CN1011220B - Molecular sieve compositions - Google Patents

Molecular sieve compositions

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CN1011220B
CN1011220B CN 85103199 CN85103199A CN1011220B CN 1011220 B CN1011220 B CN 1011220B CN 85103199 CN85103199 CN 85103199 CN 85103199 A CN85103199 A CN 85103199A CN 1011220 B CN1011220 B CN 1011220B
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phosphorus
aluminium
reaction mixture
product
dusts
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CN85103199A (en
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弗拉尼金
布伦特
佩顿
威尔逊
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Union Carbide Corp
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Union Carbide Corp
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Abstract

The present invention relates to crystalline molecular sieves in three-dimensional micropore skeleton structure with tetrahedral oxide cells of MO2, AlO2 and PO2. The empirical chemical composition (dry basis) of the molecular sieves has the following formula: mR: (MxAlyPz) O2, wherein R represents at least one organic template agent existing in the hole system in the crystal; m represents the mol number of R existing in every mol of (MxAlyPz) O2; M represents at least one of elements, such as arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium, which can form a tetrahedral oxide skeleton; x, y and z respectively represent the mol fractions of M, aluminum and phosphorus which exist in the form of a tetrahedral oxide.

Description

Molecular sieve compositions
The present invention relates to the preparation method of novel crystallization micro porous molecular sieve.The present invention touches upon and contains the novel molecular sieve of three kinds of components at least, and as following defined, is to exist with the skeleton structure of tetrahedral oxide units.Combination of molecular sieve described later can be by the gel of active compound that contains aluminium, phosphorus and at least a interpolation component (as following defined, it can form the tetrahedral oxide with skeleton structure), and is prepared by hydrothermal method.And, preferably use at least a organic formwork agent.This template can partly play the effect of determining crystallization Mechanism and crystallized product structure.
Crystalline aluminosilicate zeolitic type molecular sieve is that the present technique field is well-known.At present, this molecular sieve analog comprise kind more than 150 natural with the synthetic goods.In general, crystalline zeolite is by the AlO with shared angle 2And SiO 2Tetrahedron constitutes.Its characteristics are to have aperture of uniform size, have significant ion-exchange capacity, and can reversibly make absorption carry out desorption mutually.Said absorption is to be scattered in the whole crystalline internal void mutually, but does not replace any atom that constitutes the fixed crystal structure.
Nonzeolite, that is just do not contain AlO 2And SiO 2As basic skeleton constituent element, but can manifest the ion-exchange performance of zeolite and/or other crystalline microporous composition of absorption property, also be that people are in common knowledge.It is said metal organosilicate, in the United States Patent (USP) of being announced on March 2nd, 1,976 3941871, made report by people such as Dwyer with ion-exchange performance.This metal organosilicate has uniform duct, and can reversibly adsorb and have molecular diameter and be about 6 dusts or littler molecule.The United States Patent (USP) 4061724 announced on December 6th, 1977 according to people such as R.W.Grose, pure silicon-dioxide polymorphic form is the silicon zeolite, they have molecular sieve performance and neither contain positively charged ion, also do not contain the neutral backbone in positively charged ion site.
The United States Patent (USP) 4310440 announced in January 12 nineteen eighty-two according to people such as Wilson, the microporous compositions of report and not by first kind of skeleton Zn-Al-P-Si-oxide molecular sieve of silicon-dioxide institute synthetic then is the crystalline aluminium phosphate composition recently.These materials are by AlO 2And PO 2Tetrahedron is formed, and the same with the situation of silicon-dioxide polymorphic form, has neutral electrovalent skeleton.SiO 2 molecular sieve is the silicon zeolite, owing to lack (extra-structural) positively charged ion of superstructure, then is hydrophobic; Different with above-mentioned situation, because the electronegativity between aluminium and the phosphorus has difference, obviously aluminophosphate molecular sieve is hydrophilic to a certain extent.Their crystal pores volume and aperture can with being equal to mutually of zeolite and si molecular sieves.
In co-applications and the application for patent through assigning (application number is 400438, July 26 nineteen eighty-two), to introduce a kind of novelly by the aluminate or phosphate that silicon replaced, its existing micropore is again a crystal.This material has the PO of containing + 2, AlO - 2And SiO 2The three-dimensional crystals skeleton of tetrahedron element (except the optional any basic metal or calcium that exists), chemical constitution (butt) empirical formula of its synthetic attitude (as-synthesized) is:
mR∶（Si xAl yP z）O 2
" R " expression is present at least a organic formwork agent in the crystallization endoporus system in the formula, and " m " represents each mole (Si xAl yP z) O 2The mole number of " R " that is had, its value from 0 to 0.3, maximum value in all cases, relevant with the active porosity volume that the molecular size and the aluminosilicophosphate crystalline hole of template are; " x ", " y " and " z " represent the molar fraction of silicon, aluminium and phosphorus respectively, and they all exist with the form of tetrahedral oxide.The minimum value of each " x ", " y " and " z " is 0.01, preferably 0.02.The maximum value of " x " is 0.98; The maximum value of " y " is 0.60; The maximum value of " z " is 0.52.These aluminosilicophosphates show some aluminosilicate zeolites and peculiar physics of aluminate or phosphate and chemical property.
In co-applications and the application for patent through assigning (application number is 480738, March 31 nineteen eighty-three), introduce a kind of novel molecular sieve containing titanium, the chemical constitution of its synthetic attitude (butt) is expressed as follows with the unit empirical formula:
mR∶（Ti xAl yP z）O 2
" R " expression is present at least a organic formwork agent in the crystallization endoporus system in the formula; " m " represents each mole (Ti xAl yP z) O 2The mole number of " R " that is had, it is worth between 0 and about 5.0; " x ", " y " and " z " represent the molar fraction of the titanium, aluminium and the phosphorus that exist as tetrahedral oxide respectively.
In co-applications and the application for patent through assigning (application number is 514334, July 15 nineteen eighty-three), introduce a kind of novel crystal type metallic aluminium phosphoric acid salt, it has the MO of containing 2, AlO 2And PO 2The three-dimensional microporous framework structure of tetrahedron element, its chemical constitution (butt) empirical formula is represented with following formula:
mR∶（M xAl yP z）O 2
At least a template that is present in the crystallization endoporus system of " R " expression in the formula; " m " represents each mole (M xAl yP z) O 2The mole number of " R " that is had, its value is 0-0.3; At least a metal in " M " expression magnesium, manganese, zinc and the cobalt element; " x ", " y " and " z " represent the molar fraction of metal " M ", aluminium and phosphorus respectively, and they all exist with the form of tetrahedral oxide.
In co-applications and the application for patent through assigning (application number is 514335, July 15 nineteen eighty-three), introduce a kind of novel crystallization iron aluminium phosphate, it has the FeO of containing 2, AlO 2And PO 2The three-dimensional microporous framework structure of tetrahedron element, its chemical constitution (butt) empirical formula shows it with expression:
mR∶（M xAl yP z）O 2
At least a organic formwork agent that is present in the crystallization endoporus system of " R " expression in the formula; " M " represents each mole (Fe xAl yP z) O 2The mole number of " R " that is had, its value is 0-0.3; " x ", " y " and " z " represent the molar fraction as iron, aluminium and the phosphorus of tetrahedral oxide form existence respectively.
The present invention address contain at least a kind of as discussed below, can with AlO - 2And PO + 2Tetrahedron element forms the novel molecular sieve composition of the component of unit, skeleton four sides.
Fig. 1 is a ternary phase diagrams, and wherein the parameter that is associated with the present composition is all shown it with molar fraction.
Fig. 2 is a ternary phase diagrams, and wherein the parameter that is associated with the present composition is all shown it with molar fraction.
Fig. 3 is a ternary phase diagrams, and wherein the parameter that is associated with used reaction mixture in the present composition preparation process is all shown it with molar fraction.
The present invention addresses a kind of novel crystalline molecular sieve, and it also contains a kind of component at least except containing aluminium and phosphorus, and can form three-dimensional microporous framework by their tetrahedronal oxide of skeleton, contains AlO in order to form- 2、PO + 2And MOn 2The skeleton structure of tetrahedron element, wherein at least a conduct of " M " expression has the tetrahedron element form of electric charge " n " and the different component that exists, " n " can for-3 ,-2 ,-1,0 or+1.
These novel molecular sieves have ion-exchange, absorption and catalytic performance, so they are as sorbent material and catalyzer and obtain to use widely.Each of the composition that this class is novel all has by AlO - 2, PO + 2With the formed crystallization skeleton structure of tetrahedron element, its chemical constitution (butt) empirical formula is represented with following formula:
mR∶（M xAl yP z）O 2
At least a organic formwork agent that is present in the crystallization endoporus system of " R " expression in the formula; " m " represents each mole (M xAl yP z) O 2The mole number of " R " that is had, its numerical value are 0-0.3; " M " represents at least a component that can form tetrahedronal oxide of skeleton; " x ", " y " and " z " represent to exist as tetrahedral oxide the molar fraction of " M ", aluminium and phosphorus respectively." M " is a kind of different component at least, so that molecular sieve is except containing AlO - 2And PO + 2Also contain a kind of tetrahedronal oxide of skeleton unit in addition at least, wherein " M " is a kind of component that is selected from arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium at least.
Molecular sieve of the present invention uses abbreviation " FCAPO " to represent usually, to indicate by AlO - 2, PO + 2And MO n 2Component in the skeleton that tetrahedral oxide constituted " M ".Being called for short " FCAPO " is meant that " framework ingredient " of component " M " is with the tetrahedronal oxide of skeleton form in the skeleton of aluminium and phosphorus and exists.Concrete class wherein is to adopt with a kind of element or some elements (with MO n 2The component that the tetrahedron element form exists) method that replaces " FC " in the abbreviation is carried out mark.For example, " GeBe APO " expression molecular sieve contains AlO - 2, PO + 2, GeO 2And BeO -2 2Tetrahedron element.In order to discern the various structured sort that is made of some subclasses (Subgenric Classes), each structured sort is all put on a figure, uses such as " FCAPO-i " and is distinguished, and wherein " i " is integer.The name of above-mentioned given structured sort is not to be used for representing and any other structured sort similarity structurally of naming with same system of symbols.
The present invention introduces a kind of novel crystalline molecular sieve, wherein has at least a component that can form tetrahedronal oxide of skeleton, so that by AlO - 2, PO + 2And MO n 2Tetrahedron constitutes three-dimensional microporous framework structure.Wherein " M " expression is at least a can form tetrahedron element (" MO for example n 2") component, " M " is a kind of element (as discussed below); " n " be-3 ,-2 ,-1,0 or+1.These novel molecular sieves all have ion-exchange performance, absorption and catalytic performance, so they are as sorbent material and catalyzer and obtain to use widely.
The FCAPO composition is by at AlO - 2And PO + 2There is formation skeleton tetrahedron element MO down in tetrahedron element n 2Method be prepared, wherein " M " is at least a element that is selected from arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium.In a concrete scheme of the present invention, the FOAPO composition contains two kinds of above-mentioned elements at least, becomes MO n 2Skeleton limbs unit.
The relative quantity of element " M ", aluminium and phosphorus is represented it with chemical constitution empirical formula (butt):
mR∶（M xAl yP z）O 2
The molar fraction of " x ", " y " and " z " expression said " M ", aluminium and phosphorus in the formula.Each " M " (M 1, M 2, M 3Or the like) molar fraction separately can use " x 1", " x 2", " x 3" or the like the expression above-mentioned " M " among each M 1, M 2, M 3Deng molar fraction separately." x 1", " x 2", " x 3" to wait numerical value and front be that adopted " x " value is the same, " x "=x 1+ x 2+ x 3, and x 1, x 2, x 3Each is at least 0.01.
Molecular sieve of the present invention has by MO n 2, AlO - 2And PO + 2The skeleton structure that tetrahedron element constituted, wherein " n " be-3 ,-2 ,-1,0 or+1, its chemical constitution (butt) empirical formula is as follows:
mR∶（M xAl yP z）O 2
At least a organic formwork agent that is present in the crystallization endoporus system of " R " expression in the formula; " m " represents each (M xAl yP z) O 2The mole number of " R " that is had, its value about from 0 to 0.3; " M " represents at least a element that can form tetrahedronal oxide of skeleton and be selected from arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; " x ", " y " and " z " represent to exist as the form of tetrahedral oxide the molar fraction of " M ", aluminium and phosphorus respectively." x ", " y ", " z " molar fraction are normally determined according to the pentagon compositing area that is made of A, B, C, D and E point in accompanying drawing 1 ternary phase diagrams.A, B, C, D and E point have following numerical value for " x ", " y " and " z ":
Molar fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In preferred FCAPO subclass molecular sieve, " x " " y " and " z " value are to be arranged in by accompanying drawing 2 ternary phase diagrams a, b, c, d, e and the determined hexagon of f point to form the zone by following formula.Said a, b, c, d, e and f point are as follows for the numerical value that " x ", " y " and " z " have:
Molar fraction
Point x y z
a 0.01 0.60 0.39
b 0.01 0.39 0.60
c 0.39 0.01 0.60
d 0.60 0.01 0.39
e 0.60 0.39 0.01
f 0.39 0.60 0.01
FCAPO of the present invention can be used as sorbent material, catalyzer, ion-exchanger, and uses with the roughly the same mode of the aluminosilicate that uses so far, although the similarity of still not having certainty of the chemistry of FCAPO molecular sieve and physical properties and aluminosilicate.
The FCAPO composition generally is by hydrothermal crystallization method synthetic, used reaction mixture contains the activated feedstock of element " M ", aluminium and phosphorus, preferably contain organic formwork agent, be structure directing agent, and its compound of VA family element and/or optional basic metal or other metal in the periodic table of elements preferably.In general, reaction mixture is contained in the airtight pressurized vessel, and preferably this container inside lining inert plastic material, for example tetrafluoroethylene; Heat then, at 50-250 ℃, preferably 100-200 ℃ of temperature boosted automatically, until the crystalline product that obtains FCAPO; Reaction times normally from several hrs to several weeks.In order to obtain the FCAPO product, typical crystallization time was from about 2 hours to about 30 days, and the general crystallization time that adopts was from about 4 hours to about 20 days.Reclaim product and adopt any proper method, for example centrifugation or filtration.
When synthetic FCAPO composition of the present invention, preferably adopt reaction mixture prescription according to following mol ratio:
aR∶（M xAl yP z）O 2∶bH 2O
" R " is a kind of organic formwork agent in the formula; The amount of " a " expression organic formwork agent, its value about from 0 to 6, and also significant quantity is preferably in greater than in about 0 to 6 the scope; " b " value about from 0 to 500 is preferably between about 2 to about 300; " M " expression is at least a can be at AlO - 2And PO + 2There is formation tetrahedral oxide skeleton unit MO down in tetrahedron element n 2Element, wherein " M " is at least a element that is selected from arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; " n " value for-3 ,-2 ,-1,0 or+1; " x ", " y " and " z " represent the molar fraction of " M ", aluminium and phosphorus respectively, and " x ", " y " and " z " value are at least 0.01." x " value is relevant with the number of contained " M " element in the last FCAPO product, and its value is for each x of 0.01(, as x 1, x 2, x 3Or the like minimum value) multiply by the product of the number of the element that except aluminium and phosphorus, is occurred.This shows, except aluminium and phosphorus, can contain 1-8 kind element, then " x " value may be in 0.01 at least 0.08 the scope at least.Certainly, above-mentioned amount is a minimum value, can adopt bigger significant quantity.
The molar fraction of " x " in the reaction mixture, " y " and " z " preferably is in by in the determined pentagon compositing area of F, the G shown in the accompanying drawing 3, H, I and J point, and its F, G, H, I and J point have following numerical value for " x ", " y " and " z ":
Molar fraction
Point x y z
F 0.01 0.60 0.39
G 0.01 0.39 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01
In the expression formula of above-mentioned reactive component, reactant is to come normalized according to total x+y+z=1.0 mole.The aspect is in the example of recently representing according to oxide molar at reaction mixture in addition, can be according to 1.00 moles of P 2O 5Come normalization method.A kind of form in back is calculated by routine and is easy to be scaled the former, and used method is the mole number that the total mole number of M, aluminium and phosphorus is divided into every kind of " M ", aluminium and phosphoric.The mole number of template and water comes normalization method by the total mole number method of calculation divided by M, aluminium and phosphorus equally.
When producing the reaction mixture that is used for production molecular sieve of the present invention, used organic formwork agent can be any template former recommendation once, that be used for synthetic conventional aluminosilicate zeolites.Usually, these compounds all contain VA family element, particularly nitrogen, phosphorus, arsenic and antimony in the periodic table of elements, and reasonable is nitrogen or phosphorus, and best is nitrogen; These compounds also contain an alkyl or an aromatic group with 1-8 carbon atom at least.Good especially compound as template has amine, quaternary phosphonium compound, quaternary ammonium compound.Both generally use general formula R the back 4X +Expression, wherein " X " is nitrogen or phosphorus, each R is the alkyl or aryl that contains 1-8 carbon atom.Aggretion type quaternary ammonium salt, for example [(C 14H 32N 2) (OH) 2] x(wherein " x " is at least 2) also is suitable for.Use single, two and triamine be best, they or use separately, perhaps with quaternary ammonium compound or other template compound coupling.The mixture of two or more template maybe can produce the mixture of required FCAPO; Perhaps control this reaction process by the template of the stronger guidance capability of tool, the main effect of other template is the pH conditions of establishing this reaction gel.Typical template comprises tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium or TBuA ion; The four pentyl ammonium ion; Di-n-propylamine; 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; Rubane; 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; The 2-imidazolone.Be not that every kind of template can lead and generates every class FCAPO, promptly single template can lead and generates several FCAPO compositions by suitably controlling reaction conditions.Simultaneously, specified FCAPO composition can use several different template and produce.
The phosphorus raw material that is used for the best of present method is a phosphoric acid.But find that the organophosphate such as triethyl phosphate also is gratifying; Such as AlPO 4The crystal type or the unbodied aluminate or phosphate of composition (seeing United States Patent (USP) 4310440) and so on also are gratifying.Organo phosphorous compounds is four butyl phosphonium bromides for example, and obviously not as phosphorated reactant source, but these compounds can play the effect of template.Conventional phosphorated salt, for example sodium-metaphosphate is be that part is available at least, but this not to be best as the raw material of phosphorus.
Best aluminum feedstock, or aluminium alkoxide, for example aluminum isopropylate, or pseudobochmite.Be applicable to the crystal type or the unbodied aluminate or phosphate of phosphorus raw material, also should make the raw material of aluminium certainly.Used other aluminum feedstock in zeolite synthesis, for example hydrargillite, sodium aluminate and aluminum chloride also can be used, but are not best.
Arsenic, beryllium, boron, chromium, gallium, germanium, lithium and v element can be introduced reaction system in any way, but used mode need make used element can form activated state on the spot, promptly can react the skeleton tetrahedron element " MO that contains used element with generation n 2".Operable compound comprises: oxide compound, alkoxide, oxyhydroxide, halogenide, muriate, iodide, vitriol, bromide, such as carboxylate salt organic salt, nitrate such as (as acetates), and other.
Though the synthesis condition of FCAPO composition is not very important, but the FCAPO product that suitably shakes and/or will prepare to produce of the stirring of reaction mixture or other type or on form similar crystal seeds such as aluminate or phosphate, aluminosilicate or combination of molecular sieve add in the reaction mixture, can both promote crystallization process.
After crystallization, the FCAPO product can emanate out, preferably wash with water, and at air drying.The FCAPO of synthetic attitude contains a kind of template used when synthetic in the system of hole within it usually at least.The most common situation is, existing organic moiety, its part at least is as charge balance wound ion and exist, as the same by the situation that contains the made synthetic attitude aluminosilicate zeolites of organic reaction system.But in discrete FCAPO product, having some or all organism is the molecularities that are in the type of containing.According to general rule, the template and even the type organism of containing are too big so that can not freely pass through the channel system of FCAPO product, so must calcine FCAPO so that organism thermolysis and remove it to 200-700 ℃.Under a few cases, the hole of FCAPO product is enough big, and template is moved, and particularly when template molecule is little, can use the conventional desorption method that is adopted when production is boiled out to realize completely or the removing of part.Self-evident, " synthetic attitude " this term that the present invention is used, do not comprise that FCAPO is in the down situation of surface state: promptly occupy the situation that the organism of crystallization endoporus system reduces to some extent by the method for synthetic aftertreatment as the result of hydrothermal crystallization process, like this, in composition chemical constitution expression formula
mR∶（M xAl yP z）O 2
In " m " value be lower than in the 0.02(expression formula all the other symbols as previously mentioned).Use in the preparation process of aluminium alkoxide as the raw material of " M ", aluminium or phosphorus at those, in reaction mixture, occurred corresponding alcohols inevitably, because it is the hydrolysate of alkoxide.Whether this alcohols has participated in building-up process as template, does not determine as yet.But, for the purpose of this application, above-mentioned alcohols is omitted in template disregard artificially, it is existed in the FCAPO material of synthetic attitude.
Because FCAPO composition of the present invention is by MO n 2, AlO - 2And PO + 2Tetrahedron element constitutes, they have respectively net charge " n " ,-1 and+1, wherein " n " be-3 ,-2 ,-1,0 or+1, so the situation of relevant cation exchange capacity (CEC) is more complicated much than zeolite molecular sieve.For zeolite molecular sieve, there is AlO in theory - 2Stoichiometric relation between the positively charged ion of tetrahedron and balancing charge.In composition of the present invention, balance AlO on electric weight - 2Tetrahedron, or pass through in conjunction with PO + 2Tetrahedral method, or pass through in conjunction with simple cationic method, as alkali metal cation and proton (H +), be present in the reaction mixture " M " positively charged ion or from the organic cation of template.Equally, balance MO on electric weight n 2Tetrahedral method can be passed through in conjunction with PO + 2Or AlO - 2Tetrahedron, be present in the positively charged ion of " M " in the reaction mixture, except such as the simple positively charged ion the alkali metal cation, proton (H +), other divalence of introducing from the organic cation of template or by external source or the negatively charged ion or the positively charged ion of polyvalent metal.The somebody advocates, uses Na respectively +And OH -Come the non-conterminous AlO of balance - 2And PO + 2Tetrahedron is to [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC(1971)].
FCAPO composition of the present invention adopts when used so far ion exchange technique is carried out analytical test aspect aluminosilicate zeolites, and demonstrate cation exchange property, and have institute inherent aperture in the crystalline network of per sample (p.s.), and at least about 3 dusts.The ion-exchange of FCAPO composition generally only is being removed square possible afterwards from the hole is by template organism that produce, that occur in building-up process.Adopt usual method often can realize dehydration, to remove the water in the FCAPO composition that is present in synthetic attitude, be removed to certain degree at least and do not remove organism, but, then promote absorption and desorption process greatly if there is not organism.As following said, the FCAPO material has hydrothermal stability and thermostability in various degree, some is quite tangible in this respect, and quite powerful as adsorbent of molecular sieve, hydrocarbon conversion catalyst or catalyst substrates.
When preparation FCAPO composition, preferably use the stainless steel reaction container of liner inert plastic material (as tetrafluoroethylene), to avoid polluting reaction mixture.In the ordinary course of things, the method for preparing final reacting mixture (going out various FCAPO compositions by these crystalline mixtures) is, make a kind of mixture with the reactant that is less than sum, then other reactant, perhaps independent, perhaps the mode with the intermediate blend of two or more reactants is added in the said mixture.In some cases, mixed reactant still keeps their original features in intermediate blend, but in other cases, some or all of reactants has all participated in chemical reaction, produces new material." mixture " this term is to be applied to above-mentioned two kinds of situations.And every kind of intermediate blend and final mixture except as otherwise noted, all will stir, till reaching homogeneous basically.
The x-ray powder diffraction technique of employing standard carries out x-ray analysis to reaction product, thereby obtains the X-ray spectrogram of reaction product.Source of radiation is a kind of high-intensity copper target X-x ray tube, and it is 50 kilovolts and 40 milliamperes of operations.All can carry out record well by copper K-α radiation and the resulting diffraction spectrogram of graphite monochromator by X-x ray spectrograph x scintillometer, pulsed height analyzer and strip chart recorder.The flat powdered sample that compresses is according to timed interval in two seconds, scan under the condition of 2 ° of per minutes (2 θ).According to the diffraction peak position of representing with 2 θ, obtain spacing (d), and show it with atomic meter.Above-mentioned θ is cloth loudspeaker lattice (Bragg) angle of observing from bar chart.After the background correction signal, can measure intensity by the diffraction peak height." I 0" be the intensity at intense line or peak, " I " is the intensity at each other peak.In addition, can adopt copper K-α radiotechnology to carry out x-ray analysis, used instrument is that Siemens K-805 type X-ray source and Siemens D-500 X-ray powder diffraction instrument (are purchased in Siemens Coporation address Cherry Hill, NJ).
Just as known in the present technique field, location parameter 2 θ will have artificial and instrumental error.Comprehensive these two kinds of errors for the report value of each 2 θ, can be had an appointment ± 0.4 ° inaccurate value.Certainly, this inaccurate value also shows in the report value of the d-spacing of being calculated with 2 θ values.In this inaccuracy of present technique field ubiquity, but the composition that also is not enough to hamper crystalline material of the present invention and prior art is distinguished.In the X-of some reports ray spectrogram, the relative intensity of square is represented with symbol " vs ", " s ", " m ", " w " and " vw " between d-, they represent respectively very strong, strong, in, weak and very weak.
In some cases, a kind of purity of synthetic product can be estimated with reference to its X-ray powder diffraction spectrogram.For example,, so only mean the spectral line of X-ray spectrogram with regard to not producing of sample, but and do not mean that do not have amorphous substance to exist because of crystalline impurities if certain sample is pure.
Molecular sieve of the present invention can characterize with their X-ray powder diffraction spectrogram, and can have the spectrogram shown in following Table A-V one of them.Here said X-ray spectrogram unless otherwise, had both comprised comprising synthetic attitude again burnt.
Table A (FCAPO-5)
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
Table B(FCAPO-11)
2 θ d(dusts) relative intensity
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
Table C(FCAPO-14)
2 θ d(dusts) relative intensity
8.6-8.9 10.3-9.93 vs
13.0 6.81 w
21.9-22.2 4.06-4.00 w
25.4 3.51 w
27.5 3.24 w
29.7 3.01 w
Table D(FCAPO-16)
2 θ d(dusts) relative intensity
11.3-11.6 7.83-7.63 m-vs
18.7-18.9 4.75-4.70 w-s
21.9-22.3 4.06-3.99 m-vs
26.5-27.0 3.363-3.302 w-m
29.7-30.05 3.008-2.974 w-m
Table E(FCAPO-17)
2 θ d(dusts) relative intensity
7.7-7.75 11.5-11.4 vs
13.4 6.61 s-vs
15.5-15.55 5.72-5.70 s
19.65-19.7 4.52-4.51 w-s
20.5-20.6 4.33-4.31 vs
31.8-32.00 2.812-2.797 w-s
Table F(FCAPO-18)
2 θ d(dusts) relative intensity
9.6-9.65 9.21-9.16 vs
15.5-15.55 5.72-5.70 m
16.9-17.1 5.25-5.19 m
20.15-20.25 4.41-4.39 m
20.95-21.05 4.24-4.22 m
31.8-32.5 2.814-2.755 m
Table G(FCAPO-20)
2 θ d(dusts) relative intensity
13.7-14.25 6.46-6.22 m-vs
19.55-20.0 4.54-4.44 w-s
24.05-24.5 3.70-3.63 m-vs
34.3-35.0 2.614-2.564 vw-w
42.5-43.0 2.127-2.103 vw-w
Table H(FCAPO-31)
2 θ d(dusts) relative intensity
8.5-8.6 10.40-10.28 m-s
20.2-20.3 4.40-4.37 m
21.9-22.1 4.06-4.02 w-m
22.6-22.7 3.93-3.92 vs
31.7-31.8 2.823-2.814 w-m
Table J*(FCAPO-33)
2 θ d(dusts) relative intensity
9.25-9.55 9.56-9.26 w-m
12.5-12.9 7.08-6.86 vs
16.9-17.3 5.25-5.13 w-m
20.45-20.9 4.34-4.25 w-m
23.85-24.25 3.73-3.67 w-m
26.05-26.35 3.42-3.38 w-m
27.3-27.6 3.27-3.23 vs
* synthetic attitude
Table K*(FCAPO-33)
2 θ d(dusts) relative intensity
13.15-13.4 6.73-6.61 vs
18.05-18.35 4.91-4.83 m
18.4-18.6 4.82-4.77 m
26.55-26.7 3.36-3.34 m
32.0-32.1 2.80-2.79 m
* burnt
Table L(FCAPO-34)
2 θ d(dusts) relative intensity
9.4-9.65 9.41-9.17 s-vs
15.9-16.2 5.57-5.47 vw-m
17.85-18.4 4.97-4.82 w-s
20.3-20.9 4.37-4.25 m-vs
24.95-25.4 3.57-3.51 vw-s
30.3-30.8 2.95-2.90 w-s
Table M(FCAPO-35)
2 θ d(dusts) relative intensity
10.8-11.1 8.19-7.97 m
17.2-17.4 5.16-5.10 s-vs
21.0-21.25 4.23-4.18 m-s
21.8-22.0 4.08-4.04 vs
31.8-32.2 2.814-2.788 m
Table N(FCAPO-36)
2 θ d(dusts) relative intensity
7.7-7.9 11.5-11.2 vs
16.2-16.6 5.47-5.34 w-m
18.9-19.3 4.70-4.60 m-s
20.6-20.8 4.31-4.27 w-s
21.8-22.0 4.08-4.04 m
22.2-22.5 4.00-3.95 w-m
Table O(FCAPO-37)
2 θ d(dusts) relative intensity
6.1-6.3 14.49-14.03 vs
15.5-15.7 5.72-5.64 w-m
18.5-18.8 4.80-4.72 w-m
23.5-23.7 3.79-3.75 w-m
26.9-27.1 3.31-3.29 w-m
Table P(FCAPO-39)
2 θ d(dusts) relative intensity
9.4-9.6 9.41-9.21 w-m
13.3-13.6 6.66-6.51 m-vs
18.0-18.4 4.93-4.82 m
21.2-21.5 4.19-4.13 m-s
22.5-23.0 3.95-3.87 s-vs
30.2-30.5 2.96-2.93 w-m
Table Q(FCAPO-40)
2 θ d(dusts) relative intensity
7.5-7.7 11.79-11.48 vw-m
8.0-8.1 11.05-10.94 s-vs
12.4-12.5 7.14-7.08 w-vs
13.6-13.8 6.51-6.42 m-s
14.0-14.1 6.33-6.28 w-m
27.8-28.0 3.209-3.187 w-m
Table R(FCAPO-41)
2 θ d(dusts) relative intensity
13.6-13.8 6.51-6.42 w-m
20.5-20.6 4.33-4.31 w-m
21.1-21.3 4.21-4.17 vs
22.1-22.3 4.02-3.99 m-s
22.8-23.0 3.90-3.86 m
23.1-23.4 3.82-3.80 w-m
25.5-25.9 3.493-3.440 w-m
Table S(FCAPO-42)
2 θ d(dusts) relative intensity
7.15-7.4 12.36-11.95 m-vs
12.5-12.7 7.08-6.97 m-s
21.75-21.9 4.09-4.06 m-s
24.1-24.25 3.69-3.67 vs
27.25-27.4 3.273-3.255 s
30.05-30.25 2.974-2.955 m-s
Table T(FCAPO-44)
2 θ d(dusts) relative intensity
9.4-9.55 9.41-9.26 vs
13.0-13.1 6.81-6.76 w-m
16.0-16.2 5.54-5.47 w-m
20.6-20.85 4.31-4.26 s-vs
24.3-24.4 3.66-3.65 w-vs
30.7-30.95 2.912-2.889 w-s
Table U(FCAPO-46)
2 θ d(dusts) relative intensity
7.2-8.1 12.3-10.9 vs
21.2-21.8 4.19-4.08 w-m
22.5-23.0 3.95-3.87 vw-m
26.6-27.2 3.351-3.278 vw-w
28.5-29.0 3.132-3.079 vw-w
Table V (FCAPO-47)
2 θ d(dusts) relative intensity
9.4 9.41 vs
15.9-16.0 5.57-5.54 w-m
20.5-20.6 4.33-4.31 s
24.5-24.7 3.63-3.60 w
25.8-25.9 3.45-3.44 w
30.4-30.5 2.940-2.931 w
Further specify the present invention by example below, but be not limitation of the present invention.
The preparation of example 1(AsAPO-5)
(a) prepare AsAPO-5 from a kind of reaction mixture, the composition in this mixture recently is expressed as with the oxide molar of each component
1.0-2.0TPA∶0.05-0.2As 2O q∶0.5-1.0
Al 2O 3∶0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " represents tripropyl amine, the oxidation state of " q " expression arsenic.
Place the closed stainless steel pressurized vessel to carry out boiling reaction mixture, heat through one effective period, until the crystallized product that obtains AsAPO-5 in efficient temperature.The filtered and recycled crystallization, again through the washing, in room temperature at air drying.
The chemical analysis of AsAPO-5 product shows that the AsAPO-5 product contains arsenic, aluminium and phosphorus, and its content is to be in by A, B, C, D, E and the determined hexagon of F point in the accompanying drawing to form in the zone.
The characterization data of the X-ray powder diffraction spectrogram of AsAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X-ray powder diffraction spectrogram of burnt AsAPO-5 also meets the X-ray spectrogram characterization data of (a) part.
(c) the burnt AsAPO-5 in (b) part carries out loading capacity test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.In adsorption test, use following data:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of AsAPO-5 is greater than 6.2 dusts.
The preparation of example 2(AsAPO-11)
(a) prepare AsAPO-11 from a kind of reaction mixture, the composition of this mixture recently is expressed as with the oxide molar of each component:
1.0-2.0DPA∶0.05-0.2As 2O q∶0.5-1.0
Al 2O 3∶0.5-1.0P 2O 5∶40-100H 2O，
Wherein " DPA " represents di-n-propylamine, the oxidation state of " q " expression arsenic.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, in efficient temperature heating through one effective period, until the crystallized product that obtains AsAPO-11.The filtered and recycled crystallization after washing, is carried out drying in room temperature again in air.
The chemical analysis of AsAPO-11 product shows that the AsAPO-11 product contains arsenic, aluminium and phosphorus, and its content is to be arranged in by accompanying drawing 1 A, B, C, D, E and the determined hexagon of F point to form the zone.
The characterization data of the X-ray powder diffraction spectrogram of AsAPO-11 product is as follows:
2 θ d(dusts) relative intensity
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
(b) the X-ray powder diffraction spectrogram of burnt AsAPO-11 also meets the x-ray spectrogram characterization data of (a) part.
(c) the burnt AsAPO-11 in (b) part is used for loading capacity test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.In adsorption test, use following data:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 5
O 23.46 750 -183 6
Hexanaphthene 6.2 90 24 4
H 2O 2.65 4.3 24 6
H 2O 2.65 20 24 8
* typical adsorptive capacity
The aperture of AsAPO-11 is about 6 dusts.
The preparation of example 3(BAPO-5)
(a) prepare BAPO-5 from a kind of reaction mixture, the composition of this mixture recently is expressed as with the oxide molar of each component:
1.0-2.0TPA∶0.05-0.2B 2O 3∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " represents tripropyl amine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, until the crystallized product that obtains BAPO-5 in efficient temperature.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
BAPO-5 product chemical analysis shows that the BAPO-5 product contains boron, aluminium and phosphorus, and its content is to be arranged in by accompanying drawing 1 A, B, C, D, E and the determined hexagon of F point to form the zone.
The characterization data of the X-ray powder diffraction spectrogram of BAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X-ray powder diffraction spectrogram of burnt BAPO-5 also meets the X-ray spectrogram characterization data of (a) part.
(c) be used for loading capacity test at the burnt BAPO-5 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Following data are used in adsorption test:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of BAPO-5 is greater than 6.2 dusts.
The preparation of example 4(BAPO-11)
(a) prepare BAPO-11 from a kind of reaction mixture, the composition of this mixture recently is expressed as with the oxide molar of each component:
1.0-2.0DPA∶0.05-0.2B 2O 3∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " DPA " represents di-n-propylamine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, until obtaining the BAPO-11 product in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
BAPO-11 product chemical analysis is shown that the BAPO-11 product contains boron, aluminium and phosphorus, and its content is to be arranged in by the determined hexagon of the true point of accompanying drawing 1 A, B, C, D, E and F to form the zone.
The characterization data of the X-ray powder diffraction spectrogram of BAPO-11 product is as follows:
2 θ d(dusts) relative intensity
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
(b) the X-ray diffraction spectrogram of burnt BAPO-11 also meets the spectral characterization data of (a) part.
(c) be used for loading capacity test at the burnt BAPO-11 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, the sample that activated under 350 ℃ measures.In adsorption test, use following data:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 5
O 23.46 750 -183 6
Hexanaphthene 6.0 90 24 4
H 2O 2.65 4.3 24 6
H 2O 2.65 20 24 8
* typical adsorptive capacity
The aperture of BAPO-11 is about 6 dusts.
The preparation of example 5(BeAPO-5)
(a) prepare BeAPO-5 from a kind of reaction mixture, the composition of this mixture recently is expressed as with the oxide molar of each component
1.0-2.0TPA∶0.1-0.4BeO∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " represents tripropyl amine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, up to obtaining the BeAPO-5 product in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Characterization data to the X-ray powder diffraction spectrogram of BeAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X-ray powder diffraction spectrogram of burnt BeAPO-5 also meets the X-ray spectrogram characterization data of (a) part.
(c) be used for loading capacity test at the burnt BeAPO-5 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Following data are used in adsorption test:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of BeAPO-5 is greater than 6.2 dusts.
The preparation of example 6(BeAPO-17)
(a) prepare BeAPO-17 from a kind of reaction mixture, the composition of this mixture is expressed as with the oxide mol ratio of each component
1.0-2.0QN∶0.1-0.4BeO∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " QN " represents rubane.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, until obtaining the BeAPO-17 crystallized product in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
BeAPO-17 product chemical analysis is shown that the BeAPO-17 product contains beryllium, aluminium and phosphorus, and its content is to be arranged in by accompanying drawing 1 A, B, C, D, E and the determined hexagon of F point to form the zone.
The characterization data of the X-ray powder diffraction spectrogram of BeAPO-17 product is as follows:
2 θ d(dusts) relative intensity
7.7-7.75 11.5-11.4 vs
13.4 6.61 s-vs
15.5-15.55 5.72-5.70 s
19.65-19.7 4.52-4.51 w-s
20.5-20.6 4.33-4.31 vs
31.8-32.00 2.812-2.797 w-s
(b) the X-ray powder diffraction spectrogram of burnt BeAPO-17 also meets the X-ray spectrogram characterization data of (a) part.
(c) be used for loading capacity test at the burnt BeAPO-17 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Following data are used in adsorption test:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 10
O 23.46 750 -183 12
Normal butane 6.2 100 24 4
H 2O 2.65 4.3 24 13
H 2O 2.65 20 24 14
* typical adsorptive capacity
The aperture of BeAPO-17 is about 4.3 dusts.
The preparation of example 7(CAPO-5)
(a) prepare CAPO-5 from a kind of reaction mixture, the composition of this mixture is expressed as with the oxide mol ratio of each component
1.0-2.0TPA∶0.05-0.2Cr 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " represents tripropyl amine, the oxidation state of " q " expression chromium.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, until obtaining the CAPO-5 crystallized product in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the CAPO-5 product shows that the CAPO-5 product contains chromium, aluminium and phosphorus, and its content is that the determined hexagon of A, B, C, D, E and F point that is arranged in accompanying drawing 1 is formed area region.
The characterization data of the X-ray powder diffraction spectrogram of CAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X-ray powder diffraction spectrogram of burnt CAPO-5 also meets the X-ray spectrogram characterization data of (a) part.
(c) be used for loading capacity test at the burnt CAPO-5 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, sample after 350 ℃ of activation measures.In adsorption test, use following data:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of CAPO-5 is greater than 6.2 dusts.
The preparation of example 8(CAPO-31)
(a) prepare CAPO-31 from a kind of reaction mixture, the composition of this mixture is expressed as with the oxide mol ratio of each component
1.0-2.0DPA∶0.05-0.2Cr 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " DPA " represents di-n-propylamine, the oxidation state of " q " expression chromium.
With AlPO 4-31 crystal add in the reaction mixture (United States Patent (USP) 4310440) as crystal seed.Above-mentioned reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, until obtaining the CAPO-31 crystallized product in significant temp.The filtered and recycled crystallization, again through the washing, in room temperature at air drying.
Chemical analysis to the CAPO-31 product shows that the CAPO-31 product contains chromium, aluminium and phosphorus, and its content is arranged in the determined hexagon of accompanying drawing 1 A, B, C, D, E and F point and forms the zone.
The characterization data of the X-ray powder diffraction spectrogram of CAPO-31 product is as follows:
2 θ d(dusts) relative intensity
8.5-8.6 10.40-10.28 m-s
20.2-20.3 4.40-4.37 m
21.9-22.1 4.06-4.02 w-m
22.6-22.7 3.93-3.92 vs
31.7-31.8 2.823-2.814 w-m
(b) the X-ray powder diffraction spectrogram of burnt CAPO-31 also meets the X-ray spectrogram characterization data of (a) part.
(c) be used for loading capacity when test at the burnt CAPO-31 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Following data are used in adsorption test:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 4
O 23.46 750 -183 6
Hexanaphthene 6.0 90 24 3
Neopentane 6.2 700 24 3
H 2O 2.65 4.3 24 3
H 2O 2.65 20.0 24 10
* typical adsorptive capacity
The aperture of CAPO-31 is greater than about 6.2 dusts.
The preparation of example 9(GaAPO-5)
(a) prepare GaAPO-5 from a kind of reaction mixture, the composition of this mixture is expressed as with the oxide mol ratio of each component
1.0-2.0TPA∶0.05-0.2Ga 2O 3∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " represents tripropyl amine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one effective period, until obtaining the GaAPO-5 crystallized product in significant temp.The filtered and recycled crystallization, again through the washing, in room temperature at air drying.
Chemical analysis to the GaAPO-5 product shows that the GaAPO-5 product contains gallium, aluminium and phosphorus, and its content is to be arranged in by accompanying drawing 1 A, B, C, D, E and the determined hexagon of F to form the zone.
The characterization data of the X-ray powder diffraction spectrogram of GaAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X-ray diffraction spectrogram of burnt GaAPO-5 also meets the X-ray spectrogram characterization data of (a) part.
(c) be used for loading capacity when test at the burnt GaAPO-5 of (b) part, use the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Following data are used in adsorption test:
Adsorbate kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of GaAPO-5 is greater than 6.2 dusts.
Example 10(prepares GaAPO-44)
(a) prepare GaAPO-44 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0CHA∶0.05-0.2Ga 2O 3∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " CHA " is hexahydroaniline.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains GaAPO-44 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the GaAPO-44 product shows that the GaAPO-44 product contains gallium, aluminium and phosphorus, and its content is arranged in the determined hexagon of A, B, C, D, E and F point of accompanying drawing 1 and forms the zone.
The characterization data of the X-ray powder diffraction spectrogram of GaAPO-44 product is as follows:
2 θ d(dusts) relative intensity
9.4-9.55 9.41-9.26 vs
13.0-13.1 6.81-6.76 w-m
16.0-16.2 5.54-5.47 w-m
20.6-20.85 4.31-4.26 s-vs
24.3-24.4 3.66-3.65 w-vs
30.7-30.95 2.912-2.889 w-s
(b) baked GaAPO-44 is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated are measured.Following data are adopted in adsorption test:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) torr ℃ heavy %
O 23.46 100 -183 13
O 23.46 750 -183 16
Normal hexane 4.3 100 24 2
H 2O 2.65 4.3 24 15
H 2O 2.65 20 24 17
* typical adsorptive capacity
The aperture of GaAPO-44 is approximately 4.3 dusts.
Example 11(prepares GeAPO-5)
(a) prepare GeAPO-5 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0TPA∶0.1-0.4GeO 2∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein TPA is a tripropyl amine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains GeAPO-5 in significant temp.The filtered and recycled crystallization, again through the washing, in room temperature at air drying.
Chemical analysis to the GeAPO-5 product shows that the GeAPO-5 product contains germanium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of GeAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X light powder diffraction spectrogram of baked GeAPO-5 also meets (a) X-ray spectral characterization data partly.
(c) GeAPO-5 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) torr ℃ heavy %
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of GeAPO-5 is greater than 6.2 dusts.
Example 12(prepares GeAPO-34)
(a) prepare GeAPO-34 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0TEAOH∶0.1-0.4GeO 2∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TEAOH " is tetraethylammonium hydroxide.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains GeAPO-34 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the GeAPO-34 product shows that the GeAPO-34 product contains germanium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of GeAPO-34 product is as follows:
2 θ d(dusts) relative intensity
9.4-9.65 9.41-9.17 s-vs
15.9-16.2 5.57-5.47 vw-m
17.85-18.4 4.97-4.82 w-s
20.3-20.9 4.37-4.25 m-vs
24.95-25.4 3.57-3.51 vw-s
30.3-30.8 2.95-2.90 w-s
(b) the X light powder diffraction spectrogram of baked GeAPO-34 also meets (a) X-ray spectral characterization data partly.
(c) GeAPO-34 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated are measured.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) torr ℃ heavy %
O 23.46 100 -183 13
O 23.46 100 -183 13
Normal hexane 4.3 100 24 6
H 2O 2.65 4.3 24 15
H 2O 2.65 20 24 21
* typical adsorptive capacity
The aperture of GeAPO-34 is about 4.3 dusts.
Example 13(prepares LiAPO-5)
(a) prepare LiAPO-5 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-20TPA∶0.05-0.2Li 2O∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " is tripropyl amine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains LiAPO-5 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the LiAPO-5 product shows that the LiAPO-5 product contains lithium, aluminium and phosphorus, and its content is arranged in the determined hexagon of A, B, C, D, E and F point of accompanying drawing 1 and forms the zone.
The characterization data of the X-ray powder diffraction spectrogram of LiAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X light powder diffraction spectrogram of baked LiAPO-5 also meets (A) X-ray spectral characterization data partly.
(c) LiAPO-5 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) torr ℃ heavy %
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of LiAPO-5 is greater than 6.2 dusts.
Example 14(prepares LiAPO-11)
(a) prepare LiAPO-11 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0DPA∶0.05-0.2Li 2O∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " DPA " is di-n-propylamine.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains LiAPO-11 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the LiAPO-11 product shows that the LiAPO-11 product contains lithium, aluminium and phosphorus, and its content is arranged in the determined hexagon of A, B, C, D, E and F point of accompanying drawing 1 and forms the zone.
The characterization data of the X-ray powder diffraction spectrogram of LiAPO-11 product is as follows:
2 θ d(dusts) relative intensity
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
(b) the X light powder diffraction figure of baked LiAPO-11 also meets (a) X-ray spectral characterization data partly.
(c) LiAPO-11 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) torr ℃ heavy %
O 23.46 100 -183 5
O 23.46 750 -183 6
Hexanaphthene 6.0 90 24 4
H 2O 2.65 4.3 24 6
H 2O 2.65 20 24 8
* typical adsorptive capacity
The aperture of LiAPO-11 is approximately 6 dusts.
Example 15(prepares VAPO-5)
(a) prepare VAPO-5 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0TPA∶0.05-0.2V 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " is the oxidation state that tripropyl amine, " q " refer to vanadium.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains VAPO-5 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the VAPO-5 product shows that the VAPO-5 product contains vanadium, aluminium and phosphorus, and its content is arranged in the determined hexagon of A, B, C, D, E and F point of accompanying drawing 1 and forms the zone.
The characterization data of the X-ray powder diffraction spectrogram of VAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-vs
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X light powder diffraction spectrogram of baked VAPO-5 also meets (a) X-ray spectral characterization data partly.
(c) VAPO-5 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) ℃ heavy %
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of VAPO-5 is greater than 6.2 dusts.
Example 16(prepares VAPO-11)
(a) prepare VAPO-11 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0DPA∶0.05-0.2V 2O q∶0.5-1.0Al 2O 3∶
0.5-1P 2O 5∶40-100H 2O
Wherein " DPA " is di-n-propylamine, and " q " refers to the oxidation state of vanadium.
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains VAPO-11 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the VAPO-11 product shows that the VAPO-11 product contains vanadium, aluminium and phosphorus, and its content is arranged in the determined hexagon of A, B, C, D, E and F point of accompanying drawing 1 and forms the zone.
The characterization data of the X-ray powder diffraction spectrogram of VAPO-11 product is as follows:
2 θ d(dusts) relative intensity
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
(b) X light powder diffraction of baked VAPO-11 spectrum also meets (a) X-ray spectral characterization data partly.
(c) VAPO-11 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) ℃ heavy %
O 23.46 100 -183 5
O 23.46 750 -183 6
Hexanaphthene 6.0 90 24 4
H 2O 2.65 4.3 24 6
H 2O 2.65 20.0 24 8
* typical adsorptive capacity
The aperture of VAPO-11 is approximately 6 dusts.
Example 17(prepares AsGaAPO-5)
(a) prepare AsGaAPO-5 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide:
1.0-2.0TPA∶0.05-0.2（M） 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TPA " is tripropyl amine, and q is the oxidation state of " M " (arsenic and gallium).
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains AsGaAPO-5 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the AsGaAPO-5 product shows that the AsGaAPO-5 product contains arsenic, gallium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of AsGaAPO-5 product is as follows:
2 θ d(dusts) relative intensity
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
(b) the X light powder diffraction spectrogram of baked AsGaAPO-5 also meets (a) X-ray spectral characterization data partly.
(c) AsGaAPO-5 of (b) partial roasting is used for the capacity adsorption test, uses the McBian-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) ℃ heavy %
O 23.46 100 -183 7
O 23.46 750 -183 10
Neopentane 6.2 700 24 4
H 2O 2.65 4.3 24 4
H 2O 2.65 20.0 24 12
* typical adsorptive capacity
The aperture of AsGaAPO-5 is greater than 6.2 dusts.
Example 18(prepares BeGeAPO-11)
(a) prepare BeGeAPO-11 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0DPA∶0.05-0.2（M） 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " DPA " is di-n-propylamine, and " q " is the oxidation state of " M " (beryllium and germanium).
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains BeGaAPO-11 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the BeGeAPO-11 product shows that the BeGeAPO-11 product contains beryllium, germanium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of BeGeAPO-11 product is as follows:
2 θ d(dusts) relative intensity
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
(b) the X light powder diffraction spectrogram of baked BeGeAPO-11 also meets (a) X-ray spectral characterization data partly.
(c) BeGeAPO-11 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) ℃ heavy %
O 23.46 100 -183 5
O 23.46 750 -183 6
Hexanaphthene 6.0 90 24 4
H 2O 2.65 4.3 24 6
H 2O 2.65 20.0 24 8
* typical adsorptive capacity
The aperture of BeGeAPO-11 is approximately 6 dusts.
Example 19(prepares CrGaAPO-17)
(a) prepare CrGaAPO-17 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0QN∶0.05-0.2（M） 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " QN " is rubane, and " q " is the oxidation state of " M " (chromium and gallium).
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains CrGaAPO-17 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the CrGaAPO-17 product shows that the CrGaAPO-17 product contains chromium, gallium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of CrGaAPO-17 product is as follows:
2 θ d(dusts) relative intensity
7.7-7.75 11.5-11.4 vs
13.4 6.61 s-vs
15.5-15.55 5.72-5.70 s
19.65-19.7 4.52-4.51 w-s
20.5-20.6 4.33-4.31 vs
31.8-32.00 2.812-2.797 w-s
(b) X light powder diffraction of baked CrGaAPO-17 spectrum also meets (a) X-ray spectral characterization data partly.
(c) CrGaAPO-17 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) ℃ heavy %
O 23.46 100 -183 10
O 23.46 750 -183 12
Normal butane 6.2 100 24 4
H 2O 2.65 4.3 24 13
H 2O 2.65 20 24 14
* typical adsorptive capacity
The aperture of CrGaAPO-17 is approximately 4.3 dusts.
Example 20(prepares AsBeAPO-31)
(a) prepare AsBeAPO-31 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide.
1.0-2.0DPA∶0.05-0.2（M） 2O q∶0.5-1.0Al 2O 3∶
5.0-1.0P 2O 5∶40-100H 2O
Wherein " DPA " is di-n-propylamine, and " q " is the oxidation state of " M " (arsenic and beryllium).
Reaction mixture AlPO 4-31 crystal are made crystal seed (United States Patent (USP) 4310440), and place the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains AsBeAPO-31 in significant temp.The filtered and recycled crystallization, again through the washing after, in room temperature at air drying.
Chemical analysis to the AsBeAPO-31 product shows that the AsBeapo-31 product contains arsenic, beryllium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of AsBeAPO-31 product is as follows:
2 θ d(dusts) relative intensity
8.5-8.6 10.40-10.28 m-s
20.2-20.3 4.40-4.37 m
21.9-22.1 4.06-4.02 w-m
22.6-22.7 3.93-3.92 vs
31.7-31.8 2.823-2.814 w-m
(b) the X-ray powder of baked AsBeAPO-31 is penetrated spectrogram, also meets the X-ray spectral characterization data of (a) part.
(c) AsBeAPO-31 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated are measured.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 4
O 23.46 750 -183 6
Hexanaphthene 6.0 90 24 3
Neopentane 6.2 700 24 3
H 2O 2.65 4.3 24 3
H 2O 2.65 20 24 10
* typical adsorptive capacity
The aperture of AsBeAPO-31 is approximately greater than 6.2 dusts.
Example 21(prepares AsVBeAPO-34)
(a) prepare AsVBeAPO-34 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0TEAOH∶0.05-0.2（M） 2O q∶0.5-1.0Al 2O 3∶
0.5-1.0P 2O 5∶40-100H 2O
Wherein " TEAOH " is tetraethylammonium hydroxide, and " q " is the oxidation state of " M " (arsenic, vanadium and beryllium).
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains AsVBeAPO-34 in significant temp.The filtered and recycled crystallization, again through the washing, in room temperature at air drying.
Chemical analysis to the AsVBeAPO-34 product shows that the AsVBeAPO-34 product contains arsenic, alum, beryllium, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of AsVBeAPO-34 product is as follows:
2 θ d(dusts) relative intensity
9.4-9.65 9.41-9.17 s-vs
15.9-16.2 5.57-5.47 vw-m
17.85-18.4 4.97-4.82 w-s
20.3-20.9 4.37-4.25 m-vs
24.95-25.4 3.57-3.51 vw-s
30.3-30.8 2.95-2.90 w-s
(b) the X light powder diffraction spectrogram of baked AsVBeAPO-34 also meets (a) X-ray spectral characterization data partly.
(c) AsVBeAPO-34 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated measure.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 13
O 23.46 750 -183 18
Normal hexane 4.3 100 24 6
H 2O 2.65 4.3 24 15
H 2O 2.65 20 24 21
* typical adsorptive capacity
The aperture of AsVBeAPO-34 is approximately 4.3 dusts.
Example 22(prepares GeBAPO-44)
(a) prepare GeBAPO-44 from a kind of reaction mixture, the composition of this mixture is expressed as with the mol ratio of each component oxide
1.0-2.0CHA∶0.05-0.2（M） 2O q∶0.5-1.0Al 2O 3∶0.5-1.0P 2O 5∶40-100H 2O
Wherein " CHA " is hexahydroaniline, and " q " is the oxidation state of " M " (boron and germanium).
Reaction mixture is placed the boiling of closed stainless steel pressurized vessel, heat through one period working lipe, until the crystallized product that obtains GeBAPO-44 in significant temp.The filtered and recycled crystallization, again through the washing, in room temperature at air drying.
Chemical analysis to the GeBAPO-44 product shows that the GeBAPO-44 product contains germanium, boron, aluminium and phosphorus, and its content is arranged in the determined pentagon compositing area of A, B, C, D and E point of accompanying drawing 1.
The characterization data of the X-ray powder diffraction spectrogram of GeBAPO-44 product is as follows:
2 θ d(dusts) relative intensity
9.4-9.55 9.41-9.26 vs
13.0-13.1 6.81-6.76 w-m
16.0-16.2 5.54-5.47 w-m
20.6-20.85 4.31-4.26 s-vs
24.3-24.4 3.66-3.65 w-vs
30.7-30.95 2.912-2.889 w-s
(b) the X light powder diffraction spectrogram of baked GeBAPO-44 also meets (a) X-ray spectral characterization data partly.
(c) GeBAPO-44 of (b) partial roasting is used for the capacity adsorption test, uses the McBain-Bakr weight absorption instrument of standard, in a vacuum, 350 ℃ of samples that activated are measured.Adopt following adsorption test data:
Adsorbed material kinetic diameter pressure and temp adsorptive capacity *
(dust) (torr) (℃) (heavy %)
O 23.46 100 -183 13
O 23.46 750 -183 16
Normal hexane 4.3 100 24 2
H 2O 2.65 4.3 24 15
H 2O 2.65 20 24 17
* typical adsorptive capacity
The aperture of GeBAPO-44 is approximately 4.3 dusts.
Application process
In general FCAPO composition of the present invention is hydrophilic, and the absorption of water is had precedence over the general hydrocarbon molecules of absorption, above-mentioned hydrocarbon molecules such as paraffinic hydrocarbon, alkene and such as the aromatic hydrocarbons of benzene, dimethylbenzene and isopropyl benzene.Therefore, such FCAPO composition is as fractionation by adsorption (purification) process, such as the siccative in dry natural gas, the dry reacted gas.To the preferentially adsorbed of water, also surpassed so-called permanent gases such as carbonic acid gas, nitrogen, oxygen and hydrogen.Therefore this type of FCAPO is applicable to the drying of reformer hydrogen and is used for oxygen, nitrogen or the air drying before liquefaction.
This FCAPO composition also presents special surperficial selectivity characteristic, makes it in many hydrocarbon commentaries on classics and oxidizing fire reaction, to be used as catalyzer, or catalyst substrates and carrier.It can go up or carry and go up catalytically-active metals with the method dipping of knowing in this area, for example, produces the catalyst composition that contains silicon oxide or alumina supporter.Generally speaking, the aperture is suitable as catalyzer greater than the molecular sieve of 4 dusts.
In hydrocarbon conversion reactions, the FCAPO composition the alkylation of cracking, hydrocracking, aromatic hydrocarbons and isoparaffin, the isomerization that comprises xylene isomerization, superimposed, reformation, hydrogenation, dehydrogenation, transalkylation can catalytic reaction be arranged, take off alkyl, hydrogenation open loop and dehydrocyclization.
Use contains the FCAPO catalyst composition such as hydrogenation promotors such as platinum or palladiums, can hydrocracking heavy crude residual oil oil plant, circulating stock and other can make the oil plant of hydrocracking raw material, the temperature range of hydrocracking is 400-825 °F, hydrogen to the hydrocarbon mol ratio in the 2-80 scope, pressure is at 10-3500 pound/square inch (gauge pressure), liquid hourly space velocity 0.1-20, preferably 1.0-10.
The FCAPO catalyst composition that is used for hydrocracking, also be applicable to reforming process, the temperature that hydrocarbon feed contacts with catalyzer in this process is about 700-1000 °F, hydrogen pressure 100-500 pound/square inch (gauge pressure) liquid hourly space velocity 0.1-10, hydrogen to the hydrocarbon mol ratio at 1-20 scope, preferably 4-12.
These contain the catalyzer of hydrogenation promotor, also are applicable to hydroisomerization process, for example the n-paraffin feedstock conversion are become saturated branched isomer.The about 200-600 of the temperature of hydroisomerization °F, preferably 300-550 °F, the about 0.2-1.0 of liquid hourly space velocity.Supply to hydrogen elder generation and hydrocarbon feed formation mixture that reactor goes, its mol ratio (hydrogen/hydrocarbon) is 1-5.
As same catalyst hydrogenation cracking C 7-C 20N-paraffin the time, adopt high any temperature, for example 650-1000 °F, preferably 850-950 °F, and generally will adopt low any pressure, for example 15-50 pound/square inch (gauge pressure).The duration of contact of raw material and catalyzer is generally shorter, to avoid generation such as alkene oligomerization and the non-purpose side reaction of paraffinic hydrocarbon cracked.Liquid hourly space velocity is 0.1-10, preferably 1.0-6.0.
The crystalline texture of the uniqueness that FCAPO catalyzer of the present invention is had and can accomplish completely and need not contain alkali-metal form, help it is used for the conversion of Alkylaromatics, particularly to the catalytic disproportionation of toluene, dimethylbenzene, trimethylbenzene, durene etc.In dismutation, also isomerization and transalkylation can take place.Unite as promotor such as tungsten, molybdenum and chromium separately with VIII family precious metal, or with IV-B family metal, the content in catalyst composition preferably accounts for about the heavy % of 3-15 of whole compositions.Can be from the outside to the reaction zone hydrogen supply, but generally do not need.Keep reaction zone temperature 400-750 °F, pressure 100-2000 pound/square inch (gauge pressure) and liquid hourly space velocity 0.1-15.
The FCAPO composition is suitable for the catalytic cracking process of gasoline as the main purpose product most, and raw materials used can be gas oil, heavy naphtha, deasphalted crude residual oil or the like.Suitable condition is: temperature is 850-1100 °F, and liquid hourly space velocity is 0.5-10, and pressure is about 0-50 pound/square inch (gauge pressure).
The paraffinic hydrocarbon raw material is used in the dehydrocyclization reaction, preferably more than the n-paraffin of 6 carbon atoms, generates benzene, dimethylbenzene, toluene or the like, can use same with catalytic cracking basically reaction conditions.Preferably use the FCAPO catalyzer that has VIII family base metal positively charged ion such as cobalt and nickel for these reactions.
The catalytic dealkylation process is to wish to examine the hydrogenation that removes the alkane side chain but virtue nuclear does not take place basically from aromatic hydrocarbons, adopt higher temperature range 800-1000 and the medium about 300-1000 pound of hydrogen pressure/square inch (gauge pressure), other condition is then identical with above-mentioned catalytic hydrocracking condition.Catalyzer then preferably uses and the employed same catalyzer of above-mentioned catalytic dehydrogenation cyclisation.Special herein dealkylation of wishing, comprise from methylnaphthalene generate naphthalene and from toluene and (or) dimethylbenzene generates the conversion of benzene.
In the catalytic hydrofinishing process, main purpose be promote organosulfur in the raw material and (or) the selection hydrogenation of nitrogen compound decomposes, and do not influence hydrocarbon molecule wherein simultaneously.For this purpose, preferably adopt the general condition identical, with used identical general catalizer variety in the dehydrocyclization operation with above-mentioned catalytic hydrocracking.Raw material comprises gasoline fraction, kerosene, rocket engine fuel cut, diesel oil distillate, light, heavy gas oil, deasphalted crude residual oil or the like, wherein any, can sulfur-bearing up to 5 heavy % about, nitrogenous up to about 3 heavy %.
Same condition can be used for realizing the hydrofining to the high raw material of organonitrogen and organosulfur compound content, i.e. denitrogenation and desulfurization.It is generally accepted, have these a large amount of components, obviously suppress the activity of hydrocracking catalyst.Therefore, when will reaching same during to the nitrogenous raw material hydrocracking single-pass conversion degree of depth, required operational condition than the raw material harshness that contains less organic nitrogen compound many.Under given situation, denitrogenation, desulfurization and (or) hydrocracking can finish the content of knack organic nitrogen compound in raw material properties, particularly raw material rapidly under what kind of condition.Because the result that organic nitrogen compound exerts an influence for the hydrogenation cracking activity of these catalyst compositions, for the higher raw material of a kind of organic nitrogen compound content and require MIN hydrocracking, for example the fresh feed single-pass conversion is lower than the 20%(volume) situation under, then the optimum of its denitrogenation is not impossible contain less inhibition hydrocracking composition with other for example the preferred hydrocracking condition of the raw material of organic nitrogen compound is identical.Therefore, in the practice of this technical field, to the condition that a certain raw material is set up, be according to the prior result who carries out shaker test with special catalyst and raw material.
Isomerization reaction will be carried out under the condition similar to above-mentioned reformation, and adopts the acid catalyzer of any slightly by force.To the best isomerisation conditions of alkene is 500-900 °F, but the isomerisation temperature of paraffinic hydrocarbon, naphthenic hydrocarbon and alkylaromatic hydrocarbon is 700-1000 °F.Here the special isomerization reaction of wishing, comprise transform nhepene with (or) octane becomes isoheptane and octane-iso, butane becomes Trimethylmethane, methylcyclopentane becomes hexanaphthene, between-dimethylbenzene and (or) ortho-xylene in pairs-dimethylbenzene, 1-butylene become 2-butylene and (or) iso-butylene, just-hexene becomes dissident's alkene, tetrahydrobenzene is becoming methyl cyclopentene etc.Preferably the catalyzer of form is that the compound (for example sulfide) of polyvalent metal of FCAPO and II-A family, II-B family metal and rare earth metal is combined.For alkylation with take off the alkyl process, preferably the aperture of FCAPO composition is not less than 5 dusts.When be used for alkylaromatic hydrocarbon take off the alkyl process time, temperature generally is higher than 350 °F, its scope is up to raw material or converted product generation cracked temperature, generally up to about 700 °F.Preferably at least 450 of temperature are not higher than the critical temperature that compound produces dealkylation simultaneously.Pressure condition will be kept aroamtic hydrocarbon raw material at least and be in a liquid state.Alkylating temperature can be hanged down and be reached 250 °F, but preferably at least 350 °F.To the alkylation of benzene, toluene and dimethylbenzene, best alkylating agent is an alkene, for example ethene and propylene.

Claims (9)

1, a kind of method for preparing crystalline molecular sieve, this crystalline molecular sieve has by MO 2, AlO 2, PO 2The three-dimensional microporous framework structure that tetrahedral oxide units constitutes, and the composition empirical formula of its anhydrous benchmark is as follows:
mR：(M xAl yP z)O 2
Wherein R is at least a organic formwork agent that exists in its intracrystalline hole system; M is every mole of (M xAl yP z) O 2Existing R mole number, its numerical value is for being equal to or less than 0.3; M is at least a elementary composition that is selected from arsenic, beryllium, boron, chromium, gallium, germanium, lithium, vanadium; X, y, z represent that respectively described molar fraction value is to be positioned at M as the molar fraction of the M of tetrahedral oxide form existence, aluminium, phosphorus x, Al y, P gIn the pentagon compositing area that is become by A, B, C, D, E each point in the ternary composition diagram on summit, A, B, C, D, E each point coordinate position in the drawings are as follows:
Molar fraction
The point x y z
A?0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
This method comprises uses the reaction source and one or more organic formwork agents that contain element M, aluminium and phosphorus to prepare a kind of reaction mixture, and its mole of forming with its oxide compound recently is expressed as follows:
aR∶(M xAl yP z)O 2∶bH 2O
Wherein R is a kind of organic formwork agent; A represents the amount of R, and its value is served as reasons greater than 0 to 6; The b value is by greater than 0 to 500; All the other symbol implications are the same; And this mixture is heated in 50-250 ℃ of temperature, last 2 hours to 30 days, thereby make this molecular sieve by the hydrothermal crystallization method.
2, by the process of claim 1 wherein that the phosphorus source in the reaction mixture is an ortho-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 pseudobochmite and the aluminium alkoxide.
4, by the method for claim 3, aluminium alkoxide wherein is an aluminum isopropylate.
5, be to be selected from muriate, bromide, iodide, vitriol, acetate, formate by " M " source that the process of claim 1 wherein.
6, by the process of claim 1 wherein that organic formwork agent is the quaternary ammonium Huo quaternary phosphonium compound with following formula
R 4X +
Wherein X is nitrogen or phosphorus, and each R is the alkyl or aryl that contains 1 to 8 carbon atom.
7, by the process of claim 1 wherein that organic formwork agent is a kind of amine.
8, by the process of claim 1 wherein that organic formwork agent is selected from:
The tetrapropyl ammonium ion; The tetraethyl ammonium ion; Tripropyl amine; Triethylamine; Trolamine; Piperidines; Hexahydroaniline; The 2-picoline; N, N-dimethyl benzylamine, N, N-diethylethanolamine; 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; Rubane; 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; Polymeric quaternary ammonium salt [(C 14H 32N 2) (OH) 2] x, wherein the x value is at least 2.
9,, also comprise made molecular sieve the template at least a portion that is present in the system of intracrystalline hole being removed in high-temperature roasting by the method for claim 1.
CN 85103199 1984-04-13 1985-04-25 Molecular sieve compositions Expired CN1011220B (en)

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