CN1033445C - Synthetic porous crystalline material its synthesis and use - Google Patents
Synthetic porous crystalline material its synthesis and use Download PDFInfo
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- CN1033445C CN1033445C CN 91103656 CN91103656A CN1033445C CN 1033445 C CN1033445 C CN 1033445C CN 91103656 CN91103656 CN 91103656 CN 91103656 A CN91103656 A CN 91103656A CN 1033445 C CN1033445 C CN 1033445C
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Abstract
This invention relates to a composition of matter comprising an inorganic, porous crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than 1.8 nm and having a benzene adsorption capacity of greater than 15 grams benzene per 100 grams of said material at 6.7 kPa (50 torr) and 25 DEG C. Preferably, the crystalline phase material has a hexagonal arrangement of uniformly-sized pores at least 1.3 nm in diameter and exhibiting, after calcination, a hexagonal electron diffraction pattern that can be indexed with a d100 value greater than 1.8 nm.
Description
The present invention relates to a kind of synthetic method of synthetic porous crystalline material.
Have been found that the porous inorganic solid has very multi-usage industrial as catalyzer and separating medium.The opening of their microstructures makes various molecules can touch the sizable surface-area of this class material, thereby has promoted their catalysis and sorption activity.The porous material that uses can be divided into three major types as basis of classification roughly with the details of their microstructures at present.Here it is amorphous and para-crystal material, crystalline molecular sieve and modified layer laminate materials.The details difference of these materials on microstructure shows as the gross differences of material catalysis and sorption property, also show as and be used for the difference of various observability matter of exosyndrome material, as their surface-area, size of their holes and change conditions thereof, whether X ray diffracting spectrum exists the details with collection of illustrative plates, and the difference of each side such as viewed phenomenon when coming the research material microstructure with transmission electron microscopy and electron diffraction.
The important porous, inorganic solid of one class of amorphous and para-crystal material representative industrial application for many years.The exemplary of this class material is to be generally used for preparing the amorphous silica of catalyzer and through being usually used in the excessive property of the para-crystal aluminum oxide of solid acid catalyst and petroleum reforming support of the catalyst.
Here " amorphous " this speech is meant and does not have long-range order, thereby its pore dimension tends to be distributed in the material of broad range.Another speech that is used for describing this class material is " adiaphorous to X ray ", also finds expression in the X ray diffracting spectrum in default of order, can make it not have feature usually.The porousness of non-crystalline material (for example amorphous silica) is generally caused by the space between each particulate.
As the para-crystal material of transitional aluminum oxide and so on, its pore size distribution is also wide, but clearer and more definite X ray diffracting spectrum is arranged, and comprises a few broad peak usually.The microstructure of this class material is made of the small crystallizing field of cohesion aluminum oxide phase, and its porousness is caused by the irregular cavity between these crystallizing fields.(K.Wrfers ﹠amp; Chanakya Misra, " oxide compound of aluminium and oxyhydroxide ", Tech-nical Paper No.19 Revised, Alcoa Research Labor-atories, P.54-59,1987).
The size of amorphous and para-crystal material mesoporosity is in and is called in " mesopore " scope (mesoporoous), and in this application, this scope is 1.3 to 20nm.
Not having the solid of clear and definite structure to become sharply correlated with these is the very narrow material of pore size distribution, because its pore dimension is controlled by the accurate multiple crystal unit of material three-dimensional skeleton.This class material is called " molecular sieve ", and wherein most important example is a zeolite.The accurate crystallization microstructure of most of zeolites shows in clear and definite X ray diffracting spectrum, generally contains many sharp-pointed very big peaks in the figure, can be used to determine uniquely this material.Equally, because the microstructural accurate repetition of crystallization, the size of this class material mesoporosity is very regular.The pore dimension of whole zeolites of having found so far is all at " micropore ", and (microp-orous) in the scope, this scope refers generally to 0.2 to 2nm, but the overall dimension of report is about 1.2nm.
In stacking material, the interatomic bond cooperation on the both direction of lattice use with the 3rd direction on essential distinction is arranged, get together in causing containing closely like laminar unitary structure.Usually, interatomic bonding is a height covalency bonding in these thin slices, and is interacted and combined by ionic forces or Van der Waals between contiguous slices.These back two kinds of power usually can be offset by more weak relatively chemical action, and the bonding action in the thin layer between the atom then is kept perfectly and is unaffected.
Therefore in some stacking material, can force adjacent layer separately, by inserting pillar they are fixed on this separation point position then, have highly porous material thereby make with certain swelling agent.For example, some clay can water make its expand, and each of its medium clay soil layer separated by water molecules.Some other stacking material can not expand by water, but it is expanded.The example of the non-water expandable layer of this class laminate materials is at United States Patent (USP) 4,859, has in No. 648 illustratedly, comprises stacked silicate, Ma Jiadi river natural stone (magadiite), kenyaite, three titanates and uhligite.Another example of non-water expandable layer laminate materials is to make its expansible contain titanium metal hydrochlorate (titanometallate) material in cavity with some organic expander, sees United States Patent (USP) 4,831, No. 006.
The X ray diffracting spectrum of the stacking material of various struttings can have significant change, depends on that expansion and strutting are for the stacked microstructural destructiveness that is in good order state usually.In some strutting stacking material, microstructural regularity is seriously like that destroyed, so that can only observe a peak that is in the low angle zone in the X-ray diffraction figure.Its interval-d is corresponding to the interlayer repeat distance that adds in the column material.Destroy not that serious material can in this zone, present several peaks, the general and same order of magnitude of this basic repeat distance.Sometimes also can be observed X ray reflection by the crystalline structure generation of each layer.Add narrower than in amorphous and the para-crystal material of pore size distribution in the column material at these, but wide than in the crystal frame material.
Stacking material is usually taked like laminar form, and it has reflected the asymmetry of the bonding action that is present in atom level.Such morphological properties can show with transmission electron microscopy.
The present invention relates to a kind of synthetic that comprises inorganic porous non-stacked crystalline phase material, after calcining, the X ray diffracting spectrum of this synthetic at interval has a peak at least greater than 1.8nm place at d-, and in the benzene adsorptive poweies of 6.7KPa (50 torr) and 25 ℃ times these materials greater than 15g benzene/100g material.
In preferred embodiment, the present invention relates to a kind of synthetic inorganic, porous crystalline phase material that comprises, it have into hexagonal array, diameter is at least 1.3nm and the uniform array of apertures of size, and after calcining, it shows a d who can be used for 1.8nm
100The hexagonal electron diffraction pattern spectrum that value indicates.
Here the pore dimension of mentioning not is strict crystallography yardstick, but measures the active porosity size that is determined by sorption.The better method of measuring pore dimension adopts the argon physisorphtion, and this is a kind of known technology and describes in detail in embodiment 21 (a) and 21 (b).In this method, record the quality of argon adsorbed under the sample condition that relative pressure changes in steady temperature and on the sample, and be used for drawing a constant temperature absorption line.Hole corresponding to the rapid dot mark that changes of gradient on the constant temperature absorption line and fill, and can decide pore dimension with it according to the relation of the known mathematical described in the embodiment 21.
Crystalline material of the present invention (refer to here have sufficient order, making provides the material of the diffracting spectrum that has a peak at least in available X ray, electronics or neutron diffraction after the calcining) can be with the structure that comprises very large hole window unknown before it and high sorptive power as feature.Material of the present invention generally is " mesopore ", that is to say that material has diameter at 1.3 holes of uniform size to the 20nm scope.Under better situation, material of the present invention has diameter at 1.8 holes of uniform size to the 10nm scope.In this respect, pore dimension is considered to the yardstick in the maximum perpendicular cross section of hole.
Material of the present invention can make a distinction with its regularity and other porous, inorganic solid of big open space, the size of this material hole more is similar to amorphous or para-crystal material, but hole regularly arranged and big or small evenly (for example, single phase inner pore distribution of sizes this phase hole mean sizes ± 25%, usually be ± 15% or littler) then more be similar to the such crystal frame material of zeolite.
In preferable arrangement, the porosity of crystalline material of the present invention is to be provided by the array that is the open slot of hexagonal arrangement substantially, and this character can easily be observed with electron diffraction and transmission electron microscopy.Particularly, the sample of the suitable orientation of material presents the hexagonal of vat to be arranged, and corresponding electronogram then provides the diffraction maximum point that approximate hexagonal is arranged.The d of electronogram
100Spacing is exactly the distance between adjacent 2 in the hexagonal lattice hko projection, and passes through formula
And the repeat distance a on the electron microscopic figure between viewed two grooves
0Link mutually.Observed this d on electronogram
100At interval, at interval corresponding to the d-at a low angle peak on the material X ray diffracting spectrum.The product of the highest order that this material makes so far can be observed 20-40 point clearly on electronogram.These figures can be with 100,110, and the hexagonal hko subclass of the reflection that the reflection of 200,210 uniquenesses such as grade and symmetry thereof are relevant indicates.
In this respect, when should be appreciated that the hexagonal array that mentions groove, not only comprise perfect hexagonal symmetry on the mathematics, and comprise such array that most of grooves are surrounded with the essentially identical nearest neighbour groove of its distance by six in material.Defective and imperfection will make the groove of quite a lot of quantity run counter to this criterion in varying degrees.Adjacent slot presents up to ± 25% random sample that departs from average repeat distance, still can clearly provide the identifiable image of oversized hole material of the present invention.
The most regular product of preferred materials of the present invention provides a hexagonal X ray diffracting spectrum that a few clear maximal point is arranged in the low angular regions of extreme.But X-ray diffractogram is the sufficient sign that exists of this class material always not, because alignment degree in microstructure and individual particle inner structure multiple degree can influence the number at observable peak.In fact, it is found that and have only a product at peak clearly in the X ray diffracting spectrum low angle zone, also contain quite a lot of quantity material of the present invention.
Crystalline material of the present invention, in its form after calcining, can be further with such X-ray diffraction figure as feature; This collection of illustrative plates has at least a peak to be in d-at interval greater than the position of about 1.8nm (for the K-α radiation of Cu, 2 θ are 4.909 degree), and this position is corresponding to the d of described material electronics diffraction pattern
100Value.
Under better situation, burnt crystalline material of the present invention be characterised in that its X ray diffracting spectrum have at least two peaks be in d-at interval greater than about 1nm (for the K-α radiation of Cu, 2 θ be 8.842 the degree) the position, wherein have at least one to be in d-, and do not have about 20% the peak of relative intensity less than the position of 1nm at interval greater than highest peak at d-at interval greater than the position of 1.8nm.Under situation more specifically, the X ray diffracting spectrum of burnt material of the present invention does not have about 10% the peak of relative intensity greater than highest peak less than the position of 1nm at interval at d-.In preferable hexagonal is arranged, have the d of the d-interval at a peak in the X ray diffracting spectrum at least corresponding to this material electronics diffraction pattern
100Value.
The X ray diffracting data is here gathered with the automatic diffraction system of Scintag PAD X, and this system adopts θ-θ geometric relationship, Cu K-α radiation and energy dispersion X-ray detector.Use the energy dispersion X-ray detector just not need incident or diffraction bundle of rays monochromator.Incident and diffraction X-ray beam all collimate with double slit incident and diffraction colimated light system.The size of used slit from the X-ray tube source, is respectively 0.5,1.0,0.3 and 0.2nm.Different slit systems can make each peak that varying strength is arranged.The material that has the maximum pore size among the present invention will need the more highly incident X beam of collimation, comes so that the incident X-rays bundle of low angle peak and transmission is differentiated.
Note by step-scan with per 2 θ, 0.04 degree for diffraction data, and wherein θ is a Bragg angle, and the gate time in per step is 10 seconds.Interplanar distance is calculated with millimicron (nm) from d, and the relative intensity I/I of each line
0(I wherein
0Be the strongest line at one of percentage of the above intensity of background) then be to derive with a linear fitting program.Each intensity is not revised Luo Lunzi and polarization effect.Relative intensity is with VS=very strong (75-100), S=strong (50-74), and m=medium (25-49), the weak symbols such as (0-24) of W=provides.Should be appreciated that in the diffraction data and list, may contain multiple superimposed spectral line as single line, they under certain condition (for example test resolving power very high or when crystallographic change takes place) can be rendered as each bar differentiate hold or part differentiate the line of holding.Typically crystallographic change can comprise the variation of the minor variations and/or the crystal symmetry of cell parameter, and does not have substantial variation on the structure.These accessory effects, comprise the variation of relative intensity, also the history that can use because of nature and extent, heat or hydro-thermal that the composition of cations, framework, hole are filled, cause by the difference of the other factors known to the caused peak width of particle size/shape effect/peak shape variation, structure disturbance or the X-ray diffraction technician.
Material of the present invention in the benzene adsorptive power of 6.7KPa (50 torr) and 25 ℃ of demonstrations greater than about 15g benzene/100g crystal.Certainly, the equilibrium adsorption ability of benzene must be the sample determination that hole is not subjected to accidental contaminants clog.For example, water can use dehydration technique (as thermal treatment) to remove, and inorganic non-crystalline material (as silicon-dioxide) and organism can be by with acid, alkali or other chemical reagent contact and/or remove by physical method (as calcining), make chipped material be removed and not to material production deleterious effects of the present invention.
Crystalline material of the present invention generally has following composition:
M
n/q(W
aX
bY
cZ
dO
h)
Wherein W is a kind of dyad, and as first row's transition metal of divalence, for example manganese, cobalt, nickel, iron and/or magnesium are preferably cobalt; X is a kind of trivalent element, as aluminium, boron, chromium, iron and/or gallium, is preferably aluminium; Y is a kind of quadrivalent element, as silicon and/or germanium, is preferably silicon; Z is a kind of pentad, as phosphorus; M is one or more ions, ammonium for example, IA, IIA and VIIB family ion, normally hydrogen, sodium and/or fluorion; N is that mentioned component is removed M and is expressed as the electric charge of oxide compound; Q is the weighting mole flat fare of M; N/q is mole number or the molar fraction of M; A, b, c and d are respectively W, X, the molar fraction of Y and Z; H equals a number of 1 to 2.5; And (a+b+c+d)=1.
A preferred embodiment of above-mentioned crystalline material, be (a+b+c) greater than d, and h=2.Be more preferably h=2, a=0 and d=0.
Synthesize good form just, the composition of material of the present invention (by anhydrous calculating) can be expressed as with experimental formula:
rRM
n/q(W
aX
bY
cZ
dO
h)
Wherein R is synthetic and be not included in whole organic materialss within the M as an ion with helping material, and r is the coefficient of R, i.e. the mole number of R or molar fraction.
M and R component are combined in the material owing to they are present in crystallisation process, and they are removed easily, and perhaps (in the situation of M) replaces with the post crystallization method that the back more specifically illustrates.For example, the original M ion (as sodium or chlorion) in the just synthetic back of material of the present invention can be by replacing with other ionic ion-exchange.Preferable displacement ion comprises metal ion, hydrogen ion, hydrogeneous parent ion (as ammonium) and their mixture.Especially good ion is that those can make catalytic activity satisfy the ion that some hydrocarbon conversion reactions requires.These ions comprise hydrogen, IA family (as K) on the rare earth metal and the periodic table of elements, IIA family (as Ca), VIIA family (as Mn), VIIIA family (as Ni), IB family (as Cu), IIB family (as Zn), IIIB family (as In), IVB family (as Sn) and VIIB family metal and their mixtures (referring to Sargent-Wclch ScientificCo.Cat.No.S-18806,1979) such as (as F).
Material with composition that following formula defines can be made by the reaction mixture with following composition, and the composition range of representing with oxide mol ratio of this mixture is: the useful scope preferred range of reactant X
2O
3/ YO
20 to 0.5 0.001 to 0.5X
2O
3/ (YO
2+ Z
2O
5) 0.1 to 100 0.1 to 20X
2O
3/ (YO
2+ WO+Z
2O
5) 0.1 to 100 0.1 to 20 solvent/(YO
2+ WO+Z
2O
5+ X
2O
3) 1 to 1,500 5 to 1000OH
-/ YO
20 to 10 0 to 5 (M
2/eO+R
2/fO)/(YO
2+ WO+Z
2O
5+ X
2O
3) 0.01 to 20 0.05 to 5M
2/eO/ (YO
2+ WO+Z
2O
5+ X
2O
3) 0 to 10 0 to 5R
2/fO/ (YO
2+ WO+Z
2O
5+ X
2O
3) 0.01 to 2.0 0.03 to 1.0
Wherein e and f are respectively the weighted mean valencys of M and R, and solvent wherein is a kind of C
1To C
5Alcohol or glycol, perhaps be more preferably water, and R comprises that general formula is R
1R
2R
3R
4Q
+Organic directing agent, wherein Q is nitrogen or phosphorus, and R
1, R
2, R
3And R
4In have at least one to be aryl or alkyl with 6 to 36 carbon atoms, as-C
6H
13,-C
10H
21,-C
16H
33With-C
18H
37, remaining R
1, R
2, R
3And R
4The alkyl that each all is selected from hydrogen and has 1 to 5 carbon atom.Derive above-mentioned An with Phosphonium ionic compound can be oxyhydroxide, halogenide, silicate or their mixture.
The special validity of above-mentioned directing agent, when compare with directing agent of known other directed synthetic one or more other crystalline structure, it is believed that be since it the nucleus of required oversized hole material form and growth in play the ability of model effect.The nonrestrictive example of this class directing agent comprises cetyltrimethyl ammonium, octadecyl San Jia Ji Phosphonium, benzyltrimethylammon.um, cetyl pyridinium, the tetradecyl trimethyl ammonium, decyl trimethyl ammonium, compounds such as dodecyl trimethyl ammonium and dimethyl two (dodecyl) ammonium.
Be present in the total organic matter R in the reaction mixture, preferably include additional organic directing agent of the An Huo Phosphonium ionic species that a kind of above-mentioned directing agent molecular formula represents, but R wherein
1, R
2, R
3, R
4Each all is the alkyl (alkyl can two couple together constitute ring compound) that is selected from hydrogen and has 1 to 5 carbon atom.The example of additional organic directing agent comprises tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, compounds such as TBuA and tetramethyleneimine.Organic directing agent of at first mentioning can be in 100/1 to 0.01/1 scope with the mol ratio of additional organic directing agent.When existence adds organic directing agent, R in the reaction mixture
2/fO/ (YO
2+ WO+Z
2O
5+ X
2O
3) mol ratio be advisable preferably 0.12 to 1.0 with 0.1 to 2.0.
In addition, in order to change the pore dimension of final crystalline phase material, can outside above-mentioned organic directing agent, comprise a kind of auxiliary organism in the reaction mixture.Should auxiliary organism be to be selected from aromatic hydrocarbon and amine and replacement of their halogen and the C that (1) has 5-20 carbon atom
1-C
14Alkyl-substituted derivatives, (2) have ring-type and many cycloaliphatic hydrocarbon and amine and the replacement of their halogen and the C of 5-20 carbon atom
1-C
14Alkyl-substituted derivatives, (3) have straight chain and branched aliphatic hydrocarbons and the amine and their the halogen substitutive derivative of 3-16 carbon atom.
In above-mentioned auxiliary organism, halogenic substituent is bromine preferably, C
1-C
14Alkyl substituent can be straight or the ramose aliphatic chain, for example methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group and their combination.The auxiliary organic example of this class comprises p-Xylol, Three methyl Benzene, triethylbenzene and triisopropylbenzene.
In reaction mixture, be mingled with when assisting organism (auxiliary organism)/YO
2Mol ratio will be 0.05 to 20, preferably 0.1 to 10, and the mol ratio of (auxiliary organism)/(organic directing agent) will be preferably 0.05 to 35 0.02 to 100.
When in synthetic method, using a silicon source, preferably use a kind of organosilicate, for example quaternary ammonium silicate to small part.The nonrestrictive example of this silicate comprises tetramethyl-ammonium silicate and tetraethyl orthosilicate.
Imagination is used for the various W of above-mentioned reaction mixture, X, and Y, the non-limitative example of Z combination comprises:
W???????X?????????Y?????????Z
-???????Al????????Si????????-
-???????Al????????-?????????P
-???????Al????????Si????????P
Co??????Al????????-?????????P
Co??????Al????????Si????????P
-???????-?????????Si????????-
Comprise that W is a kind of element (as Mn, Co and Ni) of Mg or first row transition metal that is selected from divalence; X is B, Ga or iron; And Y is the various combinations of Ge.
In order to make crystalline material of the present invention, above-mentioned reaction mixture is the temperature at 25 to 250 ℃, is preferably at 50 to 175 ℃, pH is preferably under 9 to 14 the condition, it is maintained to the required crystal of generation, and the general time length is 5 minutes to 14 days, preferably 1 to 300 hour.
When crystalline material of the present invention was a kind of pure aluminium silicate, synthetic method can may further comprise the steps easily:
(1) organic directing agent (R) is mixed with solvent or mixed solvent, make solvent/R
2/fThe O mol ratio in 50 to 800 scope, preferably 50 to 500." original pattern " of this mixture constructive method.
(2) in the original pattern mixture of step (1), add silicon-dioxide and aluminum oxide, make R
2/fO/ (SiO
2+ Al
2O
3) ratio in 0.01 to 2.0 scope.
(3) mixture of whipping step (2) gained under 20 to 40 ℃ temperature, churning time is with better in 5 minutes to 3 hours.
(4) allow this mixture in stirring or not, put 10 minutes to 24 hours with stirring, be preferably under 20 to 50 ℃ temperature.
(5) under 50 to 150 ℃ temperature, make the product crystallization 1 to 72 hour of step (4).
When effect sorbing agent or catalyst component, synthetic of the present invention should be through handling, partly or wholly to remove its organic constituent.This synthetics also can be combined closely with a hydrogenation component in the place that needs are carried out hydrogenation-dehydrogenation function and as catalyst component, the example of hydrogenation component is a kind of precious metal or its mixture of tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or platinum, palladium and so on.Such component can be passed through cocrystallization, exchanges within the composition so that reach the degree that IIIB family metal (as aluminium) exists in the structure, is impregnated into its inside, with it closely physics mode such as be blended together and enter within the synthetics.Such component (under the situation of platinum) for example can by handle with the ion solution that contains platinum metal that silicate is impregnated within the synthetics or on.The platinic compound that is fit to this purpose comprises Platinic chloride, platinous chloride and all cpds that contains platinum and amine complex compound.
Above-mentioned crystalline material, particularly its metal, hydrogen and ammonia form can advantageously be converted into another form by thermal treatment (calcining).This thermal treatment was generally carried out 1 minute under 400-750 ℃ temperature at least, was no more than 20 hours usually, preferably 1 to 10 hour.Though can adopt pressure below atmospheric pressure during thermal treatment, for convenience's sake, more be willing to use barometric point, for example in air, nitrogen and ammonia.Be specially adapted to some hydrocarbon conversion reactions of catalysis through heat treated product.
Crystalline material of the present invention should be through dehydration when being used as sorbent material or being used as the catalyst component of organic compound conversion process, dehydration at least in part.This can be by in atmosphere such as air, nitrogen, normal pressure, alkali press and pressurized conditions under, 200-595 ℃ temperature range internal heating 30 minutes to 48 hours and reaching.Dehydration also can at room temperature only be placed on this synthetic in the vacuum to be carried out, but will obtain the longer time of dehydration needs of quantity sufficient.
Various composition useful as catalysts component of the present invention, transform (as oxide compound and hydro carbons) by acid catalyzed reaction catalysis organic compound.The size of hole is to make that the specific selectivity of spatial with respect to transition state animal kind is minimum (Chen etc. " shape in the industrial application is selected catalysis " 36CHEMICALINDUSTRIES41-61 page or leaf (1989)) in reactions such as cracking.Because material of the present invention mesoporosity is very big, thereby diffusional limitation also is reduced to minimum.Owing to these reasons, synthetics of the present invention is specially adapted to the following reaction of catalysis: these are reflected under the condition that there is acid position in catalyst surface and take place, and relate to reactant with big molecular dimension, product and transition state species, its molecular dimension too big so that can not with conventional macrovoid solid catalyst (as X zeolite, Y, L, ZSM-4, macrovoid zeolites such as ZSM-18 and ZSM-20) similar reaction takes place.
So, catalyst component of the present invention is specially adapted to have the conversion of the organic compound of macromole size, as have a hydro carbons that replaces or do not replace the height aromatics of polycyclic aromatic component, huge naphthenic compound or have the compound that the height of huge steric configuration replaces, for example molecular dimension is 1.3nm or bigger compound.The molecular weight that this catalyst component is particularly useful for raw material is reduced to the reaction (being cracking or hydrocracking) of smaller value.Cracking can be 200-800 ℃ in temperature, pressure be barometric point to 100psig (100-800KPa), be to carry out under 0.1 second to 60 minutes the condition duration of contact.Hydrocracking can be 150-550 ℃ in temperature, and pressure is 100-3000psig (800-20800KPa), and weight per hour space velocity is 0.1-100, and hydrogen/hydrocarbon mol ratio is to carry out under the condition of 0.1-100.
This catalyst component is particularly useful for using high molecular, high boiling point or the reaction of the reaction, particularly residuum feedstocks that can not the distillatory raw material be risen (promptly basically can not the distillatory raw material or play the raw material of initial boiling point [5% point] more than 1050 [565 ℃]).Can comprise that api gravity is lower than about 20 with the residuum feedstocks that this catalytic composition uses, be usually less than 15, representative value is 5-10, and Conradsen Kang Laxun carbon residue content (CCR) is at least 1% weight, more generally be at least 5% or more, as the raw material of 5-10%.CCR can be up to 20% weight even higher in some residual oil fraction.The aromaticity content of these raw materials is also correspondingly high, and the content of heteroatoms (as sulphur and nitrogen) and metal also is correspondingly high.The aromaticity content of these raw materials generally is at least 50% weight, and much higher in typical case (usually being at least 70-80% weight), all the other mainly are cycloalkanes and heterogeneous ring compound.Such refinery feedback material is typically and comprises normal pressure and vacuum column Residual oil, pitch is by the aromatics extract that solvent extraction process (as phenol or furfural extraction) obtains, deasphalting oil, waste oil, and make residual cut in the class process of lubricating oil, coking.Can comprise gas oil (as normal pressure gas oil) with the high boiling fraction that this catalyst component uses; Vacuum gas oil; Turning oil, especially heavy cycle oil; Deasphalted oil; Solvent extractable matter is as bright stock; And heavy gas oil, as heavy coking gas oil.This catalytic material also can be applicable to the feedback material of non-petroleum sources, the synthetic oil that for example gelatin liquefaction produced, the wax that obtains in the Fischer-Tropsch building-up process and its heavy oil fraction and other materials similar.
Also can be used for the selective conversion of mineral compound according to catalytic composition of the present invention, for example make and contain nitrogen oxide (NO
x) gaseous mixture (as industrial gaseous waste and hydro carbons is processed catalyst system therefor in the operation of catalytic pyrolysis particularly carry out the gas that generates in the oxidative regeneration process) in nitrogen oxide transform, this porous crystalline material can be used for this purpose with the form that matrix is arranged or do not have a matrix, and can suitably form extrudate, ball sheet or other shape are passed through catalyzer thereby allow gas to fall with the pressure of minimum.Crystalline material preferably is Hydrogen at least in part, but also can advantageously contain small amount of precious metals (particularly using metal, the especially platinum in periodictable VIIIA family the 5th and the 6th cycle, palladium, rubidium, rhodium, iridium or their mixture) as catalyst component.The typical amounts of precious metal is below 1% weight, but the most handy lower quantity, for example below 0.1 or 0.5% weight.
NO
xReduction, be that the gas that contains nitrogen oxide by catalyzer is undertaken improving under the temperature (typical temperature is 200 ℃, generally 200-600 ℃ of scope) at least.This gaseous mixture can mix with ammonia promoting the reduction of nitrogen oxide, and pre-mixing can be carried out under the temperature of height to 200 ℃.With the gaseous mixture quantity of blended ammonia mutually, it generally is 0.75 to 1.25 scope in stoichiometric, and stoichiometric quantity itself also is that the ratio according to various nitrogen oxide in the gaseous mixture becomes, shown in following reaction formula:
Crystalline material of the present invention also can be used for nitrogen oxide in the reducing gas mixture under the condition that other reductive agent (as carbon or carbon monoxide) exists.The nitrogen oxide that reduces by this way has special purposes for the regeneration of fluid catalytic cracking (FCC) catalyzer, to produce the carbon monoxide of desired concn because regenerate under proper condition, it will be used to reduce NO in the regeneration gas under the condition that catalyzer exists
xRatio.
Composition of the present invention also can be used as sorbent material and separate medium body in pharmaceutical chemistry or fine chemistry application.For example, these super large hole syntheticss can be used to purify medicine of Regular Insulin and so on or as the solid carrier of medicine sustained release.It is waste treatment that the another kind of these oversized hole gap materials is used, and this has developed its unusual volume of voids.Therefore, the mixture that has the difference sorption properties with respect to super large hole synthetics of the present invention for each component, by mixture is contacted with said composition,, just a kind of component partially or substantially all can be separated from mixture at least with a certain component of sorption optionally.This isolating example comprises and contacting with composition with the mixture of at least a hydrocarbon component containing water that this at least a hydrocarbon component is with regard to selected sorption.Another example is to select at least a hydrocarbon component of sorption from the mixture that comprises hydrocarbon component and at least a additional hydrocarbons component.
When as catalyzer, may wish the material of used temperature and other condition in crystal composition of the present invention and the another kind of anti-anti-organic transformation technology is combined.These materials comprise activity and non-active material, synthetic and natural zeolite, and the metal oxide of the inorganic materials of clay, silicon-dioxide and so on and/or aluminum oxide, titanium oxide, zirconium white and so on.The latter can be natural, also can be gum deposit or colloidal form (mixture that comprises silicon-dioxide and metal oxide).Use and new crystal combination material together,, the transformation efficiency and/or the selectivity of catalyzer in some organic transformation process are changed promptly with its chemical combination or be present in new crystal building-up process (new crystal is active).Non-active material can be suitably as thinner, controlling the inversion quantity in the given process, thereby obtains product economically and regularly and need not adopt other method to control speed of reaction.These materials can combine with natural clay (as wilkinite and kaolin), to improve the shatter strength of catalyzer under the commercial operation condition.Described material (being clay, oxide compound etc.) plays a part the tackiness agent of catalyzer.People wish to provide a kind of catalyzer with good shatter strength, can prevent catalyst breakage powdering material because wish on commercial applications.Usually these clay adhesives just adopt for the shatter strength of improving catalyzer.
Can comprise polynite family and kaolin group with the natural clay of new crystal combination, this two family comprises sub-bentonite (Subbentonite), the common Dixie of being called clay, McNamee clay, Georgia clay, the lourie that boils reach clay or essential mineral composition be halloysite (halloysite) kaolinite, open other various kaolin of face (dickite), nakrite (nacrite) or anauxite (anauxite).These clays can use in the unprocessed state that exploitation is come out, and perhaps at first re-use through calcining, acid treatment or chemical modification.
Outside above-mentioned materials, new crystal also can with as silica-alumina, silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silicon-dioxide-titanium oxide and ternary complex such as silica-alumina-Thorotrast, silica-alumina-zirconium white, certain porous matrix material of silica-alumina-magnesium oxide and silica-magnesia-zirconium white etc. combines.
Above-mentioned body material preferably can have at least a part to provide with colloidal form, so that the easily extrusion molding of bonded catalyzer various ingredients.
The crystalline material that separates subtly and the relative proportion of inorganic oxide matrix can have a great difference, and crystalline content is at the 1-90% weight range, and (particularly mixture is made under the situation of pearl) more generally is at the 2-80% of complex body weight range.
Hereinafter with reference to embodiment and accompanying drawing the present invention is described more specifically, wherein:
Fig. 1-14 is respectively the X ray diffracting spectrum of the product of embodiment 1-13 and 15.
Figure 15 is the isothermal adsorption curve that physical adsorption is measured among the embodiment 21.
Figure 16 is the figure that gained is measured in physical adsorption among the embodiment 21, shows the pore dimension of various crystalline materials.
Figure 17 is the electron diffraction collection of illustrative plates of the product of embodiment 4.
Figure 18 is the transmission electron microscopy figure of the product of embodiment 4.
Figure 19 is the transmission electron microscopy figure of the product of embodiment 5.
Figure 20 is the transmission electron microscopy figure of the product of embodiment 18.
Figure 21 is the X ray diffracting spectrum of the product of embodiment 23.
Figure 22 shows d-at interval the influence of auxiliary organism to first X-ray diffraction maximum value of embodiment 23-31.
Figure 23 is embodiment 23,25, the pore dimension of 26,28,29,31 product and X ray d-graph of a relation at interval.
Figure 24 is embodiment 23,25, the volume of voids of 26,28,29,31 product and X ray d-graph of a relation at interval.
Figure 25-28 is respectively the X ray diffracting spectrum of the product of embodiment 46-49.
In each embodiment, when providing the sorption data with relatively to the sorptive power of water, hexanaphthene, benzene and/or normal hexane the time, they are equilibrium adsorption values of measuring by the following method:
With a load weighted sample of sorbent, calcined at least about 1 hour about 540, handle through other more in case of necessity, to remove the pollutent of any block pores, in adsorption chamber, contact again with pure adsorbate gas to be measured.The increase of adsorbent weight is the adsorptive power that unit is calculated as sample with g/ (100g sorbent material) just, is benchmark with the weight of sorbent material after about 540 ℃ of calcinings during calculating.This synthetics in the balance benzene adsorptive power of 50 torrs (6.7KPa) and 25 ℃ greater than about 15g/100g, preferably greater than about 17.5g/100g, better greater than about 20g/100g.
Measuring the better method of adsorptive power, is in being evacuated to the adsorption chamber that pressure is lower than 1mm material of the present invention to be contacted with pure adsorbate gas to be measured.Making pressure keep constant by a pressurestat control adding adsorbate gas between adsorption cycle (stablizes extremely approximately ± 0.5mm).When the new crystal absorption of adsorbed material quilt, the reduction of pressure will make pressurestat open a valve, make more adsorbate inlet chamber interior to recover above-mentioned control pressure.When pressure change was not enough to start pressurestat, adsorption process had just been finished.
The another kind of method of measuring the absorption of benzene is to carry out with a suitable thermogravimetric analysis system, for example computer-controlled 990/951du Pont TGA system.With sample of sorbent in the mobile helium about 350 ℃ or 500 ℃ of following thermal dehydrations to constant weight constant (removing the moisture of physical adsorption).If sample is to have synthesized good shape just, for example contain organic directing agent, it be in air, dewater under about 540 ℃ constant rather than take above-mentioned 350 ° or 500 ℃ of processing to constant weight, the sorption isotherm of benzene is 25 ℃ of measurements, during measurement with the saturated helium flow of a branch of benzene and a branch of pure helium flow by the proper proportion fusion to obtain required benzene dividing potential drop.Try to achieve at the adsorptive value of 50 torrs (6.7KPa) benzene by the isothermal adsorption line chart.
With 100g cetyltrimethyl ammonium (CTMA) hydroxide solution-this solution is with N, N, N-trimethylammonium-1-cetyltrimethyl ammonium muriatic 29% (weight) solution contact and the aqueous silicate solution (10% silicon-dioxide) of one and the 100g tetramethyl-ammonium (TMA) that prepare mixes with hydroxide ion exchange halogen ionic ion exchange resin with a kind of.Add 25gHisil (the precipitation water of the combined moisture of a kind of free water content that contains 6% weight of having an appointment and about 4.5% weight contains silicon-dioxide, and its limit granular size is about 0.02 μ).The gained mixture is put into a polypropylene vial, and this bottle is placed in 95 ℃ the steam tank and spends the night.The ingredients of a mixture is corresponding to every mole of Al
2O
3Contain
2.7 mole Na
2O
392 moles of SiO
4
35.7 mole (CTMA)
2O
61.7 mole (TMA)
2O
6231 moles of H
2O
Reclaim by filtering the solid product that will produce, and air drying at ambient temperature.Then product was calcined 1 hour the calcining in air that continues 6 hours in 540 ℃ of following nitrogen.
It is 475m that product after the calcining records surface-area
2/ g, and have following equilibrium adsorption ability (unit is g/100g):
H
2O8.3
Hexanaphthene 22.9
Normal hexane 18.2
Benzene 21.5
The X-ray diffractogram of present embodiment calcinate as shown in Figure 1.In Ben Tu and later each figure, the d-that please notes 10 dusts (1.0nm) is at interval corresponding to 8.842 2 θ (the K-α radiation of Cu) that spend, and 18 dusts (1.8nm) are corresponding to 4.909 degree.
The feature of present embodiment product is to be spaced apart 3.78 ± 0.2nm place at d-the very strong line of one relative intensity is arranged, and 2.16 ± 0.1 and 1.92 ± 0.1nm place weak line is respectively arranged.Present described oversized hole material is present in this fact in the present embodiment product, is shown by transmission electron microscopy (TEM), and its produces resembling and d of even space that hexagonal arranges
100Equal the hexagonal electron diffraction pattern of 3.9nm.
Oxyhydroxide (25%) aqueous solution of 100g cetyltrimethyl ammonium (CTMA) oxyhydroxide (prepared as embodiment 1) with 100g tetramethyl-ammonium (TMA) is mixed.Add 25gHisiL (the precipitation water of the combined moisture of a kind of free water content that contains 6% weight of having an appointment and about 4.5% weight contains silicon-dioxide, and its limit granular size is about 0.02 μ).The mixture of gained is put into a fixed autoclave to spend the night at 150 ℃.This ingredients of a mixture is corresponding to every mole of Al
2O
3Contain:
2.7 mole Na
2O
291 moles of SiO
2
35.7 mole (CTMA)
2O
102 moles (TMA)
2O
6120 moles of H
2O
Reclaim by filtering the solid product that will produce, and air drying at ambient temperature.Then product was calcined 1 hour the calcining in air that continues 6 hours in 540 ℃ of following nitrogen.
It is 993m that product after the calcining records surface-area
2G, and have following equilibrium adsorption ability (unit is g/100g):
H
2O7.1
Hexanaphthene 47.2
Normal hexane 36.2
Benzene 49.5
The X-ray diffractogram of present embodiment calcinate as shown in Figure 2.It is characterized in that being spaced apart 3.93 ± 0.2nm place at d-has the very strong line of a relative intensity, and 2.22 ± 0.1 and 1.94 ± 0.1nm place respectively have weak line, TEM to demonstrate this product to comprise oversized hole material of the present invention.
Then the part in the above-mentioned product is contacted 2 hours with 100% water vapor at 790 ℃ (1450 °F), the surface-area that records the material of this steaming is 440m
2/ g shows through about 45% of fierce boiling rear surface to remain.
Another part calcinate of this embodiment is contacted 2 hours at 680 ℃ (1250 °F) with 100% steam, and the surface-area that records this material is 718m
2/ g shows that 72% of steam treatment rear surface under these conditions is retained.
With water, as embodiment 1 prepared cetyltrimethyl ammonium hydroxide solution, Tai-Ace S 150, HisiL and a kind of tetrapropyl ammonium (TPA) bromide (35%) aqueous solution produce a kind of mixture, and this ingredients of a mixture is with regard to every mole of Al
2O
3And opinion is:
0.65 mole Na
2O
65 moles of SiO
2
8.8 mole (CTMA)
2O
1.22 mole (TPA)
2O
1336 moles of H
2O
The mixture of gained is placed in the polypropylene vial, this bottle is placed in 95 ℃ of steam tanks 192 hours, mix with the sample cool to room temperature and with the TMA hydroxide solution of embodiment 1 prepared CTMA hydroxide solution and 25% (weight) then, mixing is by following weight ratio: 3 parts of said mixtures, 1 part of CTMA oxyhydroxide and 2 parts of TMA oxyhydroxide, the mixture that this mixing is obtained is placed in the polypropylene vial then, and preserves in 95 ℃ of steam tanks and spend the night.The composition of this mixture is with regard to every mole of Al
2O
3And opinion is:
0.65 mole Na
2O
65 moles of SiO
2
15 moles (CTMA)
2O
1.22 mole (TMA)
2O
35.6 mole (TMA)
2O
2927 moles of H
2O
Reclaim by filtering the solid product that will produce, and air drying at ambient temperature, then this product was calcined 1 hour in 540 ℃ nitrogen, that continues aloft calcined 6 hours.
It is 1085m that product after the calcining records surface-area
2/ g, and have equilibrium adsorption ability (unit is g/100g) under several:
H
2O11.5
Hexanaphthene＞50
Normal hexane 39.8
Benzene 62
The X-ray diffractogram of present embodiment calcinate as shown in Figure 3.The feature of present embodiment product is to be spaced apart 3.82 ± 0.2nm place at d-the very strong line of one relative intensity is arranged, and 2.22 ± 0.1 and 1.94 ± 0.1nm place respectively have weak line, TEM to demonstrate this product to comprise oversized hole gap material of the present invention.
With 200g such as embodiment 1 prepared cetyltrimethyl ammonium (CTMA) hydroxide solution and 2gCatapalalumina (α-Al
2O
3-hydrate, 74%Al
2O
3) and 100 gram tetramethyl-ammonium (TAM) silicate (10%SiO
2) aqueous solution mixes.Add 25gHisiL (precipitated hydrated silica of the combined moisture of a kind of free water content that contains 6% weight of having an appointment and about 4.5% weight, its limit granular size is about 0.02 μ).The gained mixture is put into a fixed autoclave, placed 48 hours at 150 ℃, the composition of this mixture is with regard to every mole of Al
2O
3And opinion is:
0.23 mole Na
2O
33.2 mole SiO
2
6.1 mole (CTMA)
2O
5.2 mole (TMA)
2O
780 moles of H
2O
Reclaim by filtering the solid product that will produce, and air drying at ambient temperature, the calcining in air that continues 6 hours then this product was calcined 1 hour in 540 ℃ nitrogen.
It is 1043m that product after the calcining records surface-area
2/ g, and have following equilibrium adsorption ability (unit is g/100g):
Water 6.3
Hexanaphthene＞50
Normal hexane 49.1
Benzene 66.7
The X-ray diffractogram of the burnt product of present embodiment as shown in Figure 4.It is characterized in that being spaced apart 4.08 ± 0.2nm place at d-has the very strong line of a relative intensity, and 2.31 ± 0.1 and 2.01 ± 0.1nm place weak line is respectively arranged.TEM shows that this product comprises oversized hole gap material of the present invention (seeing example 22).
With 260g and 77g phosphoric acid (85%), 46g Catapal aluminum oxide (74% aluminum oxide) and 24g tetramethyleneimine (PYr) mix in stirring.The autoclave pressure that this first mixture is put into stirring is heated to 150 ℃ and kept 6 days.Filtration of material is come out, clean and dry air.Product 50g and 200g water and 200g are made into slurry by the cetyltrimethyl ammonium hydroxide solution of embodiment 1 preparation.And then add 400g tetraethyl ammonium silicate solutions (10% silicon-dioxide) and form second mixture, this mixture is put into a polypropylene vial, and be placed in 95 ℃ the steam tank and spend the night.First the ingredients of a mixture is corresponding to every mole of Al
2O
3Contain:
1.0 mole P
2O
5
0.51 mole (PYr)
2O
47.2 mole H
2O
Reclaim by filtering the solid product that will produce, and dry under air at room temperature, and product was calcined 1 hour in 540 ℃ nitrogen then, calcined 6 hours in air again.
Recording burnt product, to record surface-area be 707m
2/ g, and have following equilibrium adsorption ability (is unit with g/100g):
H
2O33.2
Hexanaphthene 19.7
Normal hexane 20.1
Benzene 23.3
The X-ray diffractogram of the burnt product of present embodiment as shown in Figure 5.Its feature is to be spaced apart 2.54 ± 0.15nm place at d-the very strong line of a kind of relative intensity is arranged.TEM represents that product contains oversized hole gap material of the present invention (seeing embodiment 22).
With 1.35gNaAlO
2(43.5%Al
2O
3, 30%Na
2O) be dissolved in the solution and the 17.3gNaOH of 45.2g water gained, 40% aqueous solution of 125.3g colloid silica (40%, Ludox HS-40) and 42.6g tetraethyl ammonium (TEA) oxyhydroxide together.After stirring is spent the night, mixture is placed in the steam tank (95 ℃) heating 7 days.After the filtration, 151g solution and 31g are mixed by the cetyltrimethyl ammonium hydroxide solution of embodiment 1 preparation, and seasoning 13 days in 95 ℃ steam tank.Mixture has following relative mole and forms:
0.25 mole Al
2O
3
10 moles of Na
2O
36 moles of SiO
2
0.95 mole (CTMA)
2O
2.5 mole (TEA)
2O
445 moles of H
2O
Reclaim by the solid product that filters gained, and water and ethanol cleaning.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.
The product that alkene burnt contains 0.14% weight Na, 68.5% weight SiO
2With 5.1% weight Al
2O
3, and the equilibrium benzene adsorptive power that records it is 58.6g/100g.
The X-ray diffractogram of the burnt product of present embodiment as shown in Figure 6.Its feature is to be spaced apart 3.14 ± 0.15nm place at d-a line that relative intensity is very strong is arranged.TEM shows that product contains oversized hole gap material of the present invention.
With 150g by the mixture (initial pH is 12.64) of cetyltrimethyl ammonium (CTMA) oxyhydroxide of embodiment 1 preparation and 21g colloid silica (40% Ludox HS-40) in-300cc autoclave under 150 ℃ with 200rpm stirring heating 48 hours.The ingredients of a mixture is to contain corresponding to every mole of SiO:
0.5 mole (CTMA)
2O
46.5 mole H
2O
Reclaim by filtering the solid product that will produce, water cleans, and calcines 6 hours in 540 ℃ air then.
Record 0.01% weight sodium that consists of of burnt product, 93.2% weight SiO
2With 0.016% weight Al
2O
3, its surface-area is 992m
2/ g, and have following equilibrium adsorption ability (is unit with g/100g):
Water 4.6
Hexanaphthene＞50
Normal hexane＞50
Benzene 62.7
The X-ray diffractogram of the burnt product of present embodiment its feature as shown in Figure 7 is to be spaced apart 4.36 ± 0.2nm place at d-the very strong line of one relative intensity is arranged, and 2.51 ± 0.15 and 2.17 ± 0.1nm place weak line is respectively arranged.TEM shows that this product comprises oversized hole gap material of the present invention.
The 4.15g sodium aluminate slowly is added to 100g water contains 16g tetradecyl TMA (TriMethylAmine) bromide (C
14TMABr) in the solution.And then in this mixture, add tetramethyl-ammonium silicate (100g-10%SiO
2), HiSil (25g) and tetramethyl-ammonium oxyhydroxide (14.2g-25% solution).This mixture has following relative mol composition:
1.9 mole Al
2O
3
3.0 mole NaO
2
54 moles of SiO
2
2.4 mole (C
14TMA)
2O
6.1 mole (TMA)
2O
628 moles of H
2O
Mixture was placed in the inherent 120 ℃ of stirrings of autoclave crystallization 24 hours.Products therefrom is filtered, clean and dry air.Ultimate analysis shows that product contains 53.3% weight SiO
2, 3.2% weight Al
2O
3, 15.0% weight C, 1.88% weight N, 0.11% weight Na, and 1000 ℃ ash content is 53.5% weight.Fig. 8 calcines 1 hour X ray diffracting spectrum of 6 hours material of calcining in air again through 540 ℃ in nitrogen.This diffractogram d-is spaced apart 3.53 ± 0.2nm place the very strong line of a relative intensity, and be spaced apart 2.04 ± 0.1 and 1.77 ± 0.1 places at d weak line is arranged.TEM shows that product contains oversized hole gap material of the present invention.
Burnt again product has 827m after washing also at room temperature exchanges with the 1N ammonium nitrate solution
2The surface-area of/g and following equilibrium adsorption ability (unit is that g/100g does not have water absorbent):
Water 30.8
Hexanaphthene 33.0
Normal hexane 27.9
Benzene 40.7
The 8.3g sodium aluminate slowly is added to the water-reducible 184g dodecyl trimethyl ammonium of 480g oxyhydroxide (C
12TMAOH, 50%) in the solution.In this mixture, add Ultra Sil (50g) and tetramethyl-ammonium silicate (200g-10%SiO again
2) aqueous solution and tetramethyl-ammonium oxyhydroxide (26.38g-25% solution).Mixture has following relative mol composition:
0.36 mole Al
2O
3
0.55 mole Na
2O
11 moles of SiO
2
1.9 mole (C
12TMA)
2O
1.2 mole (TMA)
2O
394 moles of H
2O
11.1 mole Virahol
Mixture is put into autoclave crystallization 24 hours under 100 ℃ of stirrings.Products therefrom is filtered, clean and dry air.Fig. 9 is the X ray diffracting spectrum that 6 hours material was calcined in calcining in 1 hour then in air in 540 ℃ of nitrogen.Being spaced apart 3.04 ± 0.15nm place at d on the X ray diffracting spectrum has the very strong line of a relative intensity, and d be spaced apart 1.77 ± 0.1 and 1.53 ± 0.1nm place weak line is arranged.TEM shows that product contains oversized hole material of the present invention.
Through cleaning, burnt again sample has 1078m after at room temperature exchanging with the 1N ammonium nitrate solution
2The surface-area of/g and following equilibrium adsorption ability (unit is that g/100 does not have water absorbent):
Water 32.6
Hexanaphthene 38.1
Normal hexane 33.3
Benzene 42.9
With 4.9gNaAlO
2(43.5%Al
2O
3, 30%Na
2) solution in 37.5g water and 40% aqueous solution of 46.3cc tetraethyl ammonium oxyhydroxide and 96g colloid silica (40%, LudoxHS-40) mix.With gel vigorous stirring 0.5 hour, mixes by the cetyltrimethyl ammonium hydroxide solution of embodiment 1 preparation with isopyknic (150ml) again, reacted 168 hours down at 100 ℃.The composition of this mixture is corresponding to every mole of Al
2O
3Contain:
1.1 mole Na
2O
30.6 mole SiO
2
3.0 mole (TEA)
2O
3.25 mole (CTMA)
2O
609 moles of H
2O
Reclaim by filtering the solid product that will produce, water cleans, and calcines 6 hours in 540 ℃ of air then.
Burnt product has 1352m
2The surface-area of/g and following equilibrium adsorption ability:
Water 23.6
Hexanaphthene＞54
Normal hexane 49
Benzene 67.5
The X ray diffracting spectrum of the burnt product of present embodiment as shown in figure 10.It is characterized in that being spaced apart 3.85 ± 0.2nm place at d-has the very strong line of a relative intensity, and one weak line is arranged at 2.03 ± 0.1nm place.TEM shows that product contains oversized hole gap material of the present invention.
Cetyltrimethyl ammonium (CTMA) hydroxide solution of 200g being pressed embodiment 1 preparation under agitation mixes with 4.15g sodium aluminate and 100g tetramethyl-ammonium TMA aqueous silicate solution (10% silicon-dioxide).Add 25g HiSiL (a kind of have an appointment 6% weight percent free moisture and about 4.5% weight combined moisture of containing, limit particle size is the precipitated hydrated silica of 0.02 μ m).The mixture of gained is put into the immobilized autoclave pressure to be put 24 hours down at 150 ℃.The composition of mixture is corresponding to every mole of Al
2O
3Contain:
1.25 mole Na
2O
27.8 mole SiO
2
5.1 mole (CTMA)
2O
4.40 mole (TMA)
2O
650 moles of H
2O
Reclaim by filtering the solid product that will produce, and dry under the envrionment temperature in air.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.TEM shows that this product contains oversized hole material of the present invention.The X-ray diffractogram of the burnt product of present embodiment as shown in figure 11.It is characterized in that being spaced apart 4.42 ± 0.2nm place at d has the very strong line of a relative intensity, and 2.52 ± 0.15 and 2.2 ± 0.1nm place weak line is arranged.
Record the incinerating product and have 932m
2The surface-area of/g and following equilibrium adsorption ability (unit is g/100g):
Water 39.3
Hexanaphthene 46.6
Normal hexane 37.5
Then with the product and the 1N NH of present embodiment
4NO
3Solution is made ammonium ion exchange, calcines 10 hours under 540 ℃ in air again.
Embodiment 12
Cetyltrimethyl ammonium (CTMA) hydroxide solution of 200g being pressed embodiment 1 preparation under agitation mixes with the aqueous solution (10% silicon-dioxide) of 4.15g sodium aluminate and 100g tetramethyl-ammonium (TMA) silicate.Add 25gHiSiL (a kind of contain have an appointment 6% weight free water and about 4.5% weight combined moisture limit particle size be the precipitated hydrated silica of about 0.02 μ).The mixture of gained was put 48 hours under 100 ℃ in steam tank.The composition of mixture is corresponding to every mole of Al
2O
3Contain:
1.25 mole Na
2O
27.8 mole SiO
2
5.1 mole (CTMA)
2O
4.4 mole (TMA)
2O
650 moles of H
2O
Reclaim by filtering the solid product that will produce, and air drying at ambient temperature.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.
Record burnt product and have following equilibrium adsorption ability (unit is g/100g):
Water 35.2
Hexanaphthene＞50
Normal hexane 40.8
Benzene 53.5
The X ray diffracting spectrum of the burnt product of present embodiment as shown in figure 12.It is characterized in that being spaced apart 3.91 ± 0.2nm place at d has the very strong line of a relative intensity.And 2.24 ± 0.1 and 1.94 ± 0.1nm place weak line is arranged.TEM shows that this product contains oversized hole gap material of the present invention.
Then with the product and the 1N NH of present embodiment
4NO
3Solution is made ammonium ion exchange, calcines 10 hours in 540 ℃ of air again.
With muriatic 29% aqueous solution of 125gCTMA, 200g water, 3g sodium aluminate (in the 50g water), 65g UltraSiL (the amorphous precipitated silica of buying from Pq Corp.) and the mixture of 21gNaOH (50g water) fully stir, and 150 ℃ of crystallizations 168 hours.Reaction mixture has following relative mol composition corresponding to every mole of silicon-dioxide:
0.10 mole (CTMA)
2O
21.89 mole H
2O
0.036 mole NaAlO
2
0.53 moles of NaOH
By filtering solid product is separated, water cleans, and at room temperature dry 16 hours, calcines 10 hours in 540 ℃ of air again.
Record burnt product and have 840m
2The surface-area of/g and following equilibrium adsorption ability (unit is g/100g):
Water 15.2
Hexanaphthene 42.0
Normal hexane 26.5
Benzene 62
The X ray diffracting spectrum of the burnt product of present embodiment is characterized in that being spaced apart 4.05 ± 0.2nm place at d has the very strong line of a relative intensity as shown in figure 13.TEM shows that product contains oversized hole gap material of the present invention.
Embodiment 14
In order to contrast, take out a kind of overstable zeolite Y of industrial preparation.Its equilibrium benzene adsorptive power is 20.7g/100g.Its X-ray diffractogram has the line of whole zeolite Y, and the climax is spaced apart the 1.40nm place about d.
In order to prepare the original pattern mixture of present embodiment, 240g water is added to 92g contains 50% dodecyl trimethyl ammonium oxyhydroxide, in the solution of 36% Virahol (IPA) and 14% water, make (solvent)/(R
2/fO) mol ratio is 155.Water/R in this mixture
2/fThe O mol ratio is 149, and IPA/R
2/fThe O mol ratio is 6.In this original pattern mixture, add 4.15g sodium aluminate, 25gHiSiL, the aqueous solution (10%SiO of 100gTMA silicate
2) and 25% aqueous solution of 13.2gTMA oxyhydroxide.The R of this solution
2/fO (SiO
2+ Al
2O
3) mol ratio is 0.28.
This mixture was stirred 1 hour at 25 ℃.Then the gained mixture being put into autoclave stirred 24 hours with 100rpm for inherent 100 ℃.Mixture in the autoclave is corresponding to every mole of SiO
2Have following relative mol composition:
0.05 mole Na
2O
0.036 mole Al
2O
3
0.18 mole (C
12TMA)
2O
0.12 mole (TMA)
2O
36.0 mole H
2O
1.0 mole IPA
Reclaim by the solid product that filters gained, water cleans and is dry under air at room temperature.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.
Record burnt product and have 1223m
2The surface-area of/g and following equilibrium adsorption ability (unit is g/100g):
Water 25.5
Hexanaphthene 41.1
Normal hexane 35.1
Benzene 51
The X ray diffracting spectrum of the burnt product of present embodiment as shown in figure 14.It is characterized in that being spaced apart 3.08 ± 0.15nm place at d has the very strong line of a relative intensity, and 1.79 ± 0.1 and 1.55 ± 0.1nm place weak line is arranged.TEM shows that this product contains oversized hole gap material of the present invention.
50.75g decyl trimethyl ammonium oxyhydroxide (the decyl trimethyl ammonium bromide solution that by concentration is about 29% weight makes with a kind of the contact with hydroxide ion exchange halogen ionic ion exchange resin) is mixed with the 8.75g tetraethyl orthosilicate.The mixture stirring was transferred in the polypropylene jar after 1 hour, again it was put in steam tank 24 hours.The ingredients of a mixture is corresponding to every mole of SiO
2Contain:
0.81 mole (C
10TMA)
2O
47.6 mole H
2O
The gained solid product is leached, clean several times with (60-70 ℃) distilled water of temperature with acetone.With final product at N
2Being calcined to 538 ℃ in the/air mixture placed 8 hours in air then.
Record burnt product and have 915m
2The surface-area of/g, its balance benzene adsorptive power is 35g/100g.Argon physical adsorption data show that the oxygen soakage is 0.34cc/g, and pore dimension is 1.5nm.
The feature of the X-ray diffractogram of the burnt product of present embodiment is to be spaced apart 2.75 ± 0.15nm place at d the very strong line of one relative intensity is arranged, and 1.58 ± 0.1 and 1.37 ± 0.1nm place weak line is arranged.TEM shows that this product contains oversized hole gap material of the present invention.
Embodiment 17
In cetyltrimethyl ammonium (CTMA) hydroxide solution of 80g, add 1.65gNaAlO by embodiment 1 preparation
2At room temperature stir this mixture until NaAlO
2Dissolving.The aqueous solution (the 10% weight SiO that in this solution, adds 40g tetramethyl-ammonium (TMA) silicate
2), 10gHiSiL, 200g water and 70g1,3,5-Three methyl Benzene (TMB).The gained mixture is at room temperature stirred some minutes.Then gel is packed in the 600cc autoclave 105 ℃ of heating 68 hours, the speed with 150rpm stirs simultaneously.The composition of mixture is corresponding to every mole of Al
2O
3Contain:
1.25 mole Na
2O
27.8 mole SiO
2
5.1 mole (CTMA)
2O
2.24 mole (TMA)
2O
2256 moles of H
2O
80.53 mole TMB
Products therefrom is leached, clean several times with (60-75 ℃) distilled water of temperature with acetone.Final product is at N
2Be fired to 538 ℃ in the/air mixture, in air, placed about 10 hours then.
Record burnt product to have＞the balance benzene adsorptive power of 25g/100g.
The feature of the X-ray diffractogram of the burnt product of present embodiment, be to be about the 10.2nm place at interval at d the very strong wide line of one relative intensity is arranged, but be difficult to accurately measure the position that is positioned at X-ray diffractogram utmost point low angle zone spectral line with conventional X-ray diffractometer.And, differentiate at the peak at these low 2 θ angles, need thinner collimating slit.Used slit in the present embodiment from X-ray tube, is respectively 0.1,0.3,0.5 and 0.2mm.TEM shows that the product of present embodiment comprises different materials, and these materials are observed d on their electron-diffraction diagrams
100Value is different.Observe the d of these materials
100Value be 8.5 and 12nmd at interval between.
Embodiment 18
In cetyltrimethyl ammonium (CTMA) hydroxide solution of 80g, add 1.65gNaAlO by embodiment 1 preparation
2At room temperature stir this mixture until NaAlO
2Dissolving.The aqueous solution (the 10% weight SiO that in this solution, adds 40gTMA silicate
2), 10gHiSiL, 200g water and 120g1,3,5-Three methyl Benzene (TMB).The gained mixture is at room temperature stirred some minutes.Then gel is packed in the 600cc autoclave 105 ℃ of heating 90 hours, the speed with 150rpm stirs simultaneously.The ingredients of a mixture is corresponding to every mole of Al
2O
3Contain:
1.25 mole Na
2O
27.8 mole SiO
2
5.1 mole (CTMA)
2O
2.24 mole (TMA)
2O
2256 moles of H
2O
132.7 mole TMB
Products therefrom is leached, and clean several times with (60-70 ℃) distilled water of temperature with acetone.Final product is at N
2Be fired to 538 ℃ in the/air mixture, in air, placed about 10 hours then.
The surface-area that records burnt product is 915m
2/ g, and balance benzene adsorptive power＞25g/100g.Argon physical adsorption data show that the argon soakage is 0.95cc/g, and the central value of pore dimension is 7.8mm (the Dollimore-Hcal method is seen embodiment 21 (b)), but is distributed to greater than 10.5nm from 7.
The feature of the X-ray diffractogram of the burnt product of present embodiment is only in the X-ray diffraction utmost point low angle district enhanced scattering strength to be arranged, and can be observed by the intensity of the incident X-rays bundle of transmission in this district usually.But TEM shows the product of present embodiment and comprises different materials that these materials are observed d on their electron-diffraction diagrams
100Value is different.Observe the d that these materials have
100Value be 8.5 and 11nmd at interval between.
Embodiment 19
In cetyltrimethyl ammonium (CTMA) hydroxide solution of 80g, add 1.65gNaAlO by embodiment 1 preparation
2At room temperature stir this mixture up to NaAlO
2Dissolving.The aqueous solution (the 10% weight SiO that in this solution, adds 40g tetramethyl-ammonium (TMA) silicate
2), 10gHiSiL, and 18g1,3,5-Three methyl Benzene (TMB).The gained mixture is at room temperature stirred some minutes.Then gel is packed in the 300cc autoclave 105 ℃ of heating 4 hours, the speed with 150rpm stirs simultaneously.The composition of mixture is corresponding to every mole of Al
2O
3Contain:
1.25 mole Na
2O
27.8 mole SiO
2
5.1 mole (CTMA)
2O
2.24 mole (TMA)
2O
650 moles of H
2O
19.9 mole TMB
Products therefrom is leached, and clean several times with (60-70 ℃) distilled water of temperature with propyl alcohol.Final product is at N
2Be fired to 538 ℃ in the/air mixture, in air, placed about 8 hours then.
The surface-area that records burnt product is 975m
2/ g, and balance benzene adsorptive power＞40g/100g.Argon physical adsorption data show that the argon soakage is 0.97cc/g, and pore dimension is 6.3nm (the Dollimore-Hcal method is seen embodiment 21 (b)), and peak value is at P/P
o=0.65.
The feature of the X-ray diffractogram of the burnt product of present embodiment is to be spaced apart 6.3 ± 0.5nm place at d the very strong line of one relative intensity is arranged, and 3.64 ± 0.2,3.13 ± 0.15 and 2.38 ± 0.1nmd interval weak line is arranged.TEM shows that the product of present embodiment contains oversized hole gap material of the present invention.
In order to estimate catalytic performance of the present invention, for being that the performance of two trimethylphenylmethanes is assessed with three trimethylphenylmethanes (TTBB) dealkylation with each final product of embodiment 1-14.Assessment is to carry out under a kind of in two set conditions or two kinds: (i) temperature is 225 ℃, and weight per hour space velocity is 100hr
-1(ii) temperature is 200 ℃, and weight per hour space velocity is 200hr
-1Pressure is barometric point.Charging is made of the TTBB/ toluene of 6.3/93.7.Transformation efficiency is to measure 30 minutes the time in materials flow.
The result is as follows:
The transformation efficiency of preparation catalyzer, (weight %) embodiment numbers 225 ℃/100hr
-1200 ℃/200hr
-1
1??????????????0?????????????--
2??????????????6.2???????????--
3??????????????53.9??????????--
4??????????????10.4??????????--
5??????????????68.9??????????--
6??????????????100.0?????????--
7??????????????5.3???????????--
8??????????????--????????????61.2
9??????????????--????????????58.9
10?????????????86.3??????????--
11?????????????96.7??????????--
12?????????????92.8??????????--
13?????????????--????????????37.7
14?????????????12.0??????????0
Embodiment 21 (a)
The argon physical adsorption of the pore system that the about 6.0nm of diameter is following
In order to measure the pore diameter that pore diameter of the present invention is lower than the product of 6.0nm, the product sample 0.2g of embodiment 1-16 is put into the hyaloid QC, be connected to United States Patent (USP) 4,762, on No. 010 described physical adsorption appearance.
Sample was heated 3 hours for 300 ℃ times in a vacuum, to remove the moisture of absorption.Then sample hose is immersed in the liquid argon, sample is cooled to 87K.Again will be through the argon gas of metering, according to United States Patent (USP) 4,762, No. 010 the 20th the described method in hurdle is progressively introduced in the sample.According to argon gas quantity of leading to sample and the quantity of staying the argon gas in the gas space above the sample, just can be regarded as the argon gas quantity that is adsorbed.Used perfect gas law during calculating and through the sample volume (also can referring to S.J.Gregg etc.) of calibration, " absorption, surface-area and porosity ", second edition, Academic Press, 1982).For each example, the quantity of adsorbing when making balance and the graph of a relation of relative pressure above the sample constitute shown in Figure 15 to the such constant temperature adsorption curve of embodiment 4 product samples.Usually use relative pressure, it is the vapour pressure P by equilibrium pressure and adsorbate under the temperature of listing measurement constant temperature absorption line
oRatio obtain.The argon gas quantity introduced of each step will be small enough to produce 168 data points in relative pressure is 0 to 0.6 scope.To determine fully at length that constant temperature absorption line needs 100 points at least.
Transition point (flex point) on the constant temperature absorption line, (product of embodiment 4) is about P/P in this example
o=0.4, the filling of control hole slot sytem.The size of transition is represented the quantity of adsorbing, and with P/P
oThe transition point position of expression, then the size of the hole of absorption takes place in expression.Bigger hole is at bigger P/P
oFill.In order to determine the position of transition point on the isotherm better, calculated (P/P with respect to log
o) derivative.This is illustrated in Figure 16.Also listed among Figure 16 with the same manner obtain by United States Patent (USP) 4,880, the crystalline material of making for No. 611 and the data of other several crystalline materials.Also have a physical scale on axle, it will be with log (p/P
o) expression the adsorption peak position be converted to tangible pore diameter.Conversion is tried to achieve with following formula:
D=pore diameter (is unit with nm) wherein, K=32.17, S=0.2446, L=d+0.19, D=0.57.
This formula be according to the method for Horvath and Kawazoe derive (G.Horvath etc., J.Chem.Eng.Japan, 16 (6) 470 (1983)).Required constant when setting up this formula is to determine according to constant temperature absorption line and known pore dimension thereof that ALPO-5 is recorded.This method is specially adapted to the poromerics that pore diameter is lower than 6.0nm.
As shown in figure 16, the pore dimension of the material of embodiment 4 is 3.96nm, and peak value is at log (P/P
o)=-0.4 or P/P
o=0.4, and press United States Patent (USP) 4,880, the pore dimension of the material of No. 611 manufacturings is 1.2nm, or P/P
o=0.02.In other material, at P/P
o=0.015 observes a peak, represents with asterisk (*) in Figure 16.This peak is reflected in the absorption on the pore wall, does not resemble the pore dimension of indicating given material other.P/P
oNumerical value be 0.03 to be 1.3nm corresponding to pore dimension.
With the results are shown in following table of this method to the sample gained of embodiment 1-16. Embodiment 9,12 and 15 sample provide two peaks that separate, and it is believed that it is owing in the product two super large hole phases of separating are arranged.
Embodiment numbers pore diameter, nm
1??????????????????3.22
2??????????????????3.54
3??????????????????4.25
4??????????????????3.96
5??????????????????1.69
6??????????????????2.73
7??????????????????4.26
8??????????????????2.83
9????????????????2.28，3.08
10??????????????????3.68
11??????????????????3.61
12???????????????3.50，4.21
13??????????????????4.0
14??????????????????0.83
15???????????????2.24，3.04
16??????????????????1.50
Embodiment 21 (b)
The argon physical adsorption of the pore system that the about 6.0nm of diameter is above
In the aperture ranges of diameter, can use the Kelvin equation greater than 6.0nm.This equation generally is expressed as: ln (P/P
oThe 2V γ cos θ/r of)=-
kRT is wherein:
The surface tension of γ=adsorbate
The molecular volume of V=adsorbate
θ=contact angle (in fact generally get and make O)
The R=gas law constant
T=absolute temperature
RK=capillary condensation (hole) radius
P/P
o=relative pressure (taking from the physical adsorption isotherm)
The Kelvin equation is handled the absorption of pore system as a kind of capillary condensation phenomenon, and the surface tension by absorbate (being argon under this situation) and contact angle will adsorb the pressure and the pore dimension that take place and link.The principle of Kelvin equation institute basis is applicable to the hole of diameter in the 5-100nm scope.Under this scope, this equation no longer reflects physical reality, because in littler hole real capillary condensation can not take place; On this scope,, can not when measuring pore dimension, obtain enough precision because equation is a logarithmic function character.
Usually selecting and specifically using the kelvin equation is method (the D.Dollimore ﹠amp of Dollimore and Hcal report with what measure pore dimension; G.R.Heal, J, AppliedChem., 14,108 (1964)).This method to the Kelvin equation usually that consider, the upper layer of adsorbate on pore wall in advance influence done correction, thereby provide pore diameter observed value more accurately.Though the method for Dollimore and Hcal is to derive to be used for constant temperature desorb line, as long as simply data the other way around, it also can be applied to adsorb isotherm equally well.
Embodiment 18 and 19 product just as point out handle the argon adsorpting data with Dollimore and Heal method.
Embodiment 22
Transmission electron microscopy
In order to further specify the character of hex crystal product of the present invention, to embodiment 1-13,15-19, the sample of 23-31 and 36-38 products therefrom has been done research as the usefulness transmission electron microscopy of pointing out (TEM).TEM is a kind of microstructural technology of various materials (comprising crystalline material) that is used for showing.
In order to illustrate the microstructure of material, sample must be thinned to is enough to allow electron beam pass through it, and normally about 50-100nm is thick.Generally all requirement can be for deliberation with its preparation by ultramicrotomy for the crystal habit of material of the present invention.Though it is more time-consuming.The electron microscope technique personnel are very familiar to this sample preparation methods.Material is embedded in a kind of resin, is a kind of commercially available low viscosity propionic acid resin L.R.White (firmly) under this situation, then it is solidified 1.5 hours at 80 ℃.On ultramicrotome, cut out thin slice from sample blocks, the thin slice of thickness in the 50-100nm scope is collected on the detailed catalogue electron microscope support mesh with diamond tool.For these samples, used a LKB type ultramicrotome of being furnished with 45 ° of diamond blades; Support mesh is 400 order copper mesh.Charge in microscope preventing at skim carbon on the evaporation on the sample, (at this moment, the blank sheet of paper that is placed on the sample next door in the evaporation platform manifests light gray), sample just is ready to observe in TEM.
If only want to confirm the existence of material of the present invention, can adopt a kind of better simply sample preparation technology to most of synthetic products.This method is to allow the dispersion thing of material be deposited on the lacery Formvar electron microscopic mirror support of carbon coated, and support is in advance through polishing and the supersound process in propyl alcohol.Usually the enough thin fragment and the zone that can obtain electron-diffraction diagram and lattice image can found near the place at crystal edge.The sample that is used for analyzing among embodiment 23-31 and the 36-38 prepares with this dispersion technology.
High resolving power TEM microgram display structure is along the projection of sample direction of observation.Therefore, in order to observe microstructural some details of material, just need the sample of specific orientation.For crystallized sample, these orientations are the easiest to be to choose by observing with the produced simultaneously electron diffraction collection of illustrative plates of electronic microscopic image (EDP).The selection area visual field snoot technology that such EDP can use the electron microscope technique personnel to be familiar with produces on modern TEM instrument.When observing when showing the EDP that required point diffraction arranges, the crystalline of corresponding this EDP of generation resembles and will demonstrate the details of the projection on the direction that its microstructure points out along EDP.Like this, with regard to the projection on available tem observation and the identification crystal different directions.
In order to observe the prominent feature of crystallized product of the present invention, need on such orientation, observe this material, EDP corresponding on this direction can provide into the point diffraction that hexagonal is arranged from the discrete monocrystalline.If have polycrystalline in the snoot of visual field, the eclipsed diffractogram of explaining will take place extremely to be difficult to.Figure 17 has provided the example of the sexangle figure that the single crystal grain of the product of embodiment 4 produces.The number of viewed point diffraction is outside other thing, also at the regularity that only depends on that to a certain degree crystallization is arranged in the material.But what obtain resembles, and should observe the bright spot of inner ring at least.The discrete crystal can be regulated by the sample inclination setting device on the TEM, up to obtaining this orientation.More common situation is, utilizes more easily to comprise many these facts of randomly-oriented crystal in the sample, seeks everywhere at sample simply, up to finding the crystal that provides required EDP (thereby being required orientation).Back one technology is used to produce electron micrograph discussed below.
With the ultrathin section sample, of above-mentioned technical survey embodiment 1-13 and 15-19 gained material, electron microscope is done at 200,000 couchers in the JEOL200CX transmission electron microscope, and an effective 0.2nm lens isis is housed.The resolving power of putting in order of instrument is 0.45nm.Other experimental establishment mode that also can use high resolution (phase contrast) TEM technician to be familiar with produces of equal value resembling, as long as note the minimum contrast lens current set(ting)value of object lens is remained on focusing less than one side (underfocus side).Figure 18 be embodiment 4 crystallized products cut out the electron micrograph of thin slice with slicing machine.On scheming, can find out a quite regular vat array that becomes hexagonal to arrange.Repeat distance between the groove is about 4.5nm unit, the position (4.1nm/ at first peak on it and this material X-ray diffractogram
) be consistent.Owing to wall must be arranged between each groove, this observations also with among the embodiment 16 is measured the hole that obtains according to the argon physical adsorption of this material and is estimated that the about 3.96nm of size conforms to.
Figure 19 be embodiment 5 crystallized products cut out the electron micrograph of thin slice with slicing machine.Can see the quite regular array of the smaller slightly groove that hexagonal is arranged on scheme.Repeat distance between the groove is about 3.0nm, the position (2.5nm/ at first peak on it and this material X-ray diffractogram
) be consistent.The less argon physical adsorption of also being reported by embodiment 21 (a) of this material pore dimension is measured and is confirmed, calculates to such an extent that the numerical value among the embodiment 5 is 1.69nm there.
Figure 20 is embodiment 18 crystallized products cut out thin slice with slicing machine a electron micrograph.Groove during this resembles is very big but than irregularity, but the feature that material hexagonal of the present invention is arranged is still significantly.
Embodiment 23
This solution is with N in 80g cetyltrimethyl ammonium oxyhydroxide (CTMAOH) solution, N, N-trimethylammonium-1-cetyltrimethyl ammonium muriatic 29% (weight) solution contact and makes an adding 1.65gNaAlO with hydroxide radical exchange halogen ionic exchange resin with a kind of
2Stir this mixture until NaAlO
2Dissolving fully.In this solution, add 40.0g tetramethyl-ammonium silicate solutions (10% weight SiO
2) and 10.0gHiSiL (90% weight SiO
2).With the gained mixture at the stirring at room several minutes.Then this gel is packed into and stir with 150RPM in the 300ml autoclave pressure and be heated to 105 ℃.After heating about 4 hours, make the reaction quenching, the material in the still is taken out with cold water.Product filtered and with warm (60-70 ℃) distilled water and washing with acetone several times.At N
2In/the air mixture final product was calcined 8 hours at 538 ℃.
The composition of gel reaction mixture is corresponding to every mole of Al
2O
3Have:
1.25 mole Na
2O
27.8 mole SiO
2
5.1 mole (CTMA)
2O
2.24 mole (TMA)
2O
650 moles of H
2O
The surface-area that records the calcinate of present embodiment is 1187m
2/ g, the benzene adsorptive power is 66g/100g.
The X-ray diffractogram of the calcinate of present embodiment is gone up by figure and can be found out that this product is spaced apart 3.68 ± 0.2nm place at d-a line that relative intensity is very strong as shown in figure 21, and 2.12 ± 0.1 and the existence of 1.83 ± 0.1nm place a little less than line.Check the product of present embodiment with transmission electron microscopy (TEM), provided resembling that even hole hexagonal arranges, and d
100Approximate the hexagonal electron-diffraction diagram of 3.8nm.
Embodiment 24-31
Carry out other experiment of 8 branches by the method for embodiment 23, but in initial reaction mixture, added a kind of auxiliary organism.All be 1 (TMB) to be added in the reaction mixture as auxiliary organism become last component in each experiment.The concentration of TMB changes between each experiment, shown in Table A.Also having listed the product pore dimension in the Table A, is the volume of voids and the equilibrium benzene adsorptive value of unit with cc/g.Embodiment 24,27 and 30 pore dimension and volume of voids numerical value be by other embodiment d-at interval and the pore dimension that records and the extrapolation of the graph of a relation between the volume of voids and (seeing Figure 23 and 24).For the ease of relatively, also pointed out the strongest X-ray diffraction spectral line.Figure 22 is by the TMB mole number/mole SiO in each reaction mixture
2Show that the auxiliary organism of TMB is to first great d-influence at interval of X-ray diffractogram.Along with auxiliary organic concentration in the reaction mixture increases, the pore dimension of crystalline material product and volume increase.
TEM check to each burnt product of embodiment 24-31 is done all provides an even hole and is resembling and d of hexagonal row elephant
100Value is corresponding to the d-hexagonal electron-diffraction diagram at interval at some peaks in the X-ray diffractogram.(Table A is seen the literary composition back)
Embodiment 32-45
Be suitable as auxiliary organism among the present invention in order to illustrate which organic compound, repeated embodiment 23, but in each experiment before joining HiSiL in the reaction mixture, directly add the auxiliary organism that 10g may use earlier.The results are shown in Table B, from showing to see Octadecane (embodiment 40), 1-amylalcohol (embodiment 43) and phenol (embodiment 44) can not cause noticeable change at interval or produce amorphous product the d-of the strongest X-ray diffraction spectral line.All other materials of listing at table B all make the position of the strongest X ray spectral line that noticeable change takes place, thereby are suitable auxiliary organism.(table B sees the literary composition back)
To the check that each burnt product of embodiment 36-38 is done, all provide an even hole and be resembling and d of hexagonal arrangement
100The value cardinal principle is corresponding to the d-hexagonal electron-diffraction diagram at interval at some peaks in the X-ray diffractogram.
Embodiment 46
The 1.08g Cobaltous nitrate hexahydrate is dissolved in the 10g water makes solution.29% (weight) aqueous solution that in this solution, under agitation adds 40gCTMAOH.10g TBuA (TBA) silicate solutions (with 55% (weight) aqueous solution of 168g tetraethyl orthosilicate and 270gTBA oxyhydroxide and make) and 5gHiSiL silicon-dioxide.The mixture of gained contains following composition corresponding to every mole of silicon-dioxide:
0.21 mole (CTMA)
2O
0.07 mole (TBA)
2O
0.04 mole CoO
25.7 mole H
2O
Mixture is put into a polypropylene vial, and in steam tank, put 72 hours.Resulting solid product is leached, washing, dry air was calcined 10 hours in 540 ℃ of air then.Burnt product has the balance benzene adsorptive power of 40% weight, and its X-ray diffractogram as shown in figure 25.On scheming, can see that being spaced apart 3.7 ± 0.2nm at d-has a very strong line, and d-be spaced apart 2.1 ± 0.1 and 1.9 ± 0.1nm place weak line is arranged.
Embodiment 47
Repeat embodiment 46, but replace cobalt salt with the 1.08g Nickelous nitrate hexahydrate.The equilibrium benzene adsorptive power of the burnt product of gained is 60% weight, and its X-ray diffractogram is (being spaced apart 3.7 ± 0.2nm place at d-has a very strong line, and be spaced apart 2.1 ± 0.1nm place at d-one weak line is arranged) as shown in figure 26.
Embodiment 48
4.5g hydration chromium sulphate is dissolved in the 20g water makes solution.29% (weight) aqueous solution that in this solution, stir to add 200gCTMAOH, 50g TBuA (TBA) silicate solutions (55% (weight) aqueous solution of 168g tetraethyl orthosilicate and 270gTBA oxyhydroxide is made) and 25gHiSiL silicon-dioxide.The mixture of gained contains following composition corresponding to every mole of silicon-dioxide:
0.21 mole (CTMA)
2O
0.07 mole (TBA)
2O
0.02 mole Cr
2O
3
22.0 mole H
2O
Mixture is put into a polypropylene vial, and in steam tank, placed 72 hours.The gained solid product is leached, washing, dry air was calcined 10 hours in 540 ℃ of air again.The equilibrium benzene adsorptive power of burnt product is 40% weight, and its X-ray diffractogram as shown in figure 27.As seen being spaced apart 3.9 ± 0.2nm at d-on scheme has a very strong line, and be spaced apart 2.1 ± 0.1nm place at d-one weak line is arranged.
Embodiment 49
50g is mixed in stirring with 5g tetraethyl orthosilicate and 14.5g tetramethyl-ammonium silicate (10% silicon-dioxide) by the cetyltrimethyl ammonium oxyhydroxide of embodiment 1 preparation.Stir lasting 1 hour, and in gained solution, add gallium nitrate solution (with 1.2gGa (NO
3)
3XH
2O is dissolved in the 10g water and makes).Suppose that tensio-active agent exchanges fully, form by following corresponding to every mole of silicon-dioxide in the mixture:
0.5 mole (CTMA)
2O
0.05 mole Ga
2O
3
66 moles of H
2O
This mixture is put into a polypropylene vial, put into steam tank again and put 48 hours for inherent about 95 ℃.The gained solid is leached washing, dry air, calcining (6 hours subsequently in air in 540 ℃ of flowing nitrogens in 1 hour) again.The X-ray diffractogram of its burnt product as shown in figure 28, wherein being spaced apart 3.4 ± 0.2nm place at d-has a very strong line, and d-be spaced apart 2.1 ± 0.1 and 1.8 ± 0.1nm place weak line is arranged.The chemical analysis composition of just synthetic good product is: (weight percent)
40% carbon
2.5% nitrogen
15% silicon
2.8% gallium
0.07% aluminium
39.9% ash content (1000 ℃)
Table A
Embodiment TMB TMB/SiO
2TMB/ d-pore dimension benzene adsorption rate at interval numbers (nm) (g/100g of mole number mol ratio CTMA+ (nm);
Mol ratio is at 6.7KPA) 23 000 3.68 3.2,3.77 6,624 0.025 0.12 0.32 4.03 4.15 6,125 0.050 0.23 0.65 4.53 4.51 6,226 0.075 0.35 0.97 4.81 5.25 4,827 0.100 0.46 1.30 5.48 5.80 3,728 0.150 0.70 1.95 6.22 6.30 4,329 0.150 0.70 1.95 6.22 6.90 3,630 0.183 0.85 2.38 6.37 6.81 3,231 0.216 1.00 2.80 6.51 7.02 38
Table B
The auxiliary organic auxiliary of the auxiliary organism of embodiment/d-is benzene adsorption rate numbering thing mole number SiO at interval
2(rub (nm) (g/100g,
That ratio) 6.7KPA) 23 do not have 00 3.68 6632 p-Xylol 0.094 0.44 4.98 3,933 1,3,5-Three methyl Benzene 0.083 0.39 5.12 3,834 1,3,5-triethylbenzene 0.062 0.29 4.81 3,635 1,3,5-triisopropylbenzene 0.049 0.23 4.49 4,336 1,3-dimethyladamantane 0.061 0.28 4.89 4237 Skellysolve A 0.139 0.64 4.72 3138 n-decane 0.070 0.33 4.64 4839 n-dodecane 0.059 0.27 4.28 4840 Octadecane 0.039 0.18 3.70 5441 1-phenyl nonane 0.049 0.23 4.64 3,442 1,8-two bromooctanes 0.037 0.17 4.49 3343 1-amylalcohol 0.113 0.53 amorphous 2844 phenol 0.106 0.49 amorphous lacks 45 pyridines 0.126 0.59 4.64 and lacks
Claims (10)
1. the synthetic method of a synthetic, this synthetic comprises a kind of inorganic, porous, non-stacked crystalline phase material, after calcining, the X ray diffracting spectrum that it presents have at least a peak at d-at interval greater than the 1.8nm place, and in the benzene adsorptive power of 6.7KPa (50 torr) and 25 ℃ greater than this material of every 100g 15g benzene; Perhaps this synthetic comprises a kind of inorganic, porous crystalline phase material, it has by diameter and is at least the hexagonal array that the hole of uniform size of 1.3nm constitutes, and through after the calcining, the hexagonal electron diffraction pattern that it presents can be with a d greater than 1.8nm
100Value indicates; The method is characterized in that it carries out 5 minutes to 14 days crystallization with the reaction mixture of composition in following scope under 25 to 250 ℃ temperature: (composition is represented with the mol ratio of oxide compound):
X
2O
3/ YO
20 to 0.5
X
2O
3/ (YO
2+ Z
2O
5) 0.1 to 100
X
2O
3/ (YO
2+ WO+Z
2O
5) 0.1 to 100
Solvent/(YO
2+ WO+Z
2O
5+ X
2O
3) 1 to 1500
OH
-/ YO
20 to 10
(M
2/eO+R
2/fO)/(YO
2+WO+Z
2O
5
+ X
2O
3) 0.01 to 20
M
2/eO/(YO
2+WO+Z
2O
5
+ X
2O
3) 0 to 10
M
2/fO/(YO
2+WO+Z
2O
5
+ X
2O
3) 0.01 to 2.0
Wherein e and f are respectively the weighted average prices of M and R; Solvent is water or C
1Or C
6Alcohol or glycol; And R comprises that a kind of general formula is R
1R
2R
3R
4Q
+Organic directing agent, wherein Q is nitrogen or phosphorus; R
1, R
2, R
3, R
4In have at least one to be aryl or alkyl with 6 to 36 carbon atoms, and remaining R
1, R
2, R
3, R
4Each all is the alkyl that is selected from hydrogen and has 1 to 5 carbon atom.
2. the method for claim 1 is characterized in that wherein reaction mixture has the composition (mol ratio with oxide compound is represented) in the following scope:
X
2O
3/ YO
20.001 to 0.5
X
2O
3/ (YO
2+ Z
2O
5) 0.1 to 20
X
2O
3/ (YO
2+ WO+Z
2O
5) 0.1 to 20
Solvent/(YO
2+ WO+Z
2O
5+ X
2O
3) 5 to 1000
OH
-/ YO
20 to 5
(M
2/eO+R
2/fO)/(YO
2+WO+Z
2O
5
+ X
2O
3) 0.05 to 5
M
2/eO/(YO
2+WO+Z
2O
5
+ X
2O
3) 0 to 5
M
2/fO/(YO
2+WO+Z
2O
5
+ X
2O
3) 0.03 to 1.0
3. method as claimed in claim 1 or 2, it is characterized in that wherein said organic directing agent is to be selected from following material: cetyltrimethyl ammonium, Shi six Wan base San Jia Ji Phosphonium octadecyl trimethylammonium, benzyltrimethylammon.um, cetyl pyridinium, the tetradecyl trimethyl ammonium, decyl trimethyl ammonium, the compound of dodecyl trimethyl ammonium and dimethyl two (dodecyl) ammonium etc.
4. method as claimed in claim 1 or 2 is characterized in that wherein R comprises an additional organic directing agent, and this additional directing agent has identical expression with the directing agent of at first mentioning, but R wherein
1, R
2, R
3, R
4Each all is the alkyl that is selected from hydrogen and has 1 to 5 atom.
5. method as claimed in claim 4 is characterized in that additional organic directing agent wherein is to be selected from tetramethyl-ammonium, tetraethyl ammonium, the compound of tetrapropyl ammonium and TBuA etc.
6. method as claimed in claim 1 or 2 is characterized in that wherein R comprises an auxiliary organism, and this auxiliary organism is to be selected from: (1) have the aromatic hydrocarbon of 5-20 carbon atom and amine and a halogen replacement thereof and C
1-C
14Alkyl-substituted derivatives; (2) having the ring-type of 5-20 carbon atom or many cycloaliphatic hydrocarbon and amine and halogen thereof replaces and C
1-C
14Alkyl-substituted derivative; (3) have straight chain and branched aliphatic hydrocarbons and the amine and the halogen substitutive derivative thereof of 3-16 carbon atom.
7. method as claimed in claim 6 is characterized in that auxiliary organism wherein is a p-Xylol, Three methyl Benzene, triethylbenzene or triisopropylbenzene.
8. method as claimed in claim 6 is characterized in that wherein (auxiliary organism)/YO
2Mol ratio be 0.05 to 20.
9. method as claimed in claim 6 is characterized in that wherein the mol ratio of (auxiliary organism)/(organic directing agent) is 0.02 to 100.
10. the synthetic method of synthetic as claimed in claim 1, its feature also be, crystallization wherein is to be 50 to 175 ℃ in temperature, and pH carried out 5 to 300 hours under 9 to 14 the condition.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/625,171 US5057296A (en) | 1990-12-10 | 1990-12-10 | Method for synthesizing mesoporous crystalline material |
| US07/625,238 US5108725A (en) | 1990-01-25 | 1990-12-10 | Synthesis of mesoporous crystalline material |
| US625,238 | 1990-12-10 | ||
| US625,245 | 1990-12-10 | ||
| US625,171 | 1990-12-10 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB961010185A Division CN1143727C (en) | 1990-12-10 | 1991-05-30 | Synthetic porous crytalline material, its synthesis and use for catalytic conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062308A CN1062308A (en) | 1992-07-01 |
| CN1033445C true CN1033445C (en) | 1996-12-04 |
Family
ID=27089841
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB961010185A Expired - Lifetime CN1143727C (en) | 1990-12-10 | 1991-05-30 | Synthetic porous crytalline material, its synthesis and use for catalytic conversion |
| CN 91103656 Expired - Lifetime CN1033445C (en) | 1990-12-10 | 1991-05-30 | Synthetic porous crystalline material its synthesis and use |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB961010185A Expired - Lifetime CN1143727C (en) | 1990-12-10 | 1991-05-30 | Synthetic porous crytalline material, its synthesis and use for catalytic conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1143727C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055256C (en) * | 1994-12-21 | 2000-08-09 | 中国科学院大连化学物理研究所 | High water absorption molecular sieve adsorbent and its preparation |
| CN110102252A (en) * | 2019-05-14 | 2019-08-09 | 中钢集团马鞍山矿山研究院有限公司 | A method of removing sulfur dioxide in flue gas |
-
1991
- 1991-05-30 CN CNB961010185A patent/CN1143727C/en not_active Expired - Lifetime
- 1991-05-30 CN CN 91103656 patent/CN1033445C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1136977A (en) | 1996-12-04 |
| CN1062308A (en) | 1992-07-01 |
| CN1143727C (en) | 2004-03-31 |
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