secondary ion exchanges, calcines 2 hours subsequently under air with by NH under 500 °₄ ⁺Change into H⁺.To warp Calcining, analysis display 39.0%Si, 2.93%Al, 0.008%Na of the sample exchanged through ion.By Li Te Wald XRD The refine H to this material⁺The analysis of form provides the result being shown in table 1.

Embodiment 26

5.76g NaOH (97%) is dissolved in 111.88g water.By 1.22g Al (OH)₃(27.9wt.%Al) add To sodium hydroxide solution.When this mixture becomes solution, add 37.5g Ludox AS-40.Add 0.30g layering subsequently Material UZM-8.Mixture is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 0.89g 1,5-bis- Bromo pentane silane (97%) mixes with 7.36g Isosorbide-5-Nitrae-dibromobutane (99%), then add 9.56g 1-crassitude (97%) with Form the second mixture.Second mixture is added to cooling mixture to produce final reacting mixture.It is stirred vigorously End reaction mixture and being transferred in 300cc agitated autoclave.Soak under final reacting mixture is stirred at 160 DEG C and 100rpm Boil 176 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result show this material have with Lower mol ratio: Si/Al is 12.15, Na/Al is 0.15, N/Al is 0.90, and C/N is 7.59.

At 600 DEG C, the product synthetically produced by this is calcined 6 hours under moving air.Then by it at 75 DEG C Carry out 4 secondary ion exchanges with 1M ammonium nitrate solution, at 500 DEG C, calcine 2 hours subsequently under air with by NH₄ ⁺Change into H⁺。 Analysis display 38.6%Si, 2.85%Al, < 0.01%Na to the sample exchanged through calcining, through ion.By Li Te Wald The XRD refine H to this material⁺The analysis of form provides the result being shown in table 1.

Embodiment 27

5.76g NaOH (97%) is dissolved in 111.88g water.By 1.22g Al (OH)₃(27.9wt.%Al) add To sodium hydroxide solution.When this mixture becomes solution, add 37.5g Ludox AS-40.Subsequently, add 0.30g to divide Layer material UZM-8 and mixture is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 1.78g 1, Pentamethylene bromide (97%) mixes with 6.54g Isosorbide-5-Nitrae-dibromobutane (99%), then adds 9.56g 1-crassitude (97%) to form the second mixture.Second mixture is added to cooling mixture to produce final reacting mixture.Acute Strong stirring final reacting mixture and being transferred in 300cc agitated autoclave.By final reacting mixture at 160 DEG C and 100rpm The lower digestion of stirring 176 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result shows this material Material have following mol ratio: Si/Al be 12.24, Na/Al be 0.107, N/Al be 0.93, C/N is 6.91.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then by it at 75 DEG C Carry out 4 secondary ion exchanges with 1M ammonium nitrate solution, at 500 DEG C, calcine 2 hours subsequently under air with by NH₄ ⁺Change into H⁺。 Analysis display 38.7%Si, 2.98%Al, 158ppm Na and 333m to the sample exchanged through calcining, through ion²/ g's BET surface area, 0.201cm³The pore volume of/g and 0.164cm³The micro pore volume of/g.By the XRD refine of Li Te Wald to this material The H of material⁺The analysis of form provides the result being shown in table 1.

Embodiment 28

5.76g NaOH (97%) is dissolved in 111.88g water.By 1.22g Al (OH)₃(27.9wt.%Al) add To sodium hydroxide solution.When this mixture becomes solution, add 37.5g Ludox AS-40.Subsequently, add 0.30g to divide Layer material UZM-8 and mixture is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 2.67g 1, Pentamethylene bromide (97%) mixes with 5.73g Isosorbide-5-Nitrae-dibromobutane (99%), then adds 9.56g 1-crassitude (97%) to form the second mixture.Second mixture is added to cooling mixture to produce final reacting mixture.Acute Strong stirring final reacting mixture and being transferred in 300cc agitated autoclave.By final reacting mixture at 160 DEG C and 100rpm The lower digestion of stirring 176 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.X-ray diffraction pattern shows Shown in Figure 5.It is 12.15 that analysis result shows that this material has following mol ratio: Si/Al, and Na/Al is 0.108, and N/Al is 0.86, C/N is 7.68.

At 600 DEG C, the product synthetically produced by this is calcined 6 hours under moving air.Then by it at 75 DEG C Carry out 4 secondary ion exchanges with 1M ammonium nitrate solution, under 500 °, calcine 2 hours subsequently under air with by NH₄ ⁺Change into H⁺.Right Analysis display 38.7%Si, 2.98%Al, 79ppm Na of the sample exchanged through calcining, through ion.X-ray diffraction pattern shows In Fig. 6.By the Li Te Wald XRD refine H to this material⁺The analysis of form provides the result being shown in table 1.

Embodiment 29

5.80g NaOH (97%) is dissolved in 111.88g water.By 1.16g Al (OH)₃(29.32wt.%Al) add To sodium hydroxide solution.When this mixture becomes solution, add 37.5g Ludox AS-40.Subsequently, add 0.30g to divide Layer material UZM-8 and mixture is stirred vigorously 1-2 hour.Mixture is cooled to 0 DEG C-4 DEG C.Individually, by 4.45g 1, Pentamethylene bromide (97%) mixes with 4.09g Isosorbide-5-Nitrae-dibromobutane (99%), then adds 9.56g 1-crassitude (97%) to form the second mixture.Second mixture is added to cooling mixture to produce final reacting mixture.Acute Strong stirring final reacting mixture and being transferred in 300cc agitated autoclave.By final reacting mixture at 160 DEG C and 100rpm The lower digestion of stirring 224 hours.It is isolated by filtration product.By XRD, product is identified as UZM-39.Analysis result shows this material Material have following mol ratio: Si/Al be 11.75, Na/Al be 0.13, N/Al be 0.86, C/N is 7.59.

Under 600 °, the product synthetically produced by this is calcined 6 hours under moving air.Then by it at 75 DEG C Carry out 4 secondary ion exchanges with 1M ammonium nitrate solution, at 500 DEG C, calcine 2 hours subsequently under air with by NH₄ ⁺Change into H⁺。 Analysis display 40.1%Si, 3.32%Al, 90ppm Na and 305m to the sample exchanged through calcining, through ion²The BET of/g Surface area, 0.224cm³The pore volume of/g and 0.146cm³The micro pore volume of/g.By the XRD refine of Li Te Wald to this material H⁺The analysis of form provides the result being shown in table 1.

Table 1

Embodiment is numbered	TUN%	IMF%
			3	100	0
6	95	5
			13	83	17
17	46	54
			18	36.5	63.5
23	24	76
			24	0	100
25	19	81
			26	58	42
27	30	70
			28	13	87
29	8	92

Embodiment 30

For determining the amount of TUN or the IMF structure that can detect in UZM-39 coherent growth sandwich, implement inspection Survey limit research.Use JADE XRD analysis software (purchased from Materials Data group) by viewed embodiment 3 He The H of embodiment 24 product⁺The diffraction pattern of form electronically produces a series of simulated diffraction pattern.Mixture content is 1% to 99%TUN and being produced by following: components in certain proportion smaller for percentage is amplified to desired content, adds pattern And preserve composite pattern.

10% or the more large content of IMF's that can quantify in UZM-39 coherent growth composite construction analyzed in Li Te Wald Content, but, actually in the sample (Figure 12) being mainly made up of TUN, 5% can be measured by the peak intensity that d-spacing is 9.46A Or the IMF that more large content of percentage ratio is little, and other peaks traceable under high level, in particular, for example in 11.4A d-spacing The peak that place increases.In fig. 12, spectrum 1 is 1%IMF, 99%TUN；Spectrum 2 is about 3%IMF, 97%TUN；Spectrum 3 is about 5%IMF, 95%TUN；And spectrum 4 is about 10%IMF, 90%TUN.

10% or the more large content of TUN's that can quantify in UZM-39 coherent growth composite construction analyzed in Li Te Wald Content, but, Figure 13 shows, it practice, can be seen by the peak intensity that d-spacing is 12.25A in the sample being mainly made up of IMF Observe the TUN that 5% or more large content of percentage ratio is little, and other peaks the most traceable, in particular, for example at 9.63A At d-spacing increase peak.In fig. 13, spectrum 1 is about 1%TUN, 99%IMF；Spectrum 2 is about 3%TUN, 97%IMF； Spectrum 3 is about 5%TUN, 95%IMF；And spectrum 4 is about 10%TUN, 90%IMF.

Embodiment 31

44.9g NaOH (97%) is dissolved in 1122.3g water.10.8g liquid sodium aluminate is added in this solution (22.9%Al₂O₃, 20.2%Na₂O), 105.9g Ultrasil VN3 (90%SiO is then added₂, purchased from Evonik) and with shape Become the first mixture.Individually, combination 53.5g Isosorbide-5-Nitrae-dibromobutane (99%) and 62.6g 1-crassitude (97%) with Form the second mixture.Second mixture is added to the first mixture to produce final reacting mixture.Finally, 1g is added Layered material UZM-8 and being stirred vigorously 1-2 hour by mixture, is then transferred in 2L agitated autoclave.End reaction is mixed Compound is digestion 7 days under 160 DEG C and 200rpm stirrings.It is isolated by filtration product and is identified as UZM-39 by XRD.Analyze knot Fruit show this material have following mol ratio: Si/Al be 12.40, Na/Al be 0.21, N/Al be 1.10, C/N is 7.06.

Embodiment 32

Combination NaOH, Al (OH)₃、Ga(NO3)3·9H₂O, Ludox AS-40,1,4-dibromobutane, 1-crassitude, Water and layered material UZM-8 consist of 0.5Al to be formed₂O₃:0.5Ga₂O₃:65.4SiO₂:24.6Na₂O:9.9C₄Br₂:29.41- MP:2636H₂The mixture of O and being stirred vigorously 1-2 hour, is then transferred in 2L agitated autoclave.By final reacting mixture Digestion 150 hours under stirring at 160 DEG C and 250rpm.It is isolated by filtration product and is identified as UZM-39 by XRD.Analyze knot It is 21.61 that fruit shows that this material has following mol ratio: Si/Al, and Si/Ga is 31.35, and Si/ (Al+Ga) is 12.79, Na/ (Al + Ga) it is 0.10, N/ (Al+Ga) is 0.91, and C/N is 7.39.

Embodiment 33

The UZM-39 containing a large amount of TUN and a small amount of IMF in H+ form is loaded to vertical type steam generator (steamer) in.At 725 DEG C, UZM-39 is exposed in 100% steam 12 hours or 24 hours.Initial UZM-39 has 385m²The BET surface area of/g, 0.248cm³The pore volume of/g and 0.180cm³The micro pore volume of/g.After steam processes 12 hours, This UZM-39 is identified as UZM-39 yet by XRD, but the intensity at front 5 peaks increases to strong, strong, extremely strong, strong and medium the most respectively. Every other peak is respectively provided with the position described in table B and intensity.This material has 331m²The BET surface area of/g, 0.243cm³/g Pore volume and 0.151cm³The micro pore volume of/g.After steam processes 24 hours, this UZM-39 is identified as UZM-yet by XRD 39, but the intensity at front 5 peaks increases to medium-strong, strong, strong, medium-strong and medium the most respectively.Every other peak is respectively provided with table B Described in position and intensity.This material has 327m²The BET surface area of/g, 0.241cm³The pore volume of/g and 0.150cm³/g Micro pore volume.

Embodiment 34

The UZM-39 containing a large amount of TUN and a small amount of IMF in H+ form is placed in containing 6N HNO₃And condensation has been installed In the round-bottomed flask of device and agitator.Will be containing UZM-39 and HNO₃Mixture boil 8h or 16h under reflux.Filter gained Material, washs and is dried.XRD analysis shows that this material is the UZM-39 consistent with table B.

Embodiment 35

By the method synthesis UZM-14 described in US 7,687,423.After carrying out ion exchange with ammonium nitrate solution, Zeolite it is dried at a temperature of 100 DEG C.UZM-14 is made to be shaped to catalyst (hereinafter referred to as catalyst the most in the following manner A): the mixture of mixing 75%UZM-14 and 25% peptization Catapal B boehmite has 5% with Ammoniun Heptamolybdate Solution to obtain The catalyst preparation agent of molybdenum.In extrusion 1/16 " after cylinder, by catalyst calcination 2 hours: 540 DEG C under following 2 kinds of different conditions With 15% steam, and 580 DEG C with 0% steam.

Catalyst (hereinafter referred to as catalyst B) containing UZM-39 is prepared by same program, and substitutes three with UZM-39 The UZM-14 of/mono-has the catalysis of 5%Mo on the carrier of 50%UZM-14/25%UZM-39/25%Al2O3 to obtain Agent.

Then these catalyst are used to make toluene and C9+ aromatic compounds turn alkylation by Standard test programme.Institute in table 2 The feed composition of display contains 75wt% toluene and 25wt%C9+ aromatic compounds, and test is at 1725kPa (250psig) Reactor pressure, weight (hourly) space velocity (WHSV)=4 and H₂: implement under HC=6.By making for initial 40 hours in test in test cell Charging carrys out sulphurized catalyst with excess dimethyl disulfide (150ppm) doping.S/Mo mol ratio on dead catalyst generally exists In the range of 0.6-0.9.Under 4 different temperatures, collect data and be reported in table 3.

Table 2

Component	Weight %
		Toluene	75
Propylbenzene	2
		Ethyl methyl benzene	10
Trimethylbenzene	9.7
		Dihydroindene	0.8
Methyl-propyl benzene	1.0
		Diethylbenzene	0.4
Dimethyl ethyl benzene	1.0
		C11⁺Aromatic compounds	0.1

Table 3

Figure 14 shows for catalyst A (hollow triangle) and catalyst B (solid squares), two kinds of calcinings (540 DEG C with 15% steam (solid line) and 580 DEG C and 0% steam (dotted line)) under, the curve that benzene purity changes with toluene conversion.As by implementing Example is visible, and the catalyst containing UZM-39 Yu UZM-14 in catalytic composite has increased the conversion ratio of ethyl methyl benzene (MEB), Under equivalent conversion rate, improve dimethylbenzene productivity, and under equivalent conversion rate, improve benzene purity.

Embodiment 36

Loading before catalysis test device, suppressing 250mg height TUN content H⁺-UZM-39 and be sieved into 40-60 Mesh.At 50mL/min N₂Under stream, catalytic composite is heated to 550 DEG C and keeps 60min.Then device is cooled to 400 DEG C, will feed by N subsequently₂The N saturated through toluene of conversion extremely identical flow velocity₂.At a temperature in the range of 400 DEG C to 550 DEG C in fact Execute toluene and turn alkylation.Then SiO is used₂/Al₂O₃The mol ratio MFI zeolite equal to 38 repeats experiment.

Table 4

Claims

1. one kind makes to comprise C₇、C₉、C₁₀And C₁₁The charging circulation alkylation of one or more in+aromatic compounds is to obtain C₈ The method turning alkylate stream that aromatic compounds substrate concentration increases relative to this feed stream, it includes making this feed stream turn Contact with selected from following catalyst under alkylation conditions:

A) include the catalyst of TUN and the IMF zeolite type complex of coherent growth, in post synthesis former state and anhydrous on the basis of, should Catalyst has at least AlO₂And SiO₂Three-dimensional framework and the experience represented by following empirical formula of tetrahedron element form:

Na_nM_m ^k+T_tAl_1-xE_xSi_yO_z

Wherein " n " be Na with the mol ratio of (Al+E) and have 0.05 to 0.5 value, M represents that at least one is selected from following gold Belonging to: zinc, the 1st race, the 2nd race, the 3rd race and the lanthanide series of IUPAC periodic chart and any combination thereof, " m " is M and the rubbing of (Al+E) You compare and have the value of 0 to 0.5, and " k " is the mean charge of metal M, and T is the Organic structure directing agent being derived from reactant R and Q, Wherein R is the α with 3 to 6 carbon atoms, the substituted alkane of ω-two halogen, and Q is that at least one has 6 or less carbon is former The neutral monoamine of son, " t " be from the N of this Organic structure directing agent and the mol ratio of (Al+E) and to have 0.5 to 1.5 Value, E is the element of group that choosing free gallium, ferrum, boron and combinations thereof form, " x " be the molar fraction of E and have 0 to 1.0 value, " y " is Si and the mol ratio of (Al+E) and by more than 9 to 25 changes, and " z " be O with the mol ratio of (Al+E) and have by with The value that lower equation determines:

Z=(n+k m+3+4 y)/2

And it is characterized in that it has the TUN region of coherence arrangement and IMF region so that [010]_TUNCrystal zone axis and [001]_IMF Crystal zone axis is parallel to each other and makes (002)_TUNType and (060)_IMFType crystal face has seriality, wherein indexing relate separately to TUN and Monocline C of IMF_2/mWith tiltedly side C_mcmStructure cell；

B) include the catalyst of TUN and the IMF zeolite type complex of coherent growth, calcining, ion exchange and calcining after and On the basis of anhydrous, this catalyst has at least AlO₂And SiO₂The three-dimensional framework of tetrahedron element and being represented by following empirical formula Experience composition in hydrogen form:

M1_a ^N+Al_(l-x)E_xSi_y’O_z”

And wherein M1 is that at least one is selected from following exchangeable cations: alkali metal, alkaline-earth metal, rare earth metal, zinc, ammonium from Son, hydrion and combinations thereof, " a " is M1 and the mol ratio of (Al+E) and by 0.05 to 50 change, and " N " is the weighted average of M1 Conjunction valency and have+1 to+3 value, E is the element of group that choosing free gallium, ferrum, boron and combinations thereof form, and " x " is the molar fraction of E And by 0 to 1.0 change, y ' be Si with the mol ratio of (Al+E) and by more than 9 to the purest silicon dioxide change, and z " be The mol ratio of O and (Al+E) and be there is the value determined by below equation:

Z "=(a N+3+4 y ')/2

And it is characterized in that it has the TUN region of coherence arrangement and IMF region so that being somebody's turn to do [010]_TUNCrystal zone axis with should [001]_IMFCrystal zone axis is parallel to each other and makes (002)_TUNType and (060)_IMFType crystal face has seriality, and wherein this indexing is respectively Relate to monocline C of TUN and IMF_2/mWith tiltedly side C_mcmStructure cell；

And c) a combination thereof.

Method the most according to claim 1, wherein being further characterized by it there is x-ray diffraction pattern of this catalyst a), This x-ray diffraction pattern at least has in Table A 1 listed d-spacing and intensity:

Table A 1

* the complex spike being made up of multiple overlapping reflections

And being further characterized by it there is x-ray diffraction pattern of catalyst b), this x-ray diffraction pattern at least has table B1 D-spacing listed by and intensity:

Table B1

* the complex spike being made up of multiple overlapping reflections.

Method the most according to claim 1, wherein TUN and the IMF zeolite type complex of this coherent growth has and accounts for total pore volume Percentage ratio more than 60% micro pore volume.

Method the most according to claim 1, wherein this feed stream comprises selected from following component further: benzene, C₈Aromatic compounds Thing, the aromatic compounds with 2 to 4 rings and combinations thereof.

Method the most according to claim 1, wherein this feed stream comprises freely to turn the C of alkylate stream fractional distillation further₈ The bottom stream of aromatic compounds.

Method the most according to claim 1, its transfer alkylation conditions includes temperature, the 100kPa to 6Mpa of 200 DEG C to 540 DEG C Absolute pressure and 0.1hr^-1To 20hr^-1Space velocity.

Method the most according to claim 1, wherein Q is the 1:1 mixture of 1-crassitude and dimethylethyl amine.

Method the most according to claim 1, wherein R is selected from 1,3-dichloropropane, Isosorbide-5-Nitrae-dichloroetane, 1,5-dichloropentane, 1, 6-dichloro hexane, 1,3-dibromopropane, 1,4-dibromobutane, pentamethylene bromide, 1,6-dibromo-hexane, 1,3-diiodo propane, Isosorbide-5-Nitrae-two iodobutane, 1,5-bis-iodopentane, 1,6-bis-iodohexane and combinations thereof, and wherein Q selected from 1-ethyl pyrrolidine, 1-methyl Pyrrolidine, 1-ethyl azetidine, 1-methyl azetidine, triethylamine, diethylmethyl amine, dimethylethyl amine, three Methyl amine, dimethylbutyl amine, dimethyl propyl amine, dimethyl isopropyl amine, Methylethyl propyl group amine, Methylethyl isopropyl Amine, dipropylamine, diisopropylamine, Aminocyclopentane, methylcyclohexylamine, hexamethylene imine and combinations thereof.

Method the most according to claim 1, wherein this catalyst comprises UZM-14 further.

Method the most according to claim 1, wherein turns alkylate stream by this and is divided into and comprises at least 99.3wt.% benzene Stream and at least one remaining mass flow rich in benzene.