CN102947224A - Uzm-35 zeolitic composition, method of preparation and processes - Google Patents

Uzm-35 zeolitic composition, method of preparation and processes Download PDF

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CN102947224A
CN102947224A CN2010800673919A CN201080067391A CN102947224A CN 102947224 A CN102947224 A CN 102947224A CN 2010800673919 A CN2010800673919 A CN 2010800673919A CN 201080067391 A CN201080067391 A CN 201080067391A CN 102947224 A CN102947224 A CN 102947224A
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J·G·莫斯科索
D-Y·詹
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Honeywell UOP LLC
Universal Oil Products Co
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
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Abstract

A new family of crystalline aluminosilicate zeolitic compositions, UZM-35 compositions, has been synthesized. These zeolitic compositions are represented by the empirical formula. M n+ m R + r Al (1-x) E x Si y O z where M represents a combination of potassium and sodium exchangeable cations, R is a singly charged organoammonium cation such as the dimethyldipropylammonium cation and E is a framework element such as gallium. These compositions comprise a MSE zeolite, a MFI zeolite and an ERI zeolite. The compositions are similar to MCM-68 but are characterized by unique x-ray diffraction patterns and have catalytic properties for carrying out various hydrocarbon conversion processes.

Description

UZM-35 zeolite compositions, preparation method and technique
Invention field
The present invention relates to comprise the UZM-35 composition of MSE zeolite, MFI zeolite and ERI zeolite.The UZM-35 composition is represented by following empirical formula:
M m n+R + rAl 1-xE xSi yO z
Wherein M represents the combination of potassium and sodium exchangeable cation, and R is that single electric charge organic ammonium positively charged ion such as dimethyl dipropyl ammonium and E are backbone element such as gallium.
Background of invention
Zeolite be micropore and by sharing AlO 2And SiO 2The crystal aluminosilicate composition that tetrahedral dihedral becomes.A large amount of zeolites of natural existence and synthetic preparation are used for various commercial runs.Synthetic zeolite uses suitable Si, Al source and structure directing agent such as basic metal, alkaline-earth metal, amine or organic ammonium positively charged ion to synthesize and prepare by hydrothermal solution.Structure directing agent occupy in the hole of zeolite and to the concrete structure of final formation and takes the main responsibility.These species balances the skeleton electric charge relevant with aluminium and also can be used as the space filler.Zeolite is characterised in that perforate with uniform-dimension, have significant ion-exchange capacity and reversibly desorb be scattered in the whole crystals space and significantly do not replace the Adsorption Phase of any atom, this consists of permanent zeolite crystal structure.The zeolite structured International of the being described in Zeolite Association Structure Commission of topology is retained on the http://www.iza-structure.org/databases/.Zeolites Atlas of Zeolite Framework TypesIn, it can be used as the catalyzer of hydrocarbon conversion reaction, described reaction on the outer surface and the internal surface in the hole carry out.
Have a kind of concrete zeolite of MSE structure type, be expressed as MCM-68, be disclosed in 1999 (US 6,049,018) by people such as Calabro.This patent has been described by dication directed agents N, N, N ', N '-tetraalkyl dicyclo [2.2.2] suffering-7-alkene-2R, 3S:5R, 6S-two tetramethyleneimine
Figure BDA00002572854200011
Dication and N, N, N ', N '-tetraalkyl dicyclo [2.2.2] octane-2R, 3S:5R, 6S-two tetramethyleneimine
Figure BDA00002572854200012
Dication synthesizes MCM-68.Find MCM-68 have at least one wherein each passage by 12 yuan of channel system that ring limits with four sides ligating atom, at least two wherein each passage is by 10 yuan of other autonomous channel systems that ring limits with four sides ligating atom, and wherein the number of unique 10 yuan of ring passages is twices of 12 yuan of ring number of active lanes.
The applicant has successfully prepared gang's novel material composition, is called the UZM-35 composition.A kind of topology in the said composition mesolite is similar to be observed about MCM-68.This material is by using simple commercially available structure directing agent such as dimethyl dipropyl ammonium hydroxide and a small amount of K +And Na +Together, use electric density mismatch route (the Charge Density Mismatch Approach) preparation of US 7,578,993 described zeolite synthesis.It is synthetic that UZM-35 zeolite with MSE topology can be used as the UZM-35 composition that comprises MSE topology zeolite and MFI topology zeolite and ERI topology zeolite.The topology of MSE, MFI, ERI such as International Zeolite Association Structure Commission are retained in Http:// www.iza-strucure.org/databases/On Atlas of Zeolite Framework TypesThe middle definition.
Summary of the invention
As described, the present invention relates to comprise the new aluminosilicate zeolite composition of MSE zeolite, MFI zeolite and ERI zeolite, be expressed as the UZM-35 composition.Therefore, one embodiment of the invention is microporous crystalline zeolite UZM-35 composition, and it has at least AlO 2And SiO 2The three-dimensional framework of tetrahedron element and by following empirical formula represent synthesize and the experience of moisture-free basis forms:
M m +R + rAl 1-xE xSi yO z
Wherein M represents the combination of potassium and sodium exchangeable cation, " m " be M with (Al+E) mol ratio and from approximately 0.05 to approximately 3 changing, R is selected from following single electric charge organic ammonium positively charged ion: dimethyl dipropyl ammonium (DMDPA +), dimethyl diisopropyl ammonium (DMDIP +), choline, ethyl TMA (TriMethylAmine) (ETMA +), diethyl dimethylammonium (DEDMA +), trimethylammonium the third ammonium, trimethylammonium fourth ammonium, dimethyl di-alcohol ammonium, Tetrylammonium (TEA +), tetrapropylammonium (TPA +), methyl 3 third ammoniums and composition thereof, " r " is for R and (Al+E) mol ratio and have approximately 0.25 to about 2.0 value, E is the element that is selected from gallium, iron, boron and composition thereof, " x " is for the molar fraction of E and have 0 to about 1.0 value, " y " is Si with (Al+E) mol ratio and from greater than 2 to approximately 12 changing, and " z " for O with (Al+E) mol ratio and have the value of being determined by following equation:
z=(m+r+3+4·y)/2
And be characterised in that said composition has the x x ray diffration pattern x, described x x ray diffration pattern x has at least spacing of d shown in the Table A and intensity:
Table A
Figure BDA00002572854200031
Figure BDA00002572854200041
In addition, composition is thermally-stabilised until in one embodiment greater than 400 ℃ and 600 ℃ temperature in another embodiment.The UZM-35 composition that is synthesized comprises MSE topology zeolite, MFI topology zeolite and ERI topology zeolite.Typically, in the composition amount of MSE zeolite from approximately 55 to about 75 % by weight or from approximately 55 changing to about 90 % by weight.The amount of MFI zeolite from composition approximately 20 to about 35 % by weight or from approximately 10 changing to about 35 % by weight, and the amount of ERI zeolite from composition approximately 3 to about 9 % by weight or from approximately 3 changing to about 10 % by weight.Certainly, do not have any other impurity, the amount sum of three kinds of zeolites adds up to 100 % by weight of composition.
Above-mentioned crystalline microporous zeolite UZM-35 composition can contain by formation the reaction mixture in the reactivity source of M, R, Al, Si and optional E, and with reaction mixture approximately 150 to approximately 200 ℃ or approximately 165 to about 185 ℃ the temperature the heating time enough synthesize to form composition, reaction mixture has the following composition that the mol ratio according to oxide compound represents:
aM 2O:bR 2/pO:1-cAl 2O 3:cE 2O 3:dSiO 2:eH 2O
Wherein " a " has approximately 0.05 to about 1.25 value, " b " has approximately 1.5 to about 40 value, and " p " is the weighted mean valency of R and from 1 to approximately 2 changing, and " c " has 0 to about 1.0 value, " d " has approximately 4 to about 40 value, and " e " has approximately 25 to about 4000 value.MSE type zeolite UZM-35 zeolite and other zeolite MFI and ERI are as one man synthetic to form the UZM-35 composition.
Yet another embodiment of the invention is for using the hydroconversion process of UZM-35 composition.The method comprises makes hydrocarbon contact to obtain convert hydrocarbons with the UZM-35 composition under conversion condition.
Detailed Description Of The Invention
The applicant has prepared the aluminosilicate zeolite composition that comprises MSE zeolite, MFI zeolite and ERI zeolite.The MSE zeolite have relate to as Among the Atlas of Zeolite Framework TypesTherefore the topological framework of described MSE is referred to herein as the MSE zeolite.Shown in detail, the UZM-35 composition is different from MCM-68 in its a large amount of characteristic aspect.Microporous crystalline zeolite UZM-35 composition has institute's synthesized form of being represented by following empirical formula and the experience of moisture-free basis forms:
M m +R + rAl 1-xE xSi yO z
Wherein M represents the combination of potassium and sodium exchangeable cation.R is single electric charge organic ammonium positively charged ion, and the example includes but not limited to dimethyl dipropyl ammonium cation (DMDPA +), dimethyl diisopropyl ammonium (DMDIP +), choline [(CH 3) 3N (CH 2) 2OH] +, ETMA +, DEDMA +, trimethylammonium the third ammonium, trimethylammonium fourth ammonium, dimethyl di-alcohol ammonium, methyl 3 third ammoniums, TEA +, TPA +And composition thereof, and " r " be R with (Al+E) mol ratio and from approximately 0.25 to approximately 2.0 changing, " m " be M with (Al+E) mol ratio and from approximately 0.05 to approximately 3 variations simultaneously.Silicon and (Al+E) mol ratio are by " y " expression and from approximately 2 to approximately 30 changing.E is the element of four sides coordination, is present in the skeleton and is selected from gallium, iron and boron.The molar fraction of E represents by " x " and has 0 to about 1.0 value, simultaneously " z " for O with (Al+E) mol ratio and have the value that is provided by following equation:
z=(m·n+r+3+4·y)/2。
If M is a kind of metal only, then the weighted mean valency is the valency of this a kind of metal, namely+1 or+2.Yet, when existing more than a kind of M metal, total amount:
M m n + = M m 1 ( n 1 ) + + M m 2 ( n 2 ) + + M m 3 ( n 3 ) + + . . . . .
And weighted mean valency " n " is provided by following equation:
n = m 1 · n 1 + m 2 · n 2 + m 3 · n 3 + · · · m 1 + m 2 + m 3 · · ·
Microporous crystalline zeolite UZM-35 composition is by preparing in conjunction with the reaction mixture hydrothermal crystallization for preparing by the reactivity source with M, R, aluminium, silicon and optional E.The source of aluminium includes but not limited to aluminium-alcohol salt, precipitated alumina, aluminum metal, aluminium salt and alumina sol.The specific examples of aluminium-alcohol salt includes but not limited to former aluminium secondary butylate and former aluminum isopropylate.The source of silicon-dioxide includes but not limited to tetraethyl orthosilicate, colloidal silica, precipitated silica and alkalimetal silicate.The source of E element includes but not limited to alkali metal borate, boric acid, precipitation hydroxyl oxidize gallium, gallium sulfate, ferric sulfate and iron(ic) chloride.The source of M potassium metal and sodium comprises corresponding alkali-metal halogen, nitrate, acetate and oxyhydroxide.R is the organic ammonium positively charged ion that is selected from dimethyl dipropyl ammonium, choline, ETMA, DEDMA, TEA, TPA, trimethylammonium the third ammonium, trimethylammonium fourth ammonium, dimethyl di-alcohol ammonium and composition thereof, and the source comprises oxyhydroxide, muriate, bromide, iodide and fluoride compound.Specific examples includes but not limited to dimethyl dipropyl ammonium hydroxide, dimethyl dipropyl ammonium chloride, dimethyl dipropyl brometo de amonio, dimethyl di-isopropyl ammonium hydroxide, dimethyl di-isopropyl ammonium chloride, dimethyl di-isopropyl brometo de amonio, ethyl-trimethyl ammonium hydroxide, diethyl-dimethyl ammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and 4-propyl ammonium chloride.
It should be noted that between synthesis phase, metal M is+1 valency, especially potassium and sodium.Yet in optional embodiment, composition can stand syntheticly after the other ion-exchange step to have one or more and have+material of the metal M of divalent to provide.
The reaction mixture that contains the reactivity source of required component can be described by following formula according to the mol ratio of oxide compound:
aM 2O:bR 2/pO:1-cAl 2O 3:cE 2O 3:dSiO 2:eH 2O
Wherein " a " 0.05 to approximately 1.25 changing, " b " 1.5 to approximately 40 changing, " c " from 0 to 1.0 changes from approximately from approximately, " d " 4 to approximately 40 changing, and " e " is from approximately 25 to approximately 4000 changing from approximately.If the use alkoxide then preferably includes distillation or evaporation step to remove pure hydrolysate.Reaction mixture now in sealed reaction vessel under autogenous pressure approximately 150 to approximately 200 ℃, approximately 165 to approximately 185 ℃ or approximately 170 to about 180 ℃ the temperature reaction approximately 1 day to about 3 weeks, preferred approximately 5 days to about time of 12 days.After crystallization is finished, with solid product by filtering or centrifugally from non-homogeneous mixture, separating, then with deionized water wash and in air approximately dry under 100 ℃ the envrionment temperature at the most.Should be understood that to choose wantonly the UZM-35 zeolite seeds is added in the reaction mixture to accelerate the formation of composition.
The preferred synthetic route of preparation UZM-35 composition is used US 7,578,993 and Studies in Surface Science and Catalysis, (2004), 154A volume, the disclosed electric density mismatch of 364-372 concept.US 7,578, and 993 disclosed methods use quaternary ammonium hydroxide with stable silicon aluminate species, usually introduce simultaneously crystallization inductor such as alkali and alkaline earth metal ions and higher electric charge organic ammonium positively charged ion in separating step.When some UZM-35 seeds used this route to produce, this seed can example such as the combination of dimethyl dipropyl ammonium hydroxide and alkali metal cation and to be used for the single stage of UZM-35 composition synthetic.Using commercially available dimethyl dipropyl ammonium hydroxide to prepare the UZM-35 composition provides and previous structure directing agent (N, N, N ', N '-tetraalkyl dicyclo [2.2.2] suffering-7-alkene-2R, 3S:5R, 6S – two tetramethyleneimine for the preparation of the silico-aluminate with MSE topology
Figure BDA00002572854200071
Dication and N, N, N ', N '-tetraalkyl dicyclo [2.2.2] octane-2R, 3S:5Rs, 6-two tetramethyleneimine Dication) compares large economical advantage.In addition, dimethyl dipropyl ammonium hydroxide can use electric density mismatch concept and other cheap organic ammonium oxyhydroxide as one man to use with as oxyhydroxide or muriate even further reduce cost.
The UZM-35 composition that is obtained by aforesaid method is characterised in that use J.Appl.Cryst. (1969) 2,65-71 described Rietveld refine methods (Rietveld refinement method) and has the x x ray diffration pattern x that descends at least the spacing of d shown in the Table A and relative intensity:
Table A
Figure BDA00002572854200073
As among the embodiment in detail shown in, the UZM-35 composition is thermally-stabilised until at least 400 ℃, in another embodiment until about 600 ℃ temperature.
According to synthetic, the UZM-35 composition contains some commutative or charge balance cations in its hole.These exchangeable cation can with other cationic exchange, or in the organic cations situation, they can be removed by heating under controlled condition.Because the UZM-35 composition comprises large pore zeolite, also can directly remove some organic cations by ion-exchange.The UZM-35 composition can improve in many ways so that it is applicable in concrete the application.Improvement comprises calcining, ion-exchange, decatize, various acid extraction, ammonium hexafluorosilicate processing or its any combination, and such as US 6,776,975B1 is described about the situation of UZM-4M, by reference it all is incorporated herein.Improved performance comprises porosity, absorption, Si/Al mol ratio, acidity, thermostability etc.
UZM-35 composition (UZM-35HS herein) by ' 975 described one or more technological improvements of patent is described by following empirical formula based on anhydrous:
M 1 a n + Al ( 1 - x ) E x Si y ′ O z ′ ′
Wherein M1 is at least a basic metal that is selected from, alkaline-earth metal, rare earth metal, ammonium ion, the exchangeable cation of hydrogen ion and composition thereof, " a " is M1 with (Al+E) mol ratio and from approximately 0.05 to approximately 50 changing, " n " is for the weighted mean valency of M1 and have approximately+1 to value approximately+3, E is for being selected from gallium, iron, the element of boron and composition thereof, " x " is that the molar fraction and from 0 to 1.0 of E changes, y ' is Si with (Al+E) mol ratio and from greater than approximately 4 changing to basic pure silicon dioxide, and z ' for O with (Al+E) mol ratio and have the value of being determined by following equation:
z’=(a·n+3+4·y’)/2
Basic pure silicon dioxide means basic all aluminium and/or the E metal is removed from skeleton.Know and substantially can not remove all aluminium and/or E metal.Use numeral, work as y ' and have at least 3,000, preferred 10,000, most preferably during 20,000 value, zeolite is basic pure silicon dioxide.Therefore, the scope of y ' is 4-3,000, be preferably greater than 10 to approximately 3,000; 4-10,000, be preferably greater than 10 to approximately 10,000, and 4-20,000, be preferably greater than 10 to approximately 20,000.
In the ratio of describing this paper zeolite raw material or the absorption property of zeolite product etc., unless otherwise noted, " anhydrous state " of zeolite wanted.Term " anhydrous state " is used in reference to substantially the zeolite without the water of physics absorption and chemisorption in this article.
Crystalline zeolite UZM-35 composition of the present invention can be used for the mixture of isolated molecule species, removes pollutent by ion-exchange, and the various hydroconversion process of catalysis.The separation of molecular species can be based on the degree of polarity of molecular size (kinetic diameter) or molecular species.
UZM-35 composition of the present invention also can be used as catalyzer or the support of the catalyst of various hydroconversion process.Hydroconversion process is well known in the art and comprises the disproportionation of the transalkylation of the isomerization of the alkylation of cracking, hydrocracking, aromatic hydrocarbons and isoparaffin, paraffinic hydrocarbons and polyoxyethylene alkylphenyl such as dimethylbenzene, polyoxyethylene alkylphenyl and benzene or monoalkylated benzenes, monoalkylated benzenes, polymerization, reformation, hydrogenation, dehydrogenation, alkyl exchange, dealkylation, hydration, dehydration, hydrotreatment, hydrodenitrification, hydrogenating desulfurization, methanation and synthetic gas method of converting.The concrete reaction conditions and the feed type that can be used in these methods are described in US4,310,440 and US 4,440,871 in, by reference it is incorporated herein.Preferred hydroconversion process is those of a kind of component for hydrogen wherein, such as hydrotreatment or hydrofining, hydrogenation, hydrocracking, hydrodenitrification, hydrogenating desulfurization etc.
Hydrocracking condition generally includes approximately 204 to approximately 649 ℃ (400-1200 ℉) or approximately 316 temperature to approximately 510 ℃ (600-950 ℉).Reaction pressure is normal atmosphere to approximately 24,132kPa g (3,500psig), or approximately 1379 to approximately 20,685kPa g (200-3000psig).Usually be equivalent to approximately 0.1-15hr duration of contact -1,, preferred approximately 0.2-3hr -1Liquid hourly space velocity.Hydrogen circulation rates is 178 to approximately 8,888std.m 3/ m 3(1,000-50, every barrel of charging of 000 standard cubic foot (scf)), or approximately 355 to approximately 5,333std.m 3/ m 3(approximately 2,000 to approximately 30, every barrel of charging of 000scf).Suitable hydroprocessing condition is generally in the wide region of above-mentioned hydrocracking condition.
Usually the reaction zone effluent is removed from catalyst bed, stood partial condensation and steam-liquid separation, then fractionation is to reclaim its various components.Hydrogen and some or all of unconvertedly be recycled in the reactor than heavy material if necessary.As selection, can use two stage flow processs, wherein unconverted materials enters in the second reactor.Catalyzer of the present invention can be used in only stage of these class methods or can be used for two reactors in the stage.
Catalyst cracking method preferably uses raw material such as gas oil, heavy naphtha, deasphalted crude residue etc. to carry out with UZM – 35 compositions, and wherein gasoline is main required product.The temperature condition of approximately 454 to approximately 593 ℃ (approximately 850 ℉ to approximately 1100 ℉), the LHSV value of 0.5-10 and approximately 0 to the about pressure condition of 344kPa g (approximately 0-50psig) be suitable.
The alkylation of aromatic hydrocarbons is usually directed to aromatic hydrocarbons (C 2-C 12), especially benzene reacts to produce the aromatic hydrocarbons that linear alkyl replaces with monoolefine.The method is with the aromatic hydrocarbons of 1:1-30:1: alkene (benzene for example: alkene) than, approximately 0.3 to about 10hr -1Alkene LHSV, approximately 100 to approximately 250 ℃ temperature and approximately 1379 to about 6895kPa g the pressure of (approximately 200 to approximately 1000psig) carry out.Can be at US4 about other details of equipment, find in 870,222, by reference it is incorporated herein.
With the isoparaffins with olefins alkylation to produce the applicable alkylide of making engine fuel component with-30 ℃ to 40 ℃ temperature, approximately normal atmosphere is to approximately 6, (1, pressure 000psig) and 0.1 carries out to about 120 weight hourly space velocity (WHSV) 895kPa.Can be at US 5,157 about the details of alkylation of paraffines, 196 and US 5,157,197 in find, by reference it is incorporated herein.
Following examples propose in setting forth the present invention and are not intended to be the as described in the appended claims improper restriction of the general wide region of the present invention.
The structure of UZM-35 composition of the present invention is determined by the x X-ray analysis X.The x ray diagram Application standard x ray powder diffraction technology that presents in following examples obtains.Source of radiation is the high strength x x ray tube with 45kV and 35ma operation.Obtain by suitable computer based technology from the alpha-emitting diffractogram of copper K-.With the concora crush powdered sample with 2-56 ° of (2 θ) continuous sweep.The spacing (d) that represents with atomic meter is obtained by the position of the diffraction peak that is expressed as θ, wherein the Bragg angle of θ for being observed by numerised data.Intensity is measured later on " I by the comprehensive area subtracting background of diffraction peak o" be the intensity at the strongest line or peak, " I " is other peak intensity separately.
As skilled in the art to understand, the mensuration of parameter 2 θ has artificial and mechanical error, the 2 θ values that its combination can be given each report inaccuracy approximately ± 0.4 °.This inaccuracy also can find expression in the report value of the d spacing of being calculated by 2 θ values certainly.This inaccuracy be common in the art and be not enough to get rid of crystalline material of the present invention each other and with the difference of prior art compositions.In some x ray diagrams of report, the relative intensity of d spacing represents by symbol vs, s, m and w, its represent respectively very strong, strong, medium and a little less than.According to 100 * I/I o, above demonstrative definition is:
W=0-15; M=15-60; S=60-80 and vs=80-100
In some cases, the purity of synthetic product can be with reference to its x ray powder diffraction pattern assessment.Therefore, if for example sample is described as purely, the x ray diagram that then only means sample does not contain the line owing to crystalline impurities, rather than does not have amorphous material.
In order more completely to set forth the present invention, provide following embodiment.Be to be understood that embodiment is only for setting forth and not meaning that the as described in the appended claims improper restriction of wide region of the present invention.
Embodiment 1
Be prepared as follows the silico-aluminate reaction soln: at first 16.64g aluminium hydroxide (27.78 quality %Al) and 526.79g dimethyl dipropyl ammonium hydroxide (18.8 quality % solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 252.98g Ludox TMAS-40 (40%SiO 2).With the high speed machine agitator with other one hour of reaction mixture homogenizing and put into 100 ℃ baking oven and spend the night.Analyze and show that the gained aluminosilicate solution contains 6.52 % by weight Si and 0.64 % by weight Al, obtains 9.78 Si/Al ratio.
Under vigorous stirring, add in the aluminosilicate solution of preparation in the embodiment 1 of 150g and contain the 1.44g NaOH (98%) that is dissolved in the 20.0g distilled water and the compound NaOH/KOH aqueous solution of 2.02g KOH, and with other 30 minutes of reaction mixture homogenizing.The 24g reaction mixture is transferred in the 45mlParr stainless steel autoclave, is heated to 175 ℃ and remained on this temperature lower 120 hours.By centrifugal recovery solid product, with deionized water wash and lower dry at 100 ℃.
By centrifugal recovery solid product, with deionized water wash and lower dry at 95 ℃.This product is defined as the UZM-35 zeolite by xrd.The typical diffracted ray of observing about product is shown in the table 1.Formed by following mol ratio by the determination of elemental analysis product composition: Si/Al=7.92, Na/Al=0.1, K/Al=0.48.
Table 1
Figure BDA00002572854200121
Figure BDA00002572854200131
Scanning electron microscopy (SEM) shows to have square form, is of a size of the approximately crystal of 100 * 350nm.Then this sample was being calcined 10 hours under 540 ℃ under air under the nitrogen.The typical diffracted ray of observing about calcinate is shown in the table 2.
Table 2
Figure BDA00002572854200132
Figure BDA00002572854200141
Embodiment 2
Be prepared as follows the silico-aluminate reaction soln: at first 37.17g aluminium hydroxide (27.78 quality %Al) and 1053.58g dimethyl dipropyl ammonium hydroxide (18.8 quality % solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 505.96g Ludox TMAS-40 (SiO 2, 40%)., be sealed in the Teflon bottle and under 100 ℃, put into baking oven and spend the night reaction mixture homogenizing one hour with the high speed machine agitator.Analyze and show that aluminosilicate solution contains 6.16 % by weight Si and 0.67 % by weight Al (Si/Al=8.83).
The above aluminosilicate solution of continuously stirring 100.0g.To contain and be dissolved in 15g H 2The compound aqueous solution of 2.38gKOH among the O and 0.3g NaOH dropwise adds in the aluminosilicate solution.After interpolation is finished, with gained reaction mixture homogenizing 1 hour, be transferred in (4) 45mlParr stainless steel autoclave, be heated to 175 ℃ and remained on this temperature lower 216 hours.By centrifugal recovery solid product, with deionized water wash and lower dry at 100 ℃.
By the centrifugal solid product of retrieving in these samples each, with deionized water wash and lower dry at 95 ℃.The product that is produced by all four kinds reactions is defined as the UZM-35 zeolite by xrd.Table 3 shows the typical diffracted ray of observing about the sample that reacted 9 days.Ultimate analysis obtains having the product composition of following mol ratio: Si/Al=7.58, Na/Al=0.033, K/Al=0.63, C/N=6, N/Al=0.43.
Table 3
Figure BDA00002572854200151
Figure BDA00002572854200161
Embodiment 3
Be prepared as follows the silico-aluminate reaction soln: at first 37.17g aluminium hydroxide (27.78%Al) and 1053.58g dimethyl dipropyl ammonium hydroxide (18.8 quality % solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 505.96g Ludox TMAS-40 (SiO 2, 40 quality %)., be sealed in the Teflon bottle and under 100 ℃, put into baking oven and spend the night reaction mixture homogenizing one hour with the high speed machine agitator.Analyze and show that aluminosilicate solution contains 6.16 % by weight Si and 0.67 % by weight Al (Si/Al=8.83).
The above aluminosilicate solution of continuously stirring 1200g.To contain and be dissolved in 150g H 228.56g KOH among the O and the compound aqueous solution of 3.6g NaOH dropwise add in the aluminosilicate solution.After interpolation is finished, with gained reaction mixture homogenizing 1 hour, be transferred in the 2000ml Pa Er stainless steel autoclave, be heated to 175 ℃ and remained on this temperature lower 216 hours.By centrifugal recovery solid product, with deionized water wash and lower dry at 100 ℃.
By the centrifugal solid product of retrieving in these samples each, with deionized water wash and lower dry at 95 ℃.The product that is produced by this reaction is defined as the UZM-35 zeolite by xrd.Ultimate analysis obtains having the product composition of following mol ratio: Si/Al=7.57, Na/Al=0.028, K/Al=0.73, N/Al=0.37.Then this sample was being calcined 10 hours under 540 ℃ under air under the nitrogen.The typical diffracted ray of observing about product is shown in the table 4.
Table 4
Figure BDA00002572854200171
Figure BDA00002572854200181
Embodiment 4
This embodiment describes the improvement of UZM-35 material.10g UZM-35 sample (Si/Al mol ratio=7.57) is risen to 540 ℃ and kept herein other 1 hour and calcine with 3 ℃/minute in nitrogen atmosphere, then atmosphere is changed into air and continued other 9 hours of calcining.Be prepared as follows solution: at first dilute 2g HNO 3(69 quality %) is thereafter with 10g NH 4NO 3Be dissolved in the 120g deionized water.This solution is heated to 75 ℃, then adds the UZM-35 through calcining.This slurry was stirred 1 hour under 75 ℃.By the filtering separation product, with deionized water wash and lower dry 12 hours at 100 ℃.
This product is defined as UZM-35HS by the x ray powder diffraction.Ultimate analysis confirms that the Si/Al mol ratio is increased to Si/Al=8.3, Na/Al=0.01, K/Al=0.44.
Embodiment 5
This embodiment describes the improvement of UZM-35 material.20g UZM-35 sample (Si/Al mol ratio=7.57) is risen to 540 ℃ and kept herein other 1 hour and calcine with 3 ℃/minute under nitrogen atmosphere, then atmosphere is changed into air and continued other 9 hours of calcining.Be prepared as follows dividually solution: with 20g NH 4NO 3Be dissolved in the 490g deionized water.Solution is heated to 75 ℃, then adds the UZM-35 through calcining.Slurry was stirred 1 hour under 75 ℃.By the filtering separation product, with deionized water wash and lower dry 12 hours at 100 ℃.
This product is defined as UZM-35HS by the x ray powder diffraction.The ultimate analysis of this sample confirms that the Si/Al mol ratio is increased to Si/Al=8.0, Na/Al=0.01, K/Al=0.47.
Embodiment 6
Be prepared as follows aluminosilicate solution: at first 37.17g aluminium hydroxide (27.78 quality %Al) and 1053.58g dimethyl dipropyl ammonium hydroxide (18.8 quality % solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 505.96g Ludox TMAS-40 (40 quality %SiO 2).With the high speed machine agitator with other one hour of reaction mixture homogenizing and under 100 ℃, put into baking oven and spend the night.Analyze and show that the gained aluminosilicate solution contains 6.16 % by weight Si and 0.67 % by weight Al, obtains 8.83 Si/Al mol ratio.
Along with adding the NaOH aqueous solution that contains the 1.98g NaOH (98%) that is dissolved in the 10.0g distilled water in the aluminosilicate solution of vigorous stirring preparation in the above embodiment 6 of 100g, and with other 30 minutes of this reaction mixture homogenizing.The 24g reaction mixture is transferred in the 45ml Parr stainless steel autoclave, is heated to 175 ℃ and remained on this temperature lower 144 hours.By centrifugal recovery solid product, with deionized water wash and lower dry at 100 ℃.
By centrifugal recovery solid product, with deionized water wash and lower dry at 95 ℃.This product is defined as the MOR zeolite by xrd.
Embodiment 7
Be prepared as follows aluminosilicate solution: at first 37.17g aluminium hydroxide (27.78 quality %Al) and 1053.58g dimethyl dipropyl ammonium hydroxide (18.8 quality % solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 505.96g Ludox TMAS-40 (40 quality %SiO 2).With the high speed machine agitator with other one hour of reaction mixture homogenizing and under 100 ℃, put into baking oven and spend the night.Analyze and show that the gained aluminosilicate solution contains 6.16 % by weight Si and 0.67 % by weight Al, obtains 8.83 Si/Al mol ratio.
Along with adding the KOH aqueous solution that contains the 3.84g KOH that is dissolved in the 20.0g distilled water in the aluminosilicate solution of vigorous stirring preparation in the above embodiment 6 of 150g, and with other 30 minutes of reaction mixture homogenizing.The 24g reaction mixture is transferred in the 45ml Parr stainless steel autoclave, is heated to 175 ℃ and remained on this temperature lower 264 hours.By centrifugal recovery solid product, with deionized water wash and lower dry at 100 ℃.
By centrifugal recovery solid product, with deionized water wash and lower dry at 95 ℃.This product is defined as ZSM-5 zeolite by xrd.
Embodiment 8
Be prepared as follows aluminosilicate solution: at first 86.33g aluminium hydroxide (26.97 quality %Al) and 1437.67g dimethyl dipropyl ammonium hydroxide (40.66 quality % solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 1366.88g Ludox TMAS-40 (SiO 2, 40 quality %).With reaction mixture homogenizing 20 minutes, continuously stirring silico-aluminate colloidal solution also will contain and be dissolved in 808.7g H with the high speed machine agitator 283.04g KOH among the O and the aqueous solution of 17.38g NaOH dropwise add in the aluminosilicate solution.After interpolation is finished, with gained reaction mixture homogenizing 1/2 hour, be transferred in (3) 2000ml Parr stainless steel autoclave, be heated to 175 ℃ and remained on this temperature lower 9 days.By the filtered and recycled solid product, with deionized water wash and lower dry at 100 ℃.
(J.Appl.Cryst. (1969) 2 by the x ray diffraction to react the product that produces by this, the Rietveld refine method of describing among the 65-71) be defined as the UZM-35 composition, it has the MSE type zeolite of lattice parameter of the c of a with 18.372 dusts of 72.1 % by weight and 20.285 dusts; 24.1 the MFI zeolite of the lattice parameter of the c of a with 20.101 dusts of % by weight, the b of 19.862 dusts and 13.402, and the ERI zeolite of the lattice parameter of the c with 13.222 a dust and 14.900 dusts of 3.7 % by weight.Chemical analysis obtains the product composition of mol ratio Si/Al=8.9.The BET surface area test is 408m 2/ g, and micro pore volume is 0.197cc/g.The typical diffracted ray of observing about this product is shown in the table 5.
Table 5
Figure BDA00002572854200201
Figure BDA00002572854200211
Figure BDA00002572854200221
Then this sample was being calcined 5 hours under 600 ℃ under air under the nitrogen.(J.Appl.Cryst. (1969) 2 by the x ray diffraction by calcining the product that produces, the Rietveld refine method of describing among the 65-71) be defined as a kind of mixture, it has the UZM-35 of lattice parameter of the c of a with 18.371 dusts of 64.4 % by weight and 20.235 dusts; 30.7 a with 20.048 dusts of % by weight, the MFI of the lattice parameter of the c of the b of 19.880 dusts and 13.403 dusts, and the ERI of the lattice parameter of the c of a with 13.071 dusts of 4.8 % by weight and 15.238 dusts.160g is carried out NH through the UZM-35 sample (Si/Al mol ratio=8.9) of calcining 4Exchange.Be prepared as follows solution: with 160g NH 4NO 3Be dissolved in the 1800g deionized water.Solution is heated to 75 ℃, then adds the UZM-35 through calcining.Slurry was stirred 1 hour under 75 ℃.By the filtering separation product, use deionized water wash.Repeat this NH 4Exchanger 3 times, then that it is lower dry 12 hours at 100 ℃.
The ultimate analysis of this sample shows that the Si/Al mol ratio is Si/Al=9.07, Na/Al=0.01, K/Al=0.11.
The typical diffracted ray of observing about this product is shown in the table 6.
Table 6
Figure BDA00002572854200222
Embodiment 9
Be prepared as follows the silico-aluminate reaction soln: at first 29.01g aluminium hydroxide (26.97%Al) and 483.08g dimethyl dipropyl ammonium hydroxide (40.66% solution) are mixed, simultaneously vigorous stirring.After fully mixing, add 461.58g Ludox TMAS-40 (SiO 2, 40%).With reaction mixture homogenizing 20 minutes, continuously stirring silico-aluminate colloidal solution also will contain and be dissolved in 269.98g H with the high speed machine agitator 227.90g KOH among the O and the aqueous solution of 3.46g NaOH dropwise add in the aluminosilicate solution.After interpolation is finished, with gained reaction mixture homogenizing 1/2 hour, be transferred in the 2000mlParr stainless steel autoclave, be heated to 175 ℃ and remained on this temperature lower 10 days.By the filtered and recycled solid product, with deionized water wash and lower dry at 100 ℃.
(J.Appl.Cryst. (1969) 2 by the x ray diffraction to react the product that produces by this, the Rietveld refine method of describing among the 65-71) be defined as the UZM-35 composition, it has the MSE type zeolite of lattice parameter of the c of a with 18.369 dusts of 66.3 % by weight and 20.284 dusts; 25.5 the MFI of the lattice parameter of the c of a with 20.136 dusts of % by weight, the b of 19.976 dusts and 13.443 dusts, and the ERI of the lattice parameter of the c of a with 13.152 dusts of 8.2 % by weight and 15.107 dusts.Chemical analysis obtains Si/Al=7.65, N/Al=0.38, K/Al=0.68, the product composition of Na/Al=0.03 (mol ratio).The BET surface area test is 404m 2/ g, and micro pore volume is 0.188cc/g.The typical diffracted ray of observing about this product is shown in the table 7.
Table 7
Figure BDA00002572854200241
Figure BDA00002572854200251
Then this sample was being calcined 5 hours under 600 ℃ under air under the nitrogen.(J.Appl.Cryst. (1969) 2 by the x ray diffraction by calcining the product that produces, the Rietveld refine method of describing among the 65-71) be defined as the UZM-35 composition, it has the MSE zeolite (UZM-35 zeolite) of lattice parameter of the c of a with 18.401 dusts of 61.9 % by weight and 20.280 dusts; 30.8 a with 20.114 dusts of % by weight, the MFI zeolite of the lattice parameter of the c of the b of 19.919 dusts and 13.432 dusts, and the ERI zeolite of the lattice parameter of the c of a with 13.189 dusts of 7.3 % by weight and 15.174 dusts.100g is carried out NH through the UZM-35 sample (Si/Al mol ratio=7.65) of calcining 4Exchange.Be prepared as follows solution: with 160g NH 4NO 3Be dissolved in the 1800g deionized water.Solution is heated to 75 ℃, then adds the UZM-35 through calcining.Slurry was stirred 1 hour under 75 ℃.By the filtering separation product, use deionized water wash.Repeat this NH 4Exchanger 3 times, then that it is lower dry 12 hours at 100 ℃.
The ultimate analysis of this sample shows that the Si/Al mol ratio is Si/Al=9.20, Na/Al=0.01, K/Al=0.10.
The typical diffracted ray of observing about this product is shown in the table 8.
Table 8
Figure BDA00002572854200261
Figure BDA00002572854200271

Claims (9)

1. comprise the UZM-35 composition of MFI zeolite, ERI zeolite and MSE zeolite, wherein the UZM-35 composition has at least AlO 2And SiO 2The three-dimensional framework of tetrahedron element and by following empirical formula represent synthesize and the experience of moisture-free basis forms:
M m +R rAl 1-xE xSi yO z
Wherein M represents the combination of potassium and sodium exchangeable cation, " m " is M with (Al+E) mol ratio and from approximately 0.05 to approximately 3 changing, R is single electric charge dimethyl dipropyl ammonium cation, " r " is for R and (Al+E) mol ratio and have approximately 0.25 to about 2.0 value, E is for being selected from gallium, iron, the element of boron and composition thereof, " x " is for the molar fraction of E and have 0 to about 1.0 value, " y " is Si with (Al+E) mol ratio and from greater than 2 to approximately 12 changing, and " z " for O with (Al+E) mol ratio and have the value of being determined by following equation:
z=(m+r+3+4·y)/2
And be characterised in that it has the x x ray diffration pattern x, described x x ray diffration pattern x has at least d spacing and the intensity shown in the Table A:
Table A
Figure FDA00002572854100021
Wherein the UZM-35 composition is thermally-stabilised until at least 400 ℃ temperature.
2. according to claim 1 UZM-35 composition, wherein " x " is 0.
3. according to claim 1 UZM-35 composition, wherein the amount of MSE zeolite is from approximately 55 % by weight of mixture to approximately 90 % by weight variation, the amount of MFI zeolite is from the extremely approximately 35 % by weight variation of approximately 10 % by weight of mixture, and the amount of ERI is from the extremely approximately 10 % by weight variation of approximately 3 % by weight of mixture.
4. preparation comprises the method for the UZM-35 composition of MFI zeolite, ERI zeolite and MSE zeolite, and wherein composition has at least AlO 2And SiO 2The three-dimensional framework of tetrahedron element and by following empirical formula represent synthesize and the experience of moisture-free basis forms:
M m +R rAl 1-xE xSi yO z
Wherein M represents the combination of potassium and sodium exchangeable cation, " m " is M with (Al+E) mol ratio and from approximately 0.05 to approximately 3 changing, R is single electric charge dimethyl dipropyl ammonium cation, " r " is for R and (Al+E) mol ratio and have approximately 0.25 to about 2.0 value, E is for being selected from gallium, iron, the element of boron and composition thereof, " x " is for the molar fraction of E and have 0 to about 1.0 value, " y " is Si with (Al+E) mol ratio and from greater than 2 to approximately 12 changing, and " z " for O with (Al+E) mol ratio and have the value of being determined by following equation:
z=(m+r+3+4·y)/2
And be characterised in that it has the x x ray diffration pattern x, described x x ray diffration pattern x has at least d spacing and the intensity shown in the Table A:
Table A
Figure FDA00002572854100031
Wherein the UZM-35 composition is thermally-stabilised until at least 400 ℃ temperature; Described method comprises the reaction mixture that forms the reactivity source of containing M, R, Al, Si and optional E, and with described reaction mixture approximately 150 ℃ the heating time enough is forming zeolite compositions to about 200 ℃ the temperature, described reaction mixture has following composition that the mol ratio by oxide compound represents:
aM 2O:bR 2/pO:1-cAl 2O 3:cE 2O 3:dSiO 2:eH 2O
Wherein " a " has approximately 0.05 to about 1.25 value, " b " has approximately 1.5 to about 40 value, and " p " is the weighted mean valency of R and from 1 to approximately 2 changing, and " c " has 0 to about 1.0 value, " d " has approximately 4 to about 40 value, and " e " has approximately 25 to about 4000 value.
5. according to claim 4 method, wherein the source of M is selected from halogen, nitrate, acetate, oxyhydroxide, vitriol and composition thereof; The source of E is selected from alkali metal borate, boric acid, precipitation hydroxyl oxidize gallium, gallium sulfate, ferric sulfate, iron(ic) chloride and composition thereof; The aluminium source is selected from aluminum isopropylate, aluminium secondary butylate, precipitated alumina, Al (OH) 3, aluminum metal and aluminium salt; And the silicon source is selected from tetraethyl orthosilicate, pyrogenic silica, colloidal silica and precipitated silica.
6. according to claim 4 method, wherein reaction mixture approximately 150 ℃ to about 185 ℃ the temperature reaction approximately 1 day to about time in 3 weeks.
7. according to claim 4 method, wherein R is dimethyl dipropyl ammonium hydroxide and at least aly is selected from TEA, TPA, ETMA, DEDMA, trimethylammonium the third ammonium, dimethyl diisopropyl ammonium, trimethylammonium fourth ammonium, or the cationic combination of single electric charge organic ammonium of dimethyl di-alcohol ammonium, methyl 3 third ammoniums.
8. hydroconversion process, it comprises makes hydrocarbon flow contact to obtain converted product with UZM-35 composition catalyzer under the hydrocarbon conversion condition, described UZM-35 composition catalyzer comprises MFI zeolite, ERI zeolite and MSE zeolite, and wherein the UZM-35 composition has at least AlO 2And SiO 2The three-dimensional framework of tetrahedron element and by following empirical formula represent synthesize and the experience of moisture-free basis forms:
M m +R rAl 1-xE xSi yO z
Wherein M represents the combination of potassium and sodium exchangeable cation, " m " is M with (Al+E) mol ratio and from approximately 0.05 to approximately 3 changing, R is single electric charge organic ammonium dimethyl dipropyl ammonium cation, " r " is for R and (Al+E) mol ratio and have approximately 0.25 to about 2.0 value, E is for being selected from gallium, iron, the element of boron and composition thereof, " x " is for the molar fraction of E and have 0 to about 1.0 value, " y " is Si with (Al+E) mol ratio and from greater than 2 to approximately 12 changing, and " z " for O with (Al+E) mol ratio and have the value of being determined by equation:
And be characterised in that it has the x x ray diffration pattern x, described x x ray diffration pattern x has at least d spacing and the intensity shown in the Table A:
Table A
Figure FDA00002572854100051
Figure FDA00002572854100061
Figure FDA00002572854100071
And thermally-stabilised until at least 400 ℃ temperature.
9. according to claim 8 method, wherein hydroconversion process is selected from alkylation, transalkylation, isomerization, dimerizing olefins, olefin oligomerization and dewaxing.
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