CN1011221B - Quinary and senary molecular sieve compositions - Google Patents

Quinary and senary molecular sieve compositions

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Publication number
CN1011221B
CN1011221B CN 85103203 CN85103203A CN1011221B CN 1011221 B CN1011221 B CN 1011221B CN 85103203 CN85103203 CN 85103203 CN 85103203 A CN85103203 A CN 85103203A CN 1011221 B CN1011221 B CN 1011221B
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molecular sieve
phosphorus
aluminium
reaction mixture
senapso
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CN85103203A (en
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布伦特
马库斯
弗拉尼金
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Union Carbide Corp
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Union Carbide Corp
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Abstract

The present invention discloses molecular sieves in a three-dimensional micropore skeleton structure with tetrahedral oxide cells of MO2, AIO2, SiO2 and PO2, which have the following dry basis empirical chemical composition: mR: (M<w>Al<x>P<y>Si<z>) O2, wherein R is an organic template agent existing in a hole system in the crystal; m is the mol number of R which exists in every mol of (M<w>Al<x>P<y>Si<z>) O2; M is at least two different elements of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, ferrum, lithium, magnesium, manganese, titanium, vanadium and zinc; w, x, y and z respectively represent the mol numbers of M, aluminum, phosphorus and silicon which exist in the form of tetrahedral oxides. The present invention also discloses applications of the molecular sieves as adsorbents, catalysts, etc.

Description

Quinary and senary molecular sieve compositions
The present invention relates to a kind of preparation method who is used as the new crystallization three-dimensional micropore molecular sieve of sorbent material and catalyzer.The present invention relates to except containing aluminium (AlO - 2), phosphorus (PO + 2) and silicon (SiO 2) outside, also contain two kinds or three kinds of elements " M " tetrahedronal oxide of skeleton unit (MO n 2) five yuan of novelties and senary molecular sieve.
" M " represents element hereinafter described, " n " be-3 ,-2 ,-1,0 or+1.
The technology of crystal silicon-aluminate zeolite type molecular sieve is well-known.At present, natural and synthetic molecular sieve kind are above 150 kinds.Crystalline zeolite is generally by the AlO at shared angle 2And SiO 2Tetrahedron constitutes, and its feature is, the size of perforate evenly, ion-exchange capacity by force with the ability with the mutually reversible desorb of the absorption of making.Absorption generally is to spread all over the hole of crystals and do not replace and constitute fixedly any atom of crystalline texture mutually.
Everybody also knows, does not belong to other microporous compositions of zeolite, does not promptly contain the AlO as the basic framework composition 2Tetrahedral composition, still have zeolites ion-exchange and (or) character such as absorption.According to people's such as Dwyer on the 2nd March in 1976 US3941871, many metal organosilicon aluminates have ion-exchange character and aperture and the neither also neutral backbone in cation site not of cation uniformly.
According to people's such as Wilson on the 12nd in January nineteen eighty-two US4310440, the microporous compositions of recent report, the composition that the synthetic skeleton Zn-Al-P-Si-oxide molecular sieve of individual no silicon-dioxide is the crystallization aluminophosphates.This type of material is by AlO 2And PO 2Tetrahedron constitutes, and is the same with the silicon-dioxide polymorphic form, has electricity price neutral skeleton.For the pure silicon dioxide molecular sieve, because it does not have the outer positively charged ion of structure, so it is hydrophobic.Aluminophosphate molecular sieve is unlike the pure silicon dioxide molecular sieve, and aluminophosphate molecular sieve is medium hydrophilic, because there is significant difference in the electronegativity between aluminium and the phosphorus.The pore volume of this type of molecular sieve crystal inside and aperture are equally matched with SiO 2 molecular sieve with those known zeolites.
United States Patent (USP) 4440871 reveals that various silicoaluminophosphates all are micropore and crystalline.This class material has PO + 2, AlO - 2And SiO 2The three-dimensional crystal skeleton of tetrahedron element, and do not have to choose wantonly the basic metal or the calcium of existence fully.The anhydrous benchmark empirical of synthetic silicoaluminophosphates consists of:
mR∶（Si xAl yP z）O 2
Wherein: " R " is illustrated in the one or more organic formwork agent that exists in the system of intracrystalline hole, and " m " represents every mole of (Si xAl yP z) O 2" R " mole number that exists, its value is between 0 to 0.3, the maximum value under each situation is decided by the size of template molecule and the available volume of voids of this kind silicoaluminophosphates own; " x ", " y " and " z " represent the molar fraction of silicon, aluminium and phosphorus in the tetrahedral oxide respectively, and the minimum value of " x ", " y " and " z " all is 0.01, all is 0.02 preferably, and maximum value is respectively 0.98,0.60 and 0.52.
This type of silicoaluminophosphates has aluminosilicate zeolite and peculiar some physics of aluminophosphates and chemical property.
March 31 nineteen eighty-three application number be in the patent of assigning of 480738 issued for approval, revealed the new molecular sieve containing titanium of a class.The anhydrous benchmark chemical constitution of synthesizing titanium-containing molecular sieve, available following unit empirical formula is represented:
mR∶（Ti xAl yP z）O 2
In the formula: the organic formwork agent of one or more that exist in the system of " R " expression intracrystalline hole; " m " represents every mole of (Ti xAl yP z) O 2The mole number of " R ", its value approximately is between 0 and 50; " x ", " y " and " z " are illustrated respectively in the molar fraction of titanium, aluminium and phosphorus in the tetrahedral oxide.
July 15 nineteen eighty-three application number be addressed in the patent of assigning of 514334 issued for approval a class new have a MO 2, AlO 2And PO 2The crystal metal aluminophosphates of tetrahedron element three-dimensional microporous framework structure.Its anhydrous benchmark empirical composition can be represented by the formula:
mR∶（M xAl yP z）O 2
In the formula: the organic formwork agent of one or more that exist in the system of " R " expression intracrystalline hole, " m " represents every mole of (Si xAl yP z) O 2The mole number of " R ", its value is between 0 to 0.3; In " M " expression magnesium, manganese, zinc and these metallic elements of cobalt one or more; " x ", " y " and " z " are illustrated respectively in the molar fraction of metal in the tetrahedral oxide " M ", aluminium and phosphorus.
July 15 nineteen eighty-three application number be 514335 issued for approval is assigned in the patent, addressed a class new have a FeO 2, AlO 2And PO 2The ferrous aluminate or phosphate of tetrahedron element three-dimensional microporous framework structure.Its anhydrous benchmark empirical composition can be represented by the formula:
mR∶（Fe xAl yP z）O 2
In the formula: the organic formwork agent of one or more that exist in the system of " R " expression intracrystalline hole; " m " represents every mole of (Fe xAl yP z) O 2In the mole number of " R ", its value is between 0 to 0.3; " x ", " y " and " z " are illustrated respectively in the molar fraction of iron in the tetrahedral oxide, aluminium and phosphorus.
The present invention relates to have MO n 2, AlO - 2, PO + 2And SiO 2The unitary combination of molecular sieve of tetrahedronal oxide of skeleton." MO wherein n 2" expression two or three different elements tetrahedral oxide units." n " be-3 ,-2 ,-1,0 or+1.
Fig. 1 is the ternary diagram of relevant present composition parameter.The coordinate of figure is a molar fraction.
Fig. 2 is the ternary diagram that related parameter is arranged.The coordinate of figure is a molar fraction.
Fig. 3 is the ternary diagram with preparation relevant used reaction mixture parameter during the present composition.The coordinate of figure is a molar fraction.
The present invention relates to a class new have a MOn 2、AlO - 2、PO + 2And SiO2Five yuan and senary molecular sieve of tetrahedral oxide units three-dimensional microporous framework structure. " MOn 2" in n be-3 ,-2 ,-1,0 or+1. This class recruit sieve has the character such as ion-exchange, absorption and catalysis, therefore can obtain to use widely aspect manufacturing adsorbent and catalyst. The anhydrous benchmark empirical formula of this type of new synthetic monomer is:
mR∶（M wAl xP ySi z）O 2
In the formula: the organic formwork agent of one or more that exist in the system of " R " expression intracrystalline hole; " m " represents every mole of (M wAl xP ySi z) O 2The mole number of " R " that exists, its value approximately is between 0 to 0.3; " M " expression is selected from these elements of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc is no less than 2 kinds element; " n " be-3 ,-2 ,-1,0 or+1; " w ", " x ", " y " and " z " represent the molar fraction of element in the tetrahedral oxide " M ", aluminium, phosphorus and silicon respectively, and their value all is not less than 0.01.
Molecular sieve of the present invention is generally with prefix abbreviation " SENAPSO " expression.It shows that the skeleton structure of molecular sieve of the present invention contains the tetrahedral oxide monomer " MO that is no less than two kinds of elements n 2", and AlO - 2, PO + 2And SiO 2Tetrahedral oxide units." MO n 2" in n be-3 ,-2 ,-1,0 or+1.Annotate afterwards with different numerals at " SENAPSO ", to distinguish the kind of different structure in this type of.For example " SENAPSO-i ", i are positive integer.For the SENAPSO that contains element " M ", can be with " SEN " in " M " replacement " SENAPSO-i ", to show the situation of in esse backbone element in tetrahedral oxide units.The numeral of being annotated is chosen arbitrarily, does not therefore get in touch with the other materials of representing textural property with figure.
The present invention relates to a class new have a MO n 2, AlO - 2, PO + 2And SiO 2The crystalline molecular sieve of tetrahedral oxide units three-dimensional microporous framework structure." MO n 2" in " n " be-3 ,-2 ,-1,0 or+1.This molecular sieve analog has ion-exchange, absorption and catalytic property, therefore obtains to use widely aspect manufacturing sorbent material and catalyzer.
Crystalline molecular sieve of the present invention has MO n 2, AlO - 2, PO + 2And SiO 2The tetrahedral oxide units three-dimensional microporous framework structure.Its anhydrous benchmark empirical composition can be represented by the formula:
mR∶（M wAl xP ySi z）O 2
In the formula: one or more organic formwork agents that exist in the system of " R " expression intracrystalline hole; " m " represents every mole of (M wAl xP ySi z) O 2The mole number of " R ", its value is between 0 to 0.3; " M " expression is selected from these elements of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc is no less than 2 kinds element; " n " be-3 ,-2 ,-1,0 or+1, be decided by the oxidation state of " M "; " w ", " x ", " y " and " z " represent the molar fraction of " M ", aluminium, phosphorus and silicon in the tetrahedral oxide respectively.
In the pentagonal regions that the value of " w ", " x ", " y " and " z " generally is confined to be made of A, B, C, D and E point among Fig. 1.Among the figure: " M " expression number is low two aforementioned elements not; " w " expression various element molar fraction sum, i.e. " w "=" w 1"+" w 2"+" w 3"+..., the molar fraction value of each element is not less than 0.01.In a scheme, " M " is two kinds of elements, and in another scheme, " M " is three kinds of elements.Fig. 1 mid point A, B, C, D and E have following " w ", " x ", " y " and " z " value:
Molar fraction
Point x y (z+w)
A????0.60????0.37????0.03
B????0.37????0.60????0.03
C????0.01????0.60????0.39
D????0.01????0.01????0.98
E????0.60????0.01????0.39
For preferred small portion SENAPSO molecular sieve, the value of " w " in the following formula, " x ", " y " and " z " is that the hexagon that is confined to be made of an a, b, c, d, e and f among Fig. 2 is formed in the district." w ", " x " that some a, b, c, d, e and f have, the value of " y " and " z " are as follows:
Molar fraction
Point x y (z+w)
a????0.60????0.37????0.03
b????0.37????0.60????0.03
c????0.01????0.60????0.39
d????0.01????0.39????0.60
e????0.39????0.01????0.60
f????0.60????0.01????0.39
The purposes of SENAPSO of the present invention is to make sorbent material, catalyzer and ion-exchanger.Though it exactly likes silico-aluminate on purposes, its physics and chemical property are not necessarily as silico-aluminate.
Generally will contain element " M ", aluminium, phosphorus, silicon is best and a kind of reaction mixture of suitable organic formwork agent raw materials such as (being structure directing agent), by hydrothermal crystallization, synthetic SENAPSO composition.Used structure directing agent preferably in the periodictable compound of VA family element and (or) any basic metal or other metals.Generally reaction mixture is placed on airtight, preferably use in the pressurizing vessel as tetrafluoroethylene one class inert material lining, heating then, reacting is to carry out at spontaneous pressure.Suitable temperature of reaction is 50～250 ℃.Temperature of reaction preferably is 100～200 ℃.Reaction proceeds to and obtains till the SENAPSO product.Total effectively crystallization time is generally several hours to several weeks.Typical case's crystallization time is 2 hours to 30 days.The crystallization time of making SENAPSO was generally 4 hours to 20 days.With the common method of picture centrifugation and filtration one class, can tell crystalline product.
When synthesizing the present composition, preferably press the mol ratio preparation reaction mixture of following formula.
aR∶（M wAl xP ySi z）O 2∶bH 2O
In the formula: " R " is organic formwork agent; " a " is template agent, and its value is between 0 to 6, and its effective level approximately is between greater than 0 to 6, and more suitable consumption approximately is between greater than 0 to 2; The value of b is between 0 to 500, and optimum value is between 2 to 300; For the regulation of " M " as mentioned above." w ", " x ", " y " and " z " are respectively the molar fraction of element " M ", aluminium, phosphorus and silicon, and the value of each M all is not less than 0.01.
In preferred version, generally be choosing " w ", " x ", " y " and " z " shared molar fraction in the pentagon that ternary diagram 3 is made of points such as F, G, H, I and J is formed the district, prepare reaction mixture.
The value of " w " that F, G, H, I and J are ordered among Fig. 3, " x ", " y " and " z " is as follows:
Molar fraction
x????y????（z+w）
F????0.60????0.37????0.03
G????0.37????0.60????0.03
H????0.01????0.60????0.39
I????0.01????0.01????0.98
J????0.60????0.01????0.39
Finding when checking SENAPSO in the various reaction product with x-ray analysis, is not that all reaction mixtures can both arrive crystallization SENAPSO product.Its reason it be not immediately clear.
Example hereinafter, digital person is annotated in several backs, is the reaction mixture that has obtained crystallization SENAPSO product; Alphabetical person is annotated in several backs, is reaction mixture that can not check the SENAPSO product with x-ray analysis.
When the composition of the above-mentioned reaction mixture of expression, the amount of each reactant is that the total amount to " w ", " x ", " y " and " z " obtains normalizing, i.e. (w+x+y+z)=1 mole.Zhu Lizhong in the back can be with the mol ratio of oxide compound, also can be by P 2O 5The mole number normalizing is represented the composition of reaction mixture.Use simple method of calculation, can be easy to this representation in back is converted into the representation of front.The method that converts is: remove the mole number of every kind of component (comprising template and water) with the total mole number of " M ", aluminium, phosphorus and silicon, draw with aforementioned each component total mole number and be as the criterion and the molar fraction of each component of normalizing.
Being used for making the organic formwork agent (being template) of the reaction mixture that molecular sieve of the present invention uses, can be the at present synthetic used any template of general zeolite aluminosilicate.Compound as template generally contains the periodic table of elements interior VA family element, particularly nitrogen, phosphorus, arsenic and antimony, and reasonable is nitrogen or phosphorus, preferably contains the nitrogen compound of 1 to 8 carbon atom alkyl or aryl at least.Amine, quaternary phosphine and quaternary ammonium compound are specially adapted to do template.The latter's molecular formula is R 4X +In the formula: " X " is nitrogen or phosphorus, and each R is the alkyl or aryl that contains 1 to 8 carbon, be applicable to make template resemble [(C in addition 14H 32N 2) (OH 2)] xThe polyquaternium of one class.Wherein the value of " x " is for being not less than 2.Monobasic amine, binary amine and ternary amine, no matter be itself, or the composition of itself and quaternary ammonium, or the composition of itself and other template, all be suitable for doing template.Use the mixture of two or more template, have to be beneficial to and produce the desired SENAPSO that obtains, or form the stronger template of guidance capability, can control the process that other template reactions of pH condition are provided with the formation for reaction gel.
Representational template has: tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA ion, four pentyl ammonium ion; Di-n-propylamine, Tri-n-Propylamine, triethylamine, trolamine, piperidines, hexahydroaniline, the 2-picoline, N, the N-dimethyl benzylamine, N, the N-dimethylethanolamine, choline, N, N '-lupetazin, 1,4-diazabicylo (2.2.2) octane, the N-Mono Methyl Ethanol Amine, N methyldiethanol amine, the N-methyl piperidine, the 3-methyl piperidine, N-methylcyclohexylamine, the 3-methyl piperidine, the 4-picoline, quinoline rather encircles, N, N '-dimethyl-1,4-diazabicylo (2.2.2) octane ion, Di-n-Butyl Amine, neopentyl amine, two n-amylamines, Isopropylamine, TERTIARY BUTYL AMINE, quadrol, tetramethyleneimine and 2-imidazolone.
Be not the SENAPSO that each template can both form each kind.In other words, the discrete template is mixed and is controlled reaction conditions suitably, can cause forming some SENAPSO compositions, and uses several different template, can produce given a kind of SENAPSO composition.
Many anti-applying silicons source is available, thereby can form SiO on the spot 2Tetrahedral oxide units.Anti-applying silicon source can be the silicon-dioxide that exists with solation, or smoke curing silicon-dioxide, also can be alkoxide, silicic acid or the alkalimetal silicate of reactive solid amorphous sediment silicon-dioxide, silica gel, silicon, and their mixture.
The phosphorus source of being found so far that is best suited for present method is a phosphoric acid, but has found also to be suitable for as the organophosphate of triethyl phosphate one class, the AlPO that also has picture United States Patent (USP) 4,310,400 to propose 4Crystal or the amorphous phosphorus aluminate of forming a class.The organo phosphorous compounds of picture Xiuization 4-butyl-phosphonium one class can not do reaction on the surface and use the phosphorus source, but these compounds has the effect of template.Have at least the general phosphoric acid salt of a part of kine bias sodium phosphate one class to can be used as the phosphorus source, but be not good phosphorus source.
There is the aluminium-alcohol salt as aluminum isopropylate one class in the aluminium source that is suitable for, or pseudobochmite.Be applicable to crystal or the amorphous phosphorus aluminate of doing the phosphorus source, also be applicable to the aluminium source of doing certainly.As other aluminium sources in the zeolite synthesis of being used in of gibbsite, sodium aluminate and aluminum chloride one class, also be available, but be not good aluminium source.
Making any form that forms the skeleton tetrahedron element on the spot, reaction with " M " element source (arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and/or zinc] put into reaction system.Operable compound has: oxide compound, oxyhydroxide, alkoxide and salt, and as the salt of fontanelle compound, nitrate, vitriol and carboxylate salt (for example acetate) class, and the mixture of above-claimed cpd.
Though stir or moderately stir reaction mixture, and promote the reaction mixture crystallization with the crystal seed of the SENAPSO kind that will produce or homoeomorphic aluminophosphates, silico-aluminate or combination of molecular sieve, all optional to synthetic SENAPSO composition, but can simplify crystallisation process.
After crystallization is finished, tell the SENAPSO product, fully wash, then at air drying.For this firm synthetic SENAPSO, generally in the system of intracrystalline hole, contain a kind of formation thing of template at least.Generally be called " organic moiety ".Template is used when molecular sieve forms.Mostly there is organic moiety, has a part of organic moiety at least, as the positively charged ion of balancing charge and be present in the molecular sieve.This is common for prepare firm synthetic aluminosilicate zeolite with the organism reaction system.But in specific SENAPSO kind, possible some or all organic moiety is that class envelope is stayed molecule, as universal law, stays organic molecule too big by the envelope that template forms, is difficult to run out from the hole of SENAPSO product is.So must organism wherein be decomposed with SENAPSO 200 to 700 ℃ of roastings, just can remove these envelopes and stay molecule.The aperture of SENAPSO product is quite big in some examples, can allow template pass through, and particularly under the little situation of template molecule, so just can use general solution absorbing method used when making zeolite, all or part of organic moiety of removing wherein.Must understand, the present invention selects " synthetic just " this speech for use, be meant the SENAPSO kind that does not comprise in this case, promptly the organic moiety that occupies intracrystalline hole system owing to the result of hydrothermal crystallization process is to reduce and at its constitutional chemistry formula: mR by means of synthetic aftertreatment: (M wAl xP ySi z) O 2In the numerical value of " m " less than those SENAPSO kinds of 0.02.Other symbols in the formula are with above definition.For the manufacturing processed of doing element " M " source, aluminium source, phosphorus source or silicon source with alkoxide,, therefore in reaction mixture, necessarily have the alcohol of a great deal of because alcohol is the hydrolysate of alkoxide.Whether this alcohol participates in building-up process as a kind of template, can't determine.In a little the application,, also be it not to be calculated in template one class artificially even just having this alcohol in the synthetic SENAPSO material.
Since SENAPSO composition of the present invention be by have respectively electric charge " n " ,-1 ,+1 and 0 MO n 2, AlO - 2, PO + 2And SiO 2Tetrahedron element forms, and on the possibility of cationic exchange, this manufacturing processed is more more complex than the manufacturing processed of zeolite molecular sieve.In theory, tetrahedron AlO - 2And has stoichiometric relation between the balancing charge positively charged ion.For the present composition, tetrahedron AlO - 2Can with tetrahedron PO + 2, or be present in alkali metal cation, proton (H in the reaction mixture with picture +) and the simple positively charged ion of positively charged ion one class of element " M ", or combine with positively charged ion from template, reach electrobalance.Equally, tetrahedron MO n 2(n can be-3 ,-2 ,-1,0 or+1), can with tetrahedron PO + 2, be present in alkali metal cation, proton (H in the reaction mixture with picture +) and the positively charged ion of element " M " class, with combine from the organic cation of template or with various two valencys or the polyvalent metallic cation that produce by extra source, reach electrobalance.Can also suppose non-adjacent AlO - 2And PO + 2A pair of tetrahedron, can be respectively by Na and OH institute balance [Flanigen and Grose, " Molecular Sieve Zeolites-I ", ACS, Washington, DC(1971)].
The result who analyzes SENAPSO composition gained of the present invention with the cationic exchange technology that is used for zeolite aluminosilicate at present is, SENAPSO has cation exchange capacity (CEC), and porose in the lattice of SENAPSO composition, the diameter of minimum aperture is 3 dusts.The ion-exchange of SENAPSO composition, general just just possible after the organic moiety from template that exists in the system of hole owing to the synthetic result is removed.Generally can slough the water that is contained in the firm synthetic SENAPSO composition to a certain degree.At least can under the situation of not removing organic moiety, remove portion water, but under the situation that does not have organic moiety, can promote absorption and desorption process greatly.As what hereinafter will illustrate, various SENAPSO materials have different hydro-thermals and thermostability (some is fairly obvious in this respect), and are the good adsorbent of molecular sieve of performance and hydrocarbon conversion catalyst or catalyst substrates.
Stainless steel reactor used in each example all has the inert material teflon lined, to avoid polluting reaction mixture.In general, the preparation method of the final reacting mixture that manufacturing crystallization SENAPSO composition is used is: part reagent is made into mixture, then with other reagent with single form, or add in the said mixture with the form that is made into mixture by two or more reagent.In some scenarios, require each fusion reagent in intermediate blend, to keep this sample.Make part or all of reagent participate in producing in the chemical reaction of novel agent in other cases." mixture " this notion comprises above-mentioned both of these case.In a word, except that specializing, till all requiring intermediate blend and final reacting mixture be stirred to basic homogeneous.
By the x-ray analysis of application standard X ray powder diffracting technology, obtain the X-ray analysis data of reaction product.Source of radiation is at 50 kilovolts and 40 milliamperes of operations, high strength, copper target X-ray tube.Scintillometer, pulsed height analyzer and strip chart recorder with X-ray spectrometer are applicable to the diffractogram that record is produced by copper K-alpha-ray and graphite monochromator.Under 2 ° of per minutes (2 θ) condition, use 2 seconds at interval, scanning concora crush powdered sample.According to the position of the diffraction peak of representing with 2 θ, can obtain with the dust is the interplanar distance (d) of unit.θ is a Bragg angle, is recorded by strip chart.Decide intensity according to the diffraction peak height that deducts behind the background." I 0" represent the strongest line or the intensity at climax, " I " represents the intensity at other each peaks.Another way, based on using Siemens D-500X ray powder diffraction instrument and Siemens K-850 gamma ray source (New Jersey, the Siemens company product of Cherry Hill) technology by computer and suitable interface, can obtain X ray picture by copper K-alpha-ray.
Parameter 2 θ values have certain error owing to be subjected to the influence of operator and instrumental error.This point professional is clearly.The overall error of 2 θ values is ± 0.4 ° in each analysis report.The value of the certain influence surface spacing of this error (d) is because d calculates and gets according to 2 θ values.This error is that generally acknowledge in the present technique field, and be not enough to hinder and judge all crystallized stocks of the present invention difference each other, and the composition produced of the present invention with the difference between the composition of prior art production in the report of some X ray pictures, the relative intensity of interplanar distance is symbolically.The meaning of these symbols is: vs is extremely strong, and s is strong, and ms is strong in being, a little less than w was, vw was for a little less than extremely.
In some instances, a kind of purity of sintetics can be estimated by its X-ray powder diffraction pattern of reference.For example, be pure if evaluation result is reported certain sample, this only refers to that the X ray picture of sample does not have the crest line of crystal impurity, does not show not have amorphous substance.
Molecular sieve of the present invention can be represented its characteristic with its X-ray powder diffraction pattern.Therefore a kind of molecular sieve just has a corresponding X ray picture.Below Table A to showing the X ray picture that N is the various molecular sieves of the present invention (comprise firm synthetic and through roasting).
Table A (SENAPSO-5)
2 θ d(dusts) relative intensity
7.2-7.7????12.28-11.48????m-vs
19.4-19.9????4.58-4.46????w-m
20.85-21.3????4.26-4.17????w-vs
22.1-22.6????4.02-3.93????m-vs
25.6-26.1????3.480-3.414????vw-m
Table B(SENAPSO-11)
2 θ d(dusts) relative intensity
7.8-8.2????11.19-10.85????m-s
9.0-9.8????9.83-9.03????vw-vs
12.8-13.6????6.92-6.51????vw-m
19.9-20.5????4.46-4.33????m-s
20.8-21.8????4.27-4.08????m-vs
22.0-22.6????4.04-3.93????m-vs
22.6-23.1????3.93-3.85????vw-vs
23.1-23.5????3.85-3.79????w-vs
Table C(SENAPSO-16)
2 θ d(dusts) relative intensity
11.3-11.6????7.83-7.63????w-vs
18.55-18.9????4.78-4.70????vm-m
21.85-22.2????4.07-4.00????m-vs
22.8-23.3????3.900-3.818????w-m
26.4-27.3????3.370-3.267????w-m
29.6-29.9????3.018-2.988????w-m
Table D(SENAPSO-20)
2 θ d(dusts) relative intensity
13.8-14.2????6.42-6.23????m-vs
19.6-20.15????6.53-4.41????m
24.1-24.7????3.695-3.603????m-vs
27.9-28.6????3.198-3.121????w
31.3-32.05????2.861-2.791????w
34.35-35.0????2.610-2.601????w-m
Table E(SENAPSO-31)
2 θ d(dusts) relative intensity
8.4-9.5????10.53-9.31????w-s
20.2-20.4????4.40-4.35????m
22.0-22.1????4.040-4.022????m
22.5-22.7????3.952-3.92????vs
31.6-31.8????2.831-2.814????w-m
Table F(SENAPSO-34)
2 θ d(dusts) relative intensity
9.3-9.8????9.51-9.03????m-vs
12.6-13.2????7.03-6.71????w-m
15.8-16.3????5.61-5.44????vw-m
20.25-21.2????4.39-4.19????w-vs
24.8-25.4????3.59-3.507????vw-m
30.0-30.9????2.979-2.894????vw-m
Table G(SENAPSO-35)
2 θ d(dusts) relative intensity
10.6-11.1????8.35-7.97????vw-vs
13.1-13.7????6.76-6.46????vw-vs
17.0-17.6????5.22-5.04????w-s
20.6-21.25????4.31-4.18????vw-m
21.6-22.3????4.11-3.99????m-vs
28.1-28.8????3.175-3.100????vw-m
Table H(SENAPSO-36)
2 θ d(dusts) relative intensity
7.45-8.0????11.14-11.05????vs
8.1-8.3????10.91-10.65????w-m
16.3-16.6????5.44-5.34????w-m
18.9-19.4????4.70-4.57????w-m
20.7-21.0????4.29-4.23????w-m
Table J(SENAPSO-39)
2 θ d(dusts) relative intensity
9.2-9.6????9.61-9.21????m
13.1-13.5????6.76-6.56????m
17.8-18.4????4.98-4.82????w-m
20.8-21.3????4.27-4.17????m-vs
22.2-22.85????4.00-3.892????m-vs
26.4-27.05????3.376-3.296????w-m
Table K(SENAPSO-43)
2 θ d(dusts) relative intensity
12.3-12.95????7.20-6.83????m-vs
16.8-17.45????5.28-5.09????vw-w
21.45-21.85????4.145-4.071????m-vs
27.1-27.85????3.291-3.232????w-vs
32.4-33.2????2.763-2.699????vw-m
Table L(SENAPSO-44)
2 θ d(dusts) relative intensity
9.2-9.6????9.61-9.21????m-vs
15.9-16.3????5.57-5.44????vw-m
20.5-21.0????4.33-4.23????m-vs
24.3-25.1????3.66-3.548????w-m
30.5-31.1????2.931-2.876????vw-m
Table M(SENAPSO-46)
2 θ d(dusts) relative intensity
7.2-8.1????12.28-10.92????vs
12.9-13.6????6.86-6.51????vw
21.2-22.2????4.19-4.501????vw-m
22.5-23.45????3.95-3.793????vw-m
26.6-27.9????3.351-3.198????vw-m
Table N(SENAPSO-47)
2 θ d(dusts) relative intensity
9.4-9.6????9.41-9.21????vs
12.8-13.1????6.92-6.76????vw-m
16.0-16.3????5.54-5.44????vw-m
20.5-21.0????4.31-4.23????m-vs
24.6-25.3????3.613-3.526????vm-m
30.6-31.1????2.921-2.876????vw-m
Being provided at following all examples, is for the invention will be further described, the meaning of the present invention without limits.
The preparation of example 1 to 10 agents useful for same
In following all examples, preparation CoMnAPSO composition need be used many reagent.Used reagent and abbreviation are as follows;
A) Alipro: aluminum isopropylate;
B) LUDOX-LS; LUDOX-LS is the trade(brand)name of DuPont, is a kind of SiO of containing 230(weighs %) and Na 2The heavy % of O0.1() the aqueous solution;
C) H 3PO 4: concentration is the heavy % of 85() phosphoric acid;
D) MnAc: manganous acetate, Mn(C 2H 3O 2) 24H 2O;
E) CoAc: cobaltous acetate, Co(C 2H 3O 2) 24H 2O;
F) aqueous solution TEAOH: contain the heavy % of hydroxide tetraethyl ammonium 40();
G) Pr 2NH: di-n-propylamine, (C 3H 7) 2NH.
The preparation method
Introduce the preparation example below
With H 3PO 4Mix the preparation starting mixt with the water of 1/2nd amounts.Aluminum isopropylate is added this mixture.By the time after this mixture is mixed into homogeneous, add LUDOX, be mixed into (about 2 minutes) till the homogeneous.Prepare second mixture with manganous acetate and 1/2nd remaining water.Prepare the 3rd mixture with cobaltous acetate and 1/2nd remaining water.Above-mentioned three kinds of mixtures are blended together, till being mixed into homogeneous, join organic formwork agent in the said mixture then and be mixed to homogeneous till (about 2～4 minutes).Measure the pH value of mixture, and by temperature correction.Then the mixture of gained is put into pressurizing vessel teflon lined, stainless steel, boiling at a certain temperature, whole boiling process all is to carry out at spontaneous pressure.
Example 1 to 4
Make the CoMnAPSO molecular sieve according to above-mentioned definite step.Measure the CoMnAPSO product with x-ray analysis.Example 1 to 4 the results are shown in Table I.Example A to F does not show it is the CoMnAPSO product with the x-ray method analytical results in the table I
The table I
Example (1)Die plate temperature (℃) time (my god) the CoMnMgAPSO product (2)
1????TEAOH????150????2????CoMnAPSO-34;CoMnAPSO-5
2????TEAOH????150????7????CoMnAPSO-34;CoMnAPSO-5
3 Pr 2NH 200 2 CoMnAPSO-5;CoMnAPSO-11
4 Pr 2NH 200 7 CoMnAPSO-5;CoMnAPSO-11
A????TEAOH????100????3????-
B????TEAOH????100????7????-
C Pr 2NH 150 2 -
D 3Pr 2NH 150 10 -
E 3Pr 2NH 150 6 -
F 3Pr 2NH 150 15 -
[1] reaction mixture contains:
1.0R∶0.2MnO∶0.2CoO∶0.8Al 2O 3∶0.8P 2O 5∶0.4SiO 2∶50H 2O
" R " is template in the formula.
[2] principal item that identifies with the X-ray powder diffraction figure of product, but when identifying two kinds.In the table to the amount of first kind be equal to or greater than second kind.The crystalline product that "-" expression X-ray analysis does not identify.
[3] analytical results of X ray shows, crystalline product is beginning to form.
Example 5
(a) with the CoMnAPSO product roasting in air that makes previously, so that can remove the interior a part of organic formwork agent of CoMnAPSO product at least.Measure the adsorptive power of each roasting sample with standard McBain-BaKr weight an adsorption device.Before measuring, sample is activated under vacuum (being lower than 0.04 torr) and 350 ℃ of conditions.Measured McBain-BaKr data are as follows:
(b) CoMnAPSO-34 and CoMnAPSO-5(example 2):
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity (heavy %)
Oxygen 3.46 105-183 13.8
Oxygen 3.46 733-183 18.5
Neopentane 6.2 742 23.8 2.6
Hexanaphthene 6.0 65 23.7 4.6
Normal hexane 4.3 93 23.4 5.0
H 2O 2.65 4.6 23.4 15.8
H 2O 2.65 19 23.7 23.6
*Before activation, 600 ℃ of roastings 1 hour in air.
(c) CoMnAPSO-5 and CoMnAPSO-11(example 4):
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity (heavy %) *
Oxygen 3.46 105-183 5.5
Oxygen 3.46 733-183 9.3
Neopentane 6.2 742 23.8 2.4
Hexanaphthene 6.0 65 23.7 5.9
H 2O 2.65 4.6 23.4 7.4
H 2O 2.65 19 23.7 16.2
*Before activation, 600 ℃ of roastings 1 hour in air.
Example 6
Firm synthetic product sample to example 2 and 4 carries out chemical analysis.The chemical analysis results of these CoMnAPSO samples is as follows:
(a) chemical analysis results of example 2 products is:
Component weight percentage
Al 2O 327.5
P 2O 537.7
SiO 24.98
CoO????4.3
MnO????5.2
Carbon 5.3
LOI ＊20.5
*Loss by roasting.
The product by the oxide mol ratio of anhydrous benchmark that is obtained by above-mentioned chemical analysis consists of entirely:
0.057 CoO∶0.073 MnO∶0.270 Al 2O 3∶0.266 P 2O 5∶0.083SiO 2
Chemical formula (anhydrous benchmark):
0.055R（Al 0.420P 0.414Si 0.065Co 0.044Mn 0.057）O 2
(b) chemical analysis results of example 4 products is:
Component weight percentage
Al 2O 326.6
P 2O 537.6
SiO 27.1
CoO????5.1
MnO????6.0
Carbon 1.91
LOI ＊17.9
*Loss by roasting.
The product by the oxide mol ratio of anhydrous benchmark that is obtained by above-mentioned chemical analysis consists of entirely:
0.068CoO∶0.085MnO∶0.261Al 2O 3∶0.265P 2O 5∶0.118SiO 2
Chemical formula (anhydrous benchmark) is:
0.027R（Al 0.40P 0.40Si 0.089Co 0.051Mn 0.064）O 2
Example 7
The product of example 2 and 4 is carried out the microprobe Conjoint Analysis of electron microscope scanning and X ray energy dispersion analysis (EDA).Crystal with morphological specificity CoMnAPSO product is as follows based on the analytical results of relative peak height:
(a) example 2(CoMnAPSO-5):
Microcell mean value
Al????0.81
P????0.98
Si????0.18
Co????0.10
Mn????0.17
(b) example 2(CoMnAPSO-34):
Microcell mean value
Al????0.82
P????0.93
Si????0.17
Co????0.03
Mn????0.03
(c) example 4(CoMnAPSO-5):
Microcell mean value
Al????0.93
P????0.71
Si????0.15
Co????0.05
Mn????0.07
(d) example 4(CoMnAPSO-11):
Microcell mean value
Al????0.81
P????0.95
Si????0.15
Co????0.03
Mn????0.05
Example 8
1 made CoMnAPSO carries out X-ray analysis to example.The feature of the X-ray powder diffraction figure of CoMnAPSO-5 is as follows:
2 θ d(dusts) (I/I 0) * 100
7.5????11.84????67
9.5 ＊9.29 100
12.9 ＊＊6.89 11
14.1 ＊6.29 7
14.9????5.93????14
16.0 ＊5.54 22
18.0 ＊4.93 10
19.8????4.49????19
20.6 ＊4.32 51
21.1 ＊＊4.22 40
22.4????3.96????28
25.2 ＊3.530 12
29.1????3.071????6
29.5 ＊3.024 3
30.1????2.968????10
30.5 ＊2.928 16
31.3 ＊2.862 11
33.7 ＊2.659 3
34.5????2.601????4
34.6 ＊2.591 5
37.8????2.383????6
47.7 ＊＊1.905 3
48.9 ＊1.863 2
49.9 ＊1.828 2
50.9 ＊1.794 2
55.8????1.647????2
*This peak may be a kind of impurity;
*Impurity peaks and CoMnMgAPSO-5.
(b) example 2 made firm synthetic CoMnAPSO-5 are got a part in air 600 ℃ of roastings 1 hour.The feature of the X-ray powder diffraction figure of roasting product is as follows:
2 θ d(dusts) (I/I 0) * 100
7.5????11.84????32
9.6 ＊9.20 100
13.0 ＊＊6.81 20
14.9????5.93????4
16.2 ＊5.48 8
18.0 ＊4.93 6
19.3 ＊4.60 3
19.8????4.49????8
20.9 ＊＊4.26 22
21.2 ＊＊4.20 26
21.5 ＊4.13 3
22.5????3.95????32
23.4 ＊3.81 3
25.3 ＊3.520 7
26.1????3.420????11
26.2 ＊3.396 7
28.5 ＊3.129 3
29.2????3.063????6
30.2????2.965????6
31.0 ＊2.881 11
31.5 ＊2.840 7
34.7????2.584????4
34.9????2.568????3
38.0 ＊2.368 2
*This peak may be a kind of impurity;
*Impurity peaks and CoMnAPSO-5.
(c) kind CoMnAPSO-5 has the molecular sieve that contains interplanar distance characteristic X-ray powder diagram shown in following table II at least.
The table II
2 θ d(dusts) relative intensity
7.4-7.5????11.95-11.84????m
12.9-13.1????6.89-6.76????w-m
14.9????5.93????vw-w
19.7-19.8????4.51-4.49????vw-w
20.9-21.3????4.26-4.17????m
22.4-22.5????3.97-3.95????m
(d) resulting whole CoMnAPSO-5 composition (comprise firm synthetic and through roasting) x-ray powder derivative data, comprehensively list in following table III:
The table III
2 θ d(dusts) (I/I 0) * 100
7.4-7.5????11.95-11.84????32-67
12.9-13.1????6.89-6.81????11-20
14.9????5.93????4-14
19.7-19.8????4.51-4.49????8-19
20.9-21.3????4.26-4.17????22-40
22.4-22.5????3.96-3.95????28-32
24.7-24.8????3.60-3.59????6
25.9-26.1????3.440-3.420????10-11
29.0-29.2????3.079-3.063????6
29.9-30.2????2.988-2.965????6-10
34.4-34.7????2.607-2.584????4
34.9????2.568????3
37.8????2.383????6
47.7????1.905????3
55.8????1.647????2
Example 9
(a) example 3 made CoMnAPSO-11 are carried out X-ray analysis.CoMnAPSO-11 is impure, but it has the X-ray powder diffraction figure shown in the following column data.
2 θ d(dusts) (I/I 0) * 100
7.0 ＊12.56 12
7.5 ＊11.86 68
8.1????10.88????46
9.5????9.31????68
12.9 ＊6.87 11
13.2????6.73????24
14.9 ＊5.95 12
15.7????5.64????49
16.3????5.44????9
19.0????4.67????9
19.7 ＊4.50 29
20.4????4.36????66
21.1 ＊＊4.21 37
21.2????4.19????34
22.4 ＊3.96 41
22.8????3.91????29
23.2????3.83????100
24.8 ＊＊3.59 10
25.9 ＊3.443 23
26.5????3.365????32
28.2????3.163????9
28.7????3.113????25
29.5????3.024????8
29.9 ＊2.985 15
31.5????2.838????8
32.7????2.739????2
34.2????2.622????2
36.4????2.468????2
37.6????2.392????2
*This peak may be a kind of impurity;
*Impurity peaks.
(b) example 4 made firm synthetic CoMnAPSO-11 are got a part in air and 600 ℃ of roastings 1 hour.The feature of the X-ray powder diffraction figure of roasting product is as follows:
2 θ d(dusts) (I/I 0) * 100
22.5 ＊＊3.96 62
23.4????3.80????100
26.0 ＊3.423 43
26.4????3.376????40
26.6????3.346????16
29.1 ＊3.073 27
29.2????3.061????28
30.2 ＊2.962 21
32.8????2.732????21
32.9????2.719????31
34.7 ＊2.586 28
36.2????2.481????2
7.5 ＊11.86 95
8.2????10.85????68
9.6????9.19????95
13.1 ＊6.77 45
15.9????5.58????91
19.8 ＊4.48 32
20.3????4.37????49
21.3 ＊4.17 34
*This peak may contain impurity;
*Impurity peaks.
(c) kind CoMnAPSO-11 has the molecular sieve that contains interplanar distance characteristic X-ray powder diagram shown in following table IV at least.
The table IV
2 θ d(dusts) relative intensity
9.5-9.6????9.31-9.21????m-vs
15.7-15.9????5.64-5.57????m-vs
20.3-20.4????4.37-4.36????m
21.1-21.2????4.21-4.19????m
22.1-22.5????4.02-3.95????m
23.2-23.4????3.83-3.80????vs
(d) resulting whole CoMnAPSO-11 composition (comprise firm synthetic and through roasting) x-ray powder derivative data, comprehensively list in following table V:
The table V
2 θ d(dusts) (I/I 0) * 100
8.1-8.2????10.88-10.85????46-68
9.5-9.6????9.31-9.19????68-95
13.1-13.2????6.77-6.73????24-45
15.7-15.9????5.64-5.58????49-91
16.3????5.44????9
19.0????4.67????9-10
20.3-20.4????4.37-4.36????49-66
21.1-21.2????4.21-4.19????30-37
22.1-22.5????4.02-3.96????31-62
22.7-22.8????3.92-3.91????28-29
23.2-23.4????3.83-3.80????100
24.7-24.8????3.60-3.59????10-14
26.4-26.6????3.376-3.346????16-40
28.1-28.2????3.175-3.163????9
28.7????3.113????25-26
29.2-29.5????3.061-3.024????8-28
31.5????2.838????8
32.7-32.8????2.739-2.732????2-27
32.9????2.719????31
34.2????2.622????2-11
36.2-36.4????2.481-2.468????2-9
37.6-37.9????2.392-2.374????2-3
Example 10
(a) example 1 made CoMnAPSO-34 is carried out X and penetrate analysis.CoMnMgAPSO-34 is impure, but it has the X-ray powder diffraction figure shown in the following column data.
2 θ d(dusts) (I/I 0) * 100
7.5 ＊11.84 67
9.5????9.29????100
12.9 ＊＊6.89 11
×100
14.1????6.29????7
14.9 ＊5.93 14
16.0????5.54????22
18.0????4.93????10
19.8 ＊4.49 19
20.6????4.32????51
21.1 ＊＊4.22 40
22.4 ＊3.96 28
25.2????3.530????12
29.1 ＊3.071 6
29.5????3.024????3
30.1 ＊2.968 10
30.5????2.928????16
31.3????2.862????11
33.7????2.659????3
34.5 ＊2.601 4
34.6????2.591????5
37.8 ＊2.383 6
47.7 ＊＊1.905 3
48.9????1.863????2
49.9????1.828????2
50.9????1.794????2
55.8 ＊1.647 2
*This peak may contain impurity.
*Impurity peaks.
(b) the firm synthetic CoMnAPSO-34 of example 2 system is got a part in air and 600 ℃ of roastings 1 hour.The feature of the X-ray powder diffraction figure of roasting product is as follows:
2 θ d(dusts) (I/I 0) * 100
7.5 ＊11.84 32
9.6????9.20????100
13.0 ＊＊6.81 20
14.9 ＊5.93 4
16.2????5.48????8
18.0????4.93????6
19.3????4.60????3
19.8 ＊4.49 8
20.9 ＊＊4.26 22
21.2 ＊＊4.20 26
21.5????4.13????3
22.5 ＊3.96 32
23.4????3.81????3
25.3????3.520????7
26.1 ＊3.420 11
26.2????3.396????7
28.5????3.129????3
29.2 ＊3.063 6
30.2 ＊2.965 6
31.0????2.881????11
31.5????2.840????7
34.7 ＊2.584 4
34.9 ＊2.568 3
38.0????2.368????2
*This peak may contain impurity.
*Impurity peaks.
(c) CoMnAPSO-34 is the molecular sieve that the characteristic X-ray powder diagram is arranged.This figure has the interplanar distance (d) shown in the table VI at least:
The table VI
2 θ d(dusts) relative intensity
9.5-9.6????9.29-9.20????vs
12.8-13.0????6.92-6.81????w-m
16.0-16.2????5.54-5.48????vw-m
20.6-20.9????4.32-4.26????m
21.1-21.2????4.22-4.20????m
25.2-25.3????3.530-3.520????vw-w
31.0-31.5????2.881-2.840????w
(d) (just synthetic and through roasting) X-ray powder diffraction data of all CoMnAPSO-34 compositions have been obtained.They have the figure in following generalization pattern:
The table VII
2 θ d(dusts) (I/I 0) * 100
9.5-9.6????9.29-9.20????100
12.8-13.0????6.92-6.81????11-20
14.1????6.29????7-9
16.0-16.2????5.54-5.48????8-23
18.0????4.93????6-12
19.3????4.60????3
20.6-20.9????4.32-4.26????22-57
21.1-21.2????4.22-4.20????26-40
21.5????4.13????3
23.0-23.4????3.87-3.81????2-3
25.2-25.3????3.530-3.520????7-14
25.8-26.2????3.453-3.396????7-13
27.5????3.243????2
2 θ d(dusts) (I/I 0) * 100
28.3-28.5????3.153-3.129????3-4
29.5????3.024????3
30.5????2.928????16-18
31.0-31.5????2.881-2.840????11-13
33.7-33.8????2.659-2.652????2-7
34.5-34.6????2.601-2.592????5
38.0????2.368????2
39.6????2.276????2
43.3????2.090????2
47.5-47.7????1.914-1.905????2-3
48.9-49.0????1.863-1.859????2-4
49.9????1.828????2
50.8-50.9????1.797-1.794????2-3
Reagent for each examples preparation
In following example 11-20, the CoMnMgAPSO composition is with many kinds of reagent preparation.The reagent that uses and the abbreviation (if any) of these reagent are as follows:
(a) Alipro: aluminum isopropylate;
(b) LUDOX-LS:LUDOX-LS is that the production of DuPont company contains 30 heavy %SiO 2With 0.1 heavy %Na 2The trade(brand)name of the aqueous solution of O;
(c) H 3PO 4: the aqueous solution that contains 85 heavy % phosphoric acid;
(d) MnAc: manganous acetate, Mn(C 2H 3O 2) 24H 2O;
(e) CoAc: cobaltous acetate: Co(C 2H 3O 2) 24H 2O;
(f) MgAc: magnesium acetate, Mg(C 2H 3O 2) 24H 2O;
(g) the heavy % tetraethyl ammonium hydroxide of the TEAOH:40 aqueous solution;
(h) Pr 2NH: di-n-propylamine, (C 3H 7) 2NH.
Preparation process
Below the preparation example is to use H 3PO 4The initial action mixture that adds the water generation of half amount.Aluminum isopropylate is added in this mixture.Stir this mixture then, up to the mixture that obtains homogeneous.LUDOX-LS is added in this mixture, and stir the mixture (about 2 minutes) are up to the mixture that obtains homogeneous.
Prepare other three kinds of mixtures with cobaltous acetate, magnesium acetate and manganous acetate, each mixture uses 1/3rd of surplus water, then four kinds of mixtures is mixed, and stirs the mixture that generates, up to the mixture that obtains homogeneous.And then organic formwork agent is added in the mixture of gained.Stir the mixture that is become,, for example use about 2-4 minute up to the mixture that obtains homogeneous.Then mixture is put into the stainless steel pressure container of (tetrafluoroethylene) in the belt material, and at certain temperature boiling certain hour.Whole boiling process is finished at spontaneous pressure.
The mole of preparation is each time formed and is represented H with the relative mole number of each component 3PO 4Be expressed as P 2O 5
Example 11-14
The CoMnMgAPSO molecular sieve is by top given step preparation, and the COMnMgAPSO product is measured with X-ray analysis.The result of preparation example 11-14 lists table I-1 in.Routine A-1, B-1 and the C-1 of table I-1 contain the CoMnMgAPSO product that useful X-ray analysis can identify.
Table I-1
Example (1)Die plate temperature (℃) time (my god) the CoMnMgAPSO product (2)
11????TEAOH????100????7????CoMnMgAPSO-34
12????TEAOH????150????2????CoMnMgAPSO-34;CoMnMgAPSO-5
13????TEAOH????150????7????CoMnMgAPSO-34;CoMnMgAPSO-5
14 Pr 2NH 200 13 CoMnMgAPSO-11
A-1????TEAOH????100????2????-
B-1 Pr 2NH 150 3 -
C-1 Pr 2NH 150 10 -
[1] reaction mixture contains:
1.0R∶0.2MnO∶0.2CoO∶0.2MgO∶0.7Al 2O 3∶0.8P 2O 5∶0.4SiO 2∶50H 2O
" R " is template in the formula.
[2] principal item of the X-ray powder diffraction figure evaluation of usefulness product.But when identifying two kinds, kind is listed by their content sequence in product."-" expression does not identify the SENAPSO product with X-ray analysis.
Example 15
Example 13 and 14 product are respectively got part roasting 1.5 hours in 600 ℃ of air, remove a part of organic formwork agent at least.The loading capacity of each roasting sample is measured with the McBain-Baker weight absorption instrument of standard.Sample activates in 350 ℃, vacuum (less than about 0.04 torr) before measuring.The McBain-Bakr data of CoMnMgAPSO product are as follows:
(a) example 13(CoMnMgAPSO-34 and CoMnMgAPSO-5)
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity (heavy %)
Oxygen 3.46 105-183 6.0
Oxygen 3.46 733-183 8.4
Neopentane 6.2 742 23.8 1.4
Hexanaphthene 6.0 65 23.7 2.6
Normal hexane 6.0 93 23.4 3.3
Water 2.65 4.6 23.4 7.3
Water 2.65 19 23.7 12.0
(b) example 14(CoMnMgAPSO-11)
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity (heavy %)
Oxygen 3.46 105-183 2.9
Oxygen 3.46 733-183 3.6
Neopentane 6.2 742 23.8 0.5
Hexanaphthene 6.0 65 23.7 2.1
Water 2.65 4.6 23.4 4.1
Water 2.65 19 23.7 9.1
Example 16
Example 13 and 14 product are got a part respectively and are carried out chemical analysis.Chemical analysis results is as follows:
(a) example 13
Component weight percentage
Al 2O 321.5
P 2O 540.3
SiO 26.5
CoO????4.58
MnO????4.41
MgO????2.43
Carbon 6.9
LOI ＊18.3
*Roasting weightlessness.
Above-mentioned chemical analysis obtains forming with the total product of oxide mol ratio (butt) expression:
0.575R∶0.061CoO∶0.062MnO∶0.060MgO∶0.211Al 2O 3∶0.284P 2O 5∶0.108SiO 2
Chemical formula (butt) is:
0.072R（Co 0.048Mn 0.048Mg 0.047Al 0.33P 0.44Si 0.084）O 2
(b) example 14
Component weight percentage
Al 2O 324.3
P 2O 541.8
SiO 28.5
CoO????6.0
MnO????6.8
MgO????2.8
Component weight percentage
Carbon 1.54
LOI ＊9.3
*Roasting weightlessness.
Above-mentioned chemical analysis obtains forming with total product of oxide mol ratio (butt) expression:
0.128R∶0.08CoO∶0.096MnO∶0.070MgO∶0.238Al 2O 3∶0.294P 2O 5∶0.141SiO 2
Chemical formula (butt) is:
0.0213R（Co 0.055Mn 0.066Mg 0.048Al 0.33P 0.41Si 0.097）O 2
Example 17
EDAX(X ray energy chromatic dispersion analysis) with the SEM(scanning electronic microscope) combine and carry out example 13 and the pure crystal analysis of 14 products.Have the crystal analysis of CoMnMgAPSO-5, CoMnMgAPSO-11 and CoMnMgAPSO-34 morphological specificity to obtain following analytical results based on relative peak height:
（a）CoMnMgAPSO-5：
Microcell mean value
Co????0.11
Mn????0.16
Mg????0.08
Al????0.55
P????1.0
Si????0.11
（b）CoMnMgAPSO-11：
Microcell mean value
Co????0.09
Mn????0.06
Mg????0.11
Al????0.85
P????0.99
Si????0.38
（c）CoMnMgAPSO-34：
Microcell mean value
Co????0.05
Mn????0.03
Mg????0.05
Al????0.81
P????1.0
Si????0.20
Example 18
(a) prepared CoMnMgAPSO-5 carries out X-ray analysis in example 13.Determined that this sample has the characteristic X-ray powder diagram that contains interplanar distance as follows (d):
2 θ d(dusts) 100 * I/I 0
7.4????11.89????15
9.5 ＊9.27 100
12.8 ＊＊6.90 19
14.1 ＊6.28 14
14.9????5.96????6
16.0 ＊5.54 46
18.1 ＊4.90 28
19.2 ＊4.63 12
19.7????4.50????16
20.6 ＊4.32 92
21.1????4.20????13
22.4 ＊3.97 22
22.6????3.94????5
23.1 ＊3.85 6
25.2 ＊3.529 28
25.8 ＊＊3.454 32
27.6 ＊3.237 4
28.4 ＊3.142 4
29.0????3.079????5
29.5 ＊3.025 4
29.9????2.987????7
30.5 ＊＊2.930 37
31.3 ＊2.863 25
32.4 ＊2.767 26
34.4 ＊＊2.608 11
35.4 ＊2.537 5
36.3 ＊2.473 5
37.8????2.382????4
38.7 ＊2.329 6
38.8 ＊2.323 6
39.6 ＊2.276 5
43.3 ＊2.088 5
45.1????2.010????3
46.1 ＊1.971 4
2 θ d(dusts) (I/I 0) * 100
46.3????1.962????5
47.2 ＊1.924 7
48.7????1.870????6
48.9 ＊1.863 6
51.0 ＊1.791 4
53.0 ＊1.728 4
53.1 ＊1.726 4
*This peak may be a kind of impurity;
*Impurity peaks and CoMnMgAPSO-5.
(b) (a) the firm synthetic CoMnMgAPSO-5 in the part gets part roasting 1 hour in 600 ℃ of air.Product after the roasting characterizes as follows with X-ray powder diffraction figure:
2 θ d(dusts) 100 * I/I 0
7.5????11.76????100
9.7 ＊9.14 86
13.1 ＊＊6.79 18
15.0????5.90????30
16.3 ＊5.44 8
18.1 ＊4.90 7
19.9????4.47????19
21.2 ＊＊4.19 35
21.5 ＊4.13 44
22.6????3.94????37
23.0 ＊3.87 6
26.1????3.414????21
26.4 ＊3.379 9
29.2????3.060????8
30.2????2.956????59
31.2 ＊2.871 12
2 θ d(dusts) (I/I 0) * 100
31.7 ＊2.819 7
34.7????2.582????13
35.5 ＊2.528 16
*This peak may be a kind of impurity
*Impurity peaks and CoMnMgAPSO-5
(c) CoMnMgAPSO-5 is a kind of CoO of having -2 2, MnO -2 2, MgO -2 2, AlO - 2, PO + 2And SiO 2The molecular sieve of the three-dimensional microporous framework structure of tetrahedral oxide units.Its butt empirical formula:
mR∶（Co tMn uMg vAl xP ySi z）O 2
Wherein " R " is illustrated in the organic formwork agent that exists in the system of intracrystalline hole; " m " represents each mole (Co tMn uMg vAl xP ySi z) O 2The mole number of " R " that exists, its value is about 0-0.3; " t ", " u ", " v ", " x ", " y " and " z " represent that respectively wherein " w " is the summation of " t+u+v " as the molar fraction of cobalt, manganese, magnesium, aluminium, phosphorus and the silicon of tetrahedral oxide existence.Above-mentioned molar fraction is preferably in the composition district of Fig. 2 mid point a, b, c, d, e and f qualification in the composition district that Fig. 1 mid point A, B, C, D and E limit.CoMnMgAPSO-5 has the characteristic X-ray powder diagram that contains interplanar distance as follows (d) at least:
2 θ d(dusts) relative intensity
7.2-7.7????12.28-11.48????m-vs
19.4-19.9????4.58-4.46????w-m
20.85-21.3????4.26-4.17????w-vs
22.1-22.6????4.02-3.93????m-vs
25.6-26.1????3.480-3.414????vw-m
(d) the CoMnMgAPSO-5 composition that has obtained the X-ray powder diffraction data has the figure of following data characterization:
The table III
2 θ d(dusts) 100 * I/I 0
7.4-7.5????11.89-11.76????15-100.0
12.8-13.1????6.90-6.79????16-19
14.9-15.0????5.96-5.90????6-30
19.7-19.9????4.50-4.47????16-19
21.1-21.2????4.20-4.19????10-35
22.6????3.94????5-37
25.8-26.1????3.454-3.414????18-32
29.0-29.2????3.079-3.060????4-8
29.9-30.2????2.987-2.956????7-59
30.5????2.930????28-37
34.4-34.7????2.608-2.582????11-14
37.8????2.382????4
45.1????2.010????3
46.3????1.962????5
48.7????1.870????6
Example 19
(a) CoMnMgAPSO-11 of preparation carries out X-ray diffraction analysis in the example 16.Determined that CoMnMgAPSO-11 has the characteristic X-ray powder diagram that contains interplanar distance as follows (d):
2 θ d(dusts) 100 * I/I 0
8.1????10.95????21
9.5????9.35????34
13.1????6.75????9
15.7????5.66????22
20.3????4.37????29
21.1????4.21????75
22.1????4.02????34
22.4????3.97????27
2 θ d(dusts) (I/I 0) * 100
22.7????3.92????34
23.1????3.84????53
24.7????3.61????7
26.4????3.374????23
27.6 ＊3.234 100
28.6????3.124????75
32.7????2.736????13
35.2????2.548????20
37.5????2.396????8
37.8????2.383????9
37.9????2.373????7
40.1????2.247????12
45.0????2.013????11
45.2????2.006????18
45.3????2.001????20
45.8????1.983????13
45.9????1.977????13
50.4????1.812????10
50.6????1.803????15
*This peak may contain a kind of impurity
(b) the firm synthetic CoMnMgAPSO-11 in (a) gets part roasting 1 hour in 600 ℃ of air.Product after the roasting characterizes as follows with X-ray powder diffraction figure:
2 θ d(dusts) (I/I 0) * 100
8.1????10.95????31
9.6????9.23????43
13.0????6.80????30
15.8????5.60????37
20.2????4.40????27
21.3????4.18????100
22.3????3.99????65
23.0????3.87????36
2 θ d(dusts) (I/I 0) * 100
23.4????3.80????50
24.4????3.65????11
26.3????3.392????25
28.3????3.157????83
28.9????3.090????17
29.1????3.067????11
32.8????2.734????19
34.3????2.614????12
37.9????2.373????12
39.0????2.309????15
39.3????2.294????14
44.8????2.025????16
44.9????2.021????17
(c) CoMnMgAPSO-11 is a kind of CoO of having -2 2, MnO -2 2, AlO - 2, PO + 2And SiO 2The molecular sieve of the three-dimensional microporous framework structure of tetrahedral oxide units.Its butt empirical formula is:
mR∶（Co tMn uMg vAl xP ySi z）O 2
Wherein " R " is illustrated in the organic formwork agent that exists in the system of intracrystalline hole; " m " represents each mole (Co tMn uMg vAl xP ySi z) O 2The mole number of " R " that exists, its value is from about the 0-0.3; " t ", " u ", " v ", " x ", " y " and " z " represent that respectively wherein " w " is the summation of " t+u+v " as the molar fraction of cobalt, manganese, magnesium, aluminium, phosphorus and the silicon of tetrahedral oxide existence.Above-mentioned molar fraction is put in the composition district of A, B, C, D and E qualification in the drawings, is preferably in the composition district of Fig. 2 mid point a, b, c, d, e and f qualification.CoMnMgAPSO-11 has the characteristic X-ray powder diagram that contains interplanar distance as follows (d) at least:
2 θ d(dusts) relative intensity
7.8-8.2????11.19-10.85????m-s
9.0-9.8????9.83-9.03????vw-vs
12.8-13.6????6.92-6.51????vw-m
19.9-20.5????4.46-4.33????m-s
20.8-21.8????4.27-4.08????m-vs
22.0-22.6????4.04-3.93????m-vs
22.6-23.1????3.93-3.85????vw-vs
23.1-23.5????3.85-3.79????w-vs
(d) the CoMnMgAPSO-11 composition that has recorded the X-ray powder diffraction data has the figure of following data characterization:
2 θ d(dusts) (I/I 0) * 100
8.1-8.2????10.95-10.65????17-31
9.5-9.6????9.35-9.23????34-46
13.0-13.3????6.80-6.66????9-30
15.7-15.8????5.66-5.60????22-37
20.2-20.4????4.40-4.35????27-29
21.1-21.4????4.21-4.15????75-100
22.1-22.3????4.02-3.99????34-65
22.4????3.97????27
22.7????3.92????34-100
23.0-23.2????3.87-3.83????36-53
23.3-23.4????3.82-3.80????50-70
24.4-24.7????3.65-3.61????7-11
26.3-26.5????3.392-3.363????23-25
28.3-28.7????3.157-3.110????75-83
28.9????3.090????16
29.1-30.4????3.067-2.940????11-14
32.7-32.8????2.739-2.734????13-19
34.3????2.614????12
35.2????2.548????20
37.5-37.8????2.398-2.383????8
37.9????2.373????7-12
39.0????2.309????15
39.3-40.1????2.294-2.247????12-16
44.8-45.0????2.025-2.013????11-17
45.2????2.006????18
2 θ d(dusts) (I/I 0) * 100
45.3????2.001????20
45.8????1.983????13
45.9????1.977????13
50.4????1.812????10
50.6????1.803????15
Example 20
(a) prepared CoMnMgAPSO-34 carries out X-ray analysis in the example 13.Determined that CoMnMgAPSO-34 has the characteristic X-ray powder diagram that contains interplanar distance as follows (d):
2 θ d(dusts) (I/I 0) * 100
7.4 ＊11.89 15
9.5????9.31????100
12.8 ＊＊6.90 19
14.1????6.28????14
14.9 ＊5.96 6
16.0????5.54????46
18.1????4.90????28
19.2????4.62????12
19.7 ＊4.50 16
20.6????4.32????92
21.1 ＊4.20 13
22.4????3.97????22
22.6 ＊3.94 5
23.1????3.85????6
25.2????3.534????28
25.8 ＊＊3.454 32
27.6????3.237????4
28.4????3.142????4
29.0 ＊3.079 5
29.5????3.025????4
29.9 ＊2.987 7
30.5 ＊＊2.930 37
2 θ d(dusts) (I/I 0) * 100
31.3????2.863????25
32.4????2.767????26
34.4 ＊＊2.608 11
35.4 ＊2.537 5
36.3????2.473????5
37.8 ＊2.382 4
38.7 ＊2.329 6
38.8????2.323????6
39.6????2.276????5
43.3????2.088????5
45.1 ＊2.010 3
46.1 ＊1.971 4
46.3 ＊1.962 5
47.2????1.924????7
48.7 ＊1.870 6
48.9????1.863????6
51.0????1.791????4
53.0????1.728????4
53.1????1.726????4
*This peak may contain impurity;
*This peak contains impurity and CoMnMgAPSO-34.
(b) (a) in just synthetic CoMnMgAPSO-34 get part roasting 1 hour in 600 ℃ of air.Product after the roasting characterizes as follows with X-ray powder diffraction figure:
2 θ d(dusts) (I/I 0) * 100
7.5 ＊11.76 100
9.7????9.14????86
13.1 ＊＊6.79 18
15.0 ＊5.90 30
16.3????5.44????8
18.1????4.90????7
2 θ d(dusts) (I/I 0) * 100
19.9 ＊4.47 19
21.2 ＊＊4.19 35
21.5????4.13????44
22.6 ＊3.94 37
23.0????3.87????6
26.1 ＊＊3.414 21
26.4????3.379????9
29.2 ＊3.060 8
30.2 ＊2.956 59
31.2????2.871????12
31.7????2.819????7
34.7 ＊2.582 13
35.5????2.528????16
*This peak may contain impurity;
*Impure and the CoMnMgAPSO-34 in this peak.
(c) CoMnMgAPSO-34 is a kind of CoO of having -2 2, MnO -2 2, AlO - 2, PO + 2And SiO 2The molecular sieve of the three-dimensional microporous framework structure of tetrahedral oxide units.Its butt empirical formula is:
mR∶（Co tMn uMg vAl xP ySi z）O 2
Wherein " R " is illustrated in the organic formwork agent that exists in the system of intracrystalline hole; " m " represents each mole (Co tMn uMg vAl xP ySi z) O 2The mole number of " R " that exists, its value about from 0 to 0.3; " t ", " u ", " v ", " x ", " y " and " z " represent that respectively wherein " w " is the summation of " t+u+v " as the molar fraction of cobalt, manganese, magnesium, aluminium, phosphorus and the silicon of tetrahedral oxide existence.Above-mentioned molar fraction is preferably in the compositing range that Fig. 2 mid point a, b, c, d, e and f limit, CoMnMgAPSO-34 has the characteristic X-ray powder diagram that contains interplanar distance as follows (d) at least in the composition district that Fig. 1 mid point A, B, C, D and E limit:
2 θ d(dusts) relative intensity
9.3-9.8????9.51-9.03????m-vs
12.6-13.2????7.03-6.71????w-m
15.8-16.3????5.61-5.44????vw-m
20.25-21.2????4.39-4.19????w-vs
24.8-25.4????3.59-3.507????vw-m
30.0-30.9????2.979-2.894????vw-m
(d) the CoMnMgAPSO-34 composition that has recorded the X-ray powder diffraction data has the figure of following data characterization:
2 θ d(dusts) 100 * I/I 0
9.5-9.7????9.31-9.14????100
12.8-13.1????6.90-6.79????13-19
14.1????6.28????12-14
16.0-16.3????5.54-5.44????31-46
18.0-18.1????4.93-4.90????21-28
19.2????4.62????5-12
20.5-21.2????4.33-4.19????61-92
21.5????4.13????44
22.4????3.97????4-25
23.0-23.1????3.87-3.85????4-6
25.2????3.534????21-28
25.8-26.1????3.453-3.414????13-32
26.4????3.379????9
27.6????3.237????4
28.4????3.142????4-5
29.5????3.025????4
30.2-30.5????2.960-2.930????21-37
31.2-31.3????2.871-2.863????14-25
2 θ d(dusts) (I/I 0) * 100
47.2-47.5????1.924-1.916????4-7
48.9????1.863????4-6
51.0????1.791????4
53.0????1.728????4
53.1????1.726????4
31.7????2.819????7
32.4????2.767????15-26
34.4????2.608????5-11
35.5????2.528????16
36.3????2.473????4-5
38.8????2.323????6
39.6????2.276????5
43.3????2.088????5
The preparation of example 21(MgBeMnAPSO-5)
(a) MgBeMnAPSO-5 can be by the following reaction mixture preparation of forming.Its oxide mol ratio of forming by reaction mixture components is expressed as:
1.0-2.0TPA∶0.1-0.4MgO∶0.1-0.4BeO∶0.1-0.4MnO∶0.51.0Al 2O 3∶0.5-1.0P 2O 5∶0.1-0.6SiO 2∶40-100H 2O
Wherein " TPA " represents tripropyl amine.
Reaction mixture is put into the closed stainless steel pressurizing vessel, and carries out boiling in significant temp one effective period of heating, and the result generates the MgBeMnAPSO-5 product.Reclaim solids with filtering method, and wash with water, dry in air at room temperature.
The chemical analysis of MgBeMnAPSO-5 product shows that product contains magnesium, beryllium, manganese, aluminium, phosphorus and silicon.Its amount is formed in the district at the pentagon that Fig. 1 mid point A, B, C, D and E limit.
The following data characterization of X-ray powder diffraction figure of MgBeMnAPSO-5 product:
2 θ d(dusts) relative intensity
7.2-7.7????12.28-11.48????m-vs
19.4-19.9????4.58-4.46????w-m
20.85-21.3????4.26-4.17????w-vs
22.1-22.6????4.02-3.93????m-vs
25.6-26.1????3.480-3.414????vw-m
(b) the X-ray powder diffraction figure of the MgBeMnAPSO-5 after the roasting also is the X ray picture that is characterized by (a).
(c) when the MgBeMnAPSO-5 after the roasting of (b) is used for loading capacity mensuration, after sample activates in 350 ℃ of vacuum, measure with the McBain-Bakr weight absorption instrument of standard.Following data are used for determining adsorption:
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity *(heavy %)
Oxygen 3.46 100-183 7
Oxygen 3.46 750-183 10
Neopentane 6.2 700 24 4
Water 2.65 4.3 24 4
Water 2.65 2.00 24 12
*Representational adsorptive capacity
The aperture of MgBeMnAPSO-5 is greater than 6.2 dusts.
The preparation of example 22(FeGaMgAPSO-11)
(a) FeGaMgAPSO-11 can be by the following reaction mixture preparation of forming.Its oxide mol ratio of forming by reaction mixture components is expressed as:
1.0-2.0DPA∶0.1-0.4FeO∶0.1-0.4MgO∶0.5-0.2Ga 2O 3∶0.5-1.0Al 2O 3∶0.5-1.0P 2O 5∶0.1-0.6SiO 2∶40-100H 2O
Wherein " DPA " represents di-n-propylamine.
Reaction mixture is put into the closed stainless steel pressurizing vessel, and carries out boiling in efficient temperature one effective period of heating, and the result generates the FeGaMgAPSO-11 product.Reclaim solid with filtering method, and wash with water, dry in air at room temperature.
The chemical analysis of FeGaMgAPSO-11 product shows that product contains iron, gallium, magnesium, aluminium, phosphorus and silicon.Its amount is formed in the district at the pentagon that Fig. 1 mid point A, B, C, D and E limit.
The following data characterization of X-ray powder diffraction figure of FeGaMgAPSO-11 product:
2 θ d(dusts) relative intensity
7.8-8.2????11.19-10.85????m-s
9.0-9.8????9.83-9.03????vw-vs
12.8-13.6????6.92-6.51????vw-m
19.9-20.5????4.46-4.33????m-s
20.8-21.8????4.27-4.08????m-vs
22.0-22.6????4.04-3.93????m-vs
22.6-23.1????3.93-3.85????vw-vs
23.1-23.5????3.85-3.79????m-vs
(b) the X-ray powder diffraction figure of the FeGaMgAPSO-11 after the roasting is characterized by (a) X ray picture.
(c) when the FeGaMgAPSO-11 after the roasting of (b) is used for loading capacity mensuration, after sample activates in 350 ℃ of vacuum, measure with the McBain-Bakr weight absorption instrument of standard.Following data are used for determining adsorption:
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity *(heavy %)
Oxygen 3.46 100-183 5
Oxygen 3.46 750-183 6
Hexanaphthene 6.0 90 24 4
Water 2.65 4.3 24 6
Water 2.65 20 24 8
*Representational adsorptive capacity
The aperture of FeGaMgAPSO-11 is the 6 Izod right sides.
The preparation of example 23(ZnCoMnAPSO-34)
(a) ZnCoMnAPSO-34 can be by the following reaction mixture preparation of forming.Its oxidation mol ratio of forming by reaction mixture components is expressed as:
1.0-2.0TEAOH∶0.1-0.4ZnO∶0.1-0.4CoO∶0.1-0.4MnO∶0.5-1.0Al 2O 3∶0.5-1.0P 2O 5∶0.1-0.6SiO 2∶40-100H 2O
" TEAOH " represents tetraethyl ammonium hydroxide.
Reaction mixture is put into the closed stainless steel pressurizing vessel, and carries out boiling one period working lipe in the heating of efficient temperature system, and the result generates the ZnCoMnAPSO-34 product.Reclaim solid with filtering method, and wash with water, dry in air at room temperature.
The chemical analysis of ZnCoMnAPSO-34 product shows that product contains zinc, cobalt, manganese, aluminium, phosphorus and silicon.Its amount is formed in the district at the pentagon that Fig. 1 mid point A, B, C, D and E limit.
The following data characterization of X-ray powder diffraction figure of ZnCoMnAPSO-34 product:
2 θ d(dusts) relative intensity
9.3-9.8????9.51-9.03????m-vs
12.6-13.2????7.03-6.71????w-m
15.8-16.3????5.61-5.44????vw-m
20.25-21.2????4.39-4.19????w-vs
24.8-25.4????3.59-3.507????vw-m
30.0-30.9????2.979-2.894????vw-m
(b) the X-ray powder diffraction figure of the ZnCoMnAPSO-34 after the roasting also is the X ray picture that is characterized by (a).
(c) when the ZnCoMnAPSO-34 after the roasting of (b) is used for loading capacity mensuration, after sample activates in 350 ℃ of vacuum, measure with the McBain-Bakr weight absorption instrument of standard.Following data are used for the absorption survey and study carefully:
Adsorbate kinetic diameter (dust) pressure (torr) temperature (℃) adsorptive capacity * (heavy %)
Oxygen 3.46 100-183 13
Oxygen 3.46 750-183 18
Normal hexane 4.3 100 24 6
Water 2.65 4.3 24 15
Water 2.65 20 24 21
*Representational adsorptive capacity
The aperture of ZnCoMnAPSO-34 is the 4.3 Izod right sides.
Example 24
The catalytic activity of example 13 and 14 CoMnMgAPSO composition is to carry out normal butane cracking evaluation with laboratory scale equipment.
Reactor is the cylindrical quartz tube of 254 millimeters of length, 10.3 millimeters of internal diameters.In each test, the reactor granularity of packing into is the CoMnMgAPSO particle 0.5-5 gram of 20-40 order (USS).Selected catalytic amount is to guarantee that the transformation efficiency of its normal butane under test conditions is not less than 5%, but is not more than 90%.The roasting 1.5 hours in 600 ℃ of air of CoMnMgAPSO sample is removed organic substance from the system of hole.And in reactor, activate 1 hour on the spot in 500 ℃ of helium injection gas.Charging is the helium-normal butane mixture that contains 2 moles of % normal butanes, and it passes through reactor with the flow of 50 ml/min.Carry out the analysis of charging and reaction effluent with traditional gas chromatographic technique.At 10 minutes post analysis reaction effluents of reaction.Calculate pseudo-first-order reaction velocity constant (K) according to analytical data, and be expressed as follows:
Product reaction velocity constant (the K of example number A) *
13 ＊8.8
14 ＊0.2
*Roasting is 1.5 hours in 600 ℃ of air
*(milliliter/gram. minute)
The application of SENAPSO in technological process
Usually, composition of the present invention is hydrophilic.Come compared with common hydrocarbon molecule, as alkane, alkene and aromatic hydrocarbons (as benzene, dimethylbenzene and isopropyl benzene), their preferentially adsorbed water.Therefore, this composition can be used as siccative as a class in fractionation by adsorption/purge process (as Sweet natural gas drying, reacted gas drying).Come compared with so-called permanent gases, as carbonic acid gas, nitrogen, oxygen and hydrogen, they are preferentially adsorbed water also.So they are applicable to dry reformer hydrogen stream and are applicable to oxygen, nitrogen or the air drying before liquefaction.
This composition has also shown new surface selectivity feature, thus their useful as catalysts or catalyst substrates and carriers in many hydrocarbon conversions and oxidizing fire reaction.The gold of their available catalytic activitys dipping or be loaded in above.Used method is that the present technique field is familiar with and is widely used in for example preparing the catalyst composition that silicon oxide or alumina supporter are arranged.In these compositions, the aperture is more suitable in catalytic applications greater than those kinds on the 4 Izod right sides.
By cracking, hydrocracking, alkylating aromatic hydrocarbon and isoparaffin alkylation, the isomerization that comprises xylene isomerization, polymerization, reformation, hydrogenation, dehydrogenation, transalkylation being arranged among the catalytic hydrocarbon conversion reactions of these compositions, taking off alkyl, hydrogenation open loop and dehydrocyclization.
Use contains the catalyst composition of hydrogenation promotor (as platinum or palladium), but the raw material of heavy crude residual oil, recycle feed and other hydrocracking can hydrocracking in 400-825 scope.Used hydrogen is 2-80 to the hydrocarbon mol ratio, and pressure is 10-3500 pound/square inch (gauge pressure), and liquid hourly space velocity (LHSV) is 0.1-20, is preferably 0.1-10.
The catalyst composition that is used for hydrocracking also is applicable to reforming process.In these processes, hydrocarbon raw material at 700-1000, hydrogen pressure 100-500 pound/square inch (gauge pressure), liquid hourly space velocity 0.1-10, hydrogen to the best 4-12 of hydrocarbon mol ratio 1-20() contact with catalyzer under the condition.
Similar catalyzer (catalyzer that promptly contains the hydrogenation promotor) also is used for hydroisomerization process.In these processes, raw material (as normal alkane) is converted to saturated side chain isomer.Hysomer carries out at 200-600 (preferably 300-550), liquid hourly space velocity 0.2-1.0.Hydrogen is infeeded reactor, mix with hydrocarbon raw material.Hydrogen is 1-5 to the hydrocarbon mol ratio.
In high slightly temperature range, promptly about 650-1000 °F under (preferably 850-950) and common low slightly pressure (15-50 pound/square inch (the gauge pressure)) condition, similar catalyst composition is used for the normal alkane hysomer.Paraffinic feedstock is C preferably 7-C 20Normal alkane.The duration of contact of raw material and catalyzer is quite short usually, to avoid undesirable side reaction, as olefinic polymerization and alkane cracking.Liquid hourly space velocity is 0.1-10, and the 1.0-6.0 optimum.
The crystalline structure of this catalyzer uniqueness and alkali-free metal fully thereof help the catalytic disproportionation of their application, particularly toluene in Alkylaromatics transforms, dimethylbenzene, trimethylbenzene, durene etc.In dismutation, also isomerization and transalkylation can take place.Independent VIII family precious metal or preferably be included in the catalyst composition with the VI-B family metal (as tungsten, molybdenum and chromium) is about 3-15 heavy % of its amount for total composition.
The hydrogen that adds (but not needing) can be present in the conversion zone, and this conversion zone remains on 400-750, the reaction conditions of pressure 100-2000 pound/square inch (gauge pressure), liquid hourly space velocity 0.1-15.
Raw materials such as the most handy gas oil of catalytic cracking process, heavy naphtha, deasphalted crude residual oil carry out.Gasoline is main purpose product.850-1100, liquid hourly space velocity 0.5-10, pressure 0-50 pound/square inch (gauge pressure) suit.
Use the paraffinic feedstock normal alkane of 6 carbon (preferably more than) to generate the dehydrocyclization reaction of benzene, dimethylbenzene, toluene etc., adopt the reaction conditions substantially the same with catalytic cracking.For these reactions, preferably use the catalyzer that VIII family base metal positively charged ion (as cobalt and nickel) is arranged.
In catalytic dealkylation, hope is from the aromatic ring alkyl group side chain that ruptures, and do not make the ring structure hydrogenation basically, be to adopt medium hydrogen pressure (about 300-1000 pound/square inch (gauge pressure)), quite high temperature (800-1000), the reaction conditions of catalytic hydrocracking description above other reaction conditionss are similar.Catalyzer preferably has the same type catalyzer used with above-mentioned catalytic dehydrogenation cyclisation.Wherein special dealkylation of wishing comprises that methylnaphthalene changes into naphthalene, and toluene and (or) dimethylbenzene changes into benzene.
In catalytic hydrofinishing, main purpose be to promote sulfur-containing organic compound in the charging and (or) selective hydrogenation of nitrogen-containing organic compound decomposes, and do not influence the hydrocarbon molecule in the raw material basically.For this purpose, the identical reaction conditions that catalytic hydrocracking is described above preferably adopting, the catalyzer of the same nature that employing and dehydrocyclization operation are used.Raw material comprises gasoline fraction, kerosene, rocket engine fuel cut, diesel oil distillate, light gas oil and heavy gas oil, deasphalted crude residual oil etc.Among them any one can reach and contain following sulphur of 5 heavy % and the following nitrogen of 3 heavy %.
Similarly reaction conditions can be used for containing the hydrofining of the hydrocarbon raw material of a large amount of organic nitrogen compounds and organosulfur compound, i.e. hydrodenitrification and hydrogenating desulfurization.It has been generally acknowledged that a large amount of existence of such composition have suppressed the activity of hydrocracking catalyst widely.Therefore, identical during when wishing with the quite high raw material of nitrogen content to obtain once by the hydrocracking transformation efficiency, the required condition of the raw material that contains less organic nitrogen compound than use more under the exacting terms operation be necessary.Therefore, under any given situation, hydrodenitrification, hydrogenating desulfurization and (or) reaction conditions that hydrocracking can the most promptly be finished, must determine according to property of raw material, particularly the concentration of the organic nitrogen compound in the raw material.Because organic nitrogen compound is to the influence of the hydrogenation cracking activity of these catalyst compositions, not getting rid of a kind of like this possibility exists: be suitable for the denitrogenation of the quite high raw material of organonitrogen content most, the reaction conditions that minimum hydrocracking (as the 20 volume %s of one-pass hydrocracking rate less than fresh feed) are arranged again simultaneously might be identical with the reaction conditions that is fit to another raw material that contains lower concentration hydrocracking constituents for suppressing (as organic nitrogen compound).Therefore, in the practice in present technique field, be on the basis of prescreen test, determine a certain raw material with the contacted condition of special catalyst.
Isomerization reaction is carried out being similar under the above-described the condition of reorganization, and uses acid strong slightly catalyzer.Alkene is preferably in 500-900 isomerization, and alkane, naphthenic hydrocarbon and alkylaromatic hydrocarbon are 700-1000 isomerization.The wherein special isomerization reaction of wishing comprises: normal heptane and (or) octane changes into isoheptane, octane-iso, butane changes into Trimethylmethane, methylcyclopentane changes into hexanaphthene, m-xylene and (or) o-Xylol changes into p-Xylol, 1-butylene change into 2-butylene and (or) iso-butylene, n-hexylene changes into dissident's alkene, and tetrahydrobenzene changes into methyl cyclopentene etc.The best form of catalyzer is combined with the polyvalent metal compounds (as sulfide) of the II-A family, the II-B family metal and rare earth metal.For alkylation with take off the alkyl process, the aperture of optimum SENAPSO composition is at least 5 dusts.When being used for alkylaromatic hydrocarbon and taking off alkyl, typical temperature is minimum to be 350 °F, until raw material or a large amount of cracked temperature of converted product appear, and usually to about 700 °F.Temperature is preferably in more than 450 °F, and is not higher than the critical temperature of compound generation dealkylation.The pressure that adopts will be kept aroamtic hydrocarbon raw material at least and be in liquid state.Concerning alkylation, temperature can be hanged down to 250 °F, but preferably is higher than 350 °F.In benzene, toluene and dimethylbenzene alkylation, alkylating agent is alkene preferably, as ethene and propylene.

Claims (10)

1, a kind of method for preparing crystalline molecular sieve, described molecular sieve has by MO 2, AlO 2, PO 2, SiO 2The three-dimensional microporous framework structure that tetrahedral oxide units is formed, and have the chemical constitution empirical formula of following anhydrous benchmark:
Wherein R is at least a organic formwork agent that is present in the system of intracrystalline hole; M is every mole of (M wAl xP ySi z) O 2The molar weight of existing R, its numerical value is for being equal to or less than 0.3; M is at least two kinds of elementary compositions that are selected from arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, zinc, w, x, y, z represent the molar fraction that M, aluminium, phosphorus, silicon exist with the tetrahedral oxide form respectively, described molar fraction numerical value is to be arranged in the pentagon that a ternary composition diagram is limited by A, B, C, D, E each point, and this ternary composition diagram is with Al x, P y, (M w+ Si z) being respectively leg-of-mutton three summits, the coordinate position of A, B, C, D, E each point is as follows
Molar fraction
The point x y (z+w)
A??0.60??0.37??0.03
B??0.37??0.60??0.03
C??0.01??0.60??0.39
D??0.01??0.01??0.98
E??0.60??0.01??0.39
This method comprises and will contain the reaction source of M, aluminium, phosphorus, silicon and the reaction mixture that a kind of suitable organic formwork agent is formed, carry out hydrothermal crystallization 50-250 ℃ of temperature heating and last 2 hours to 30 days, make described crystalline molecular sieve, the composition of this reaction mixture shows as follows by the oxide molar ratiometer:
aR：(M wAl xP ySi z)O 2∶bH 2O
Wherein R is a kind of organic formwork agent; A is that R is a consumption, and its numerical value is served as reasons greater than 0 to 6; The numerical value of b is by greater than 0 to 500; W, x, y, z's is described as defined above, and the numerical value of w and z all is to be at least 0.01.
2, by the process of claim 1 wherein that the phosphorus source in the reaction mixture is a phosphoric acid.
3, by the process of claim 1 wherein that the phosphorus source in the reaction mixture is an ortho-phosphoric acid, the aluminium source is at least a compound that is selected from the alkoxide of pseudobochmite and aluminium.
4, by the method for claim 3, wherein the alkoxide of this aluminium is an aluminum isopropylate.
5, by the process of claim 1 wherein that the silicon source in the reaction mixture is a silicon-dioxide.
6, by the process of claim 1 wherein that reaction is to be selected from oxide compound, oxyhydroxide, alkoxide, nitrate, vitriol, halogenide, carboxylate salt and their mixture with the source of M elementary composition.
7, by the process of claim 1 wherein that organic formwork agent is to have R 4X +The quaternary ammonium compound of chemical formula or quaternary compound, wherein X is nitrogen or phosphorus, each contains the alkyl or aryl of 1-8 carbon naturally R.
8, by the process of claim 1 wherein that this organic formwork agent is a kind of amine.
9, method by claim 1, template wherein is to be selected from the tetrapropyl ammonium ion, the tetraethyl ammonium ion, tripropyl amine, triethylamine, trolamine, piperidines, hexahydroaniline, the 2-picoline, N, the N-dimethyl benzylamine, N, the N-dimethylethanolamine, choline, N, N '-lupetazin, 1,4-diazabicylo (2.2.2) octane, N methyldiethanol amine, the N-Mono Methyl Ethanol Amine, the N-methyl piperidine, the 3-methyl piperidine, N-methylcyclohexylamine, the 3-picoline, the 4-picoline, quinoline rather encircles, N, N '-dimethyl-1,4-diazabicylo (2.2.2) octane ion, tetramethyl ammonium, the TBuA ion, the four pentyl ammonium ion, Di-n-Butyl Amine, neopentyl amine, two n-amylamines, Isopropylamine, TERTIARY BUTYL AMINE, quadrol, tetramethyleneimine, the 2-imidazolone, di-n-propylamine and polyquaternium [(C 14H 32N 2) (OH) 2] x, wherein x is at least 2.
10, by each method among the claim 1-9, further comprise prepared molecular sieve through in sufficiently high temperature roasting, remove a part at least and be present in organic formwork agent in its intracrystalline hole system.
CN 85103203 1984-04-13 1985-04-25 Quinary and senary molecular sieve compositions Expired CN1011221B (en)

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Publication number Priority date Publication date Assignee Title
CN100343370C (en) * 1998-12-17 2007-10-17 德士古发展公司 Hydrocarbon fuel composite for partial oxidation gasification reaction

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FR2837489B1 (en) * 2002-03-20 2004-06-18 Inst Francais Du Petrole IM-6 CRYSTALLIZED SOLID METALLOPHOSPHATE TYPE AND PROCESS FOR PREPARING THE SAME

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100343370C (en) * 1998-12-17 2007-10-17 德士古发展公司 Hydrocarbon fuel composite for partial oxidation gasification reaction

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