CN1011222B - Cobalt-aluminium-phosphorus-silicon-oxide molecular sieve composition - Google Patents
Cobalt-aluminium-phosphorus-silicon-oxide molecular sieve compositionInfo
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- CN1011222B CN1011222B CN 85103238 CN85103238A CN1011222B CN 1011222 B CN1011222 B CN 1011222B CN 85103238 CN85103238 CN 85103238 CN 85103238 A CN85103238 A CN 85103238A CN 1011222 B CN1011222 B CN 1011222B
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Abstract
The present invention discloses crystalline molecular sieves in a three-dimensional micropore skeleton structure with tetrahedral elements of CoO2, ALO2, SiO2 and PO2. The anhydrous base chemical composition of the molecular sieves is represented by an empirical formula mR of (Co<w>Al<x>P<y>Z<z>)O2, wherein R represents at least one organic templet agent existing in a crystallize inner pore canal system; m represents the molar weight of R, which exists in each mol of (Co<w>Al<x>P<y>Z<z>)O2; w, x, y and z respectively represent the molar fractions of cobalt, aluminum, phosphorus and silicon which exist in the tetrahedral oxide. The present invention also discloses applications of the molecular sieves used as adsorbents, catalysts, etc.
Description
The invention relates to the new crystallization three-dimensional micropore molecular sieve of a class, their preparation method, and they are as sorbent material and Application of Catalyst.Involved in the present invention is new cobalt-al-p-silicon-oxide molecular sieve, and this molecular sieve has the shape of the tetrahedral oxide skeleton of cobalt, aluminium, phosphorus, silicon.These combination of molecular sieve can prepare from gelinite and at least a organic formwork agent that contains cobalt, aluminium, phosphorus and the silicon active compound that can form the tetrahedral oxide skeleton with hydrothermal method.The partial action of organic formwork agent is to determine the coordination of crystallisation process and the structure of crystalline product.
Crystalline aluminosilicate zeolitic type molecular sieve is well known in the prior art, its existing at present natural and synthetic composition more than 150 kinds.Crystalline zeolite is usually by AlO
2And SiO
2The angle tetrahedron constitutes altogether, be characterized in having perforate of uniform size, great ion-exchange capacity, and the reverse desorption of energy can make the sorption that is distributed in the crystals slit carry out reverse desorption mutually and any atom in the permanent crystalline structure is subjected to displacement.
Other crystalline microporous molecular sieve outside the zeolite type also is well-known, and promptly the basic framework of this molecular sieve is not AlO
2, but it has the ion-exchange and/or the absorption property of zeolite.People such as Dwyer had once reported the metal organosilicate and had been considered to have ion-exchange performance in the United States Patent (USP) 3.941.871 on March 2nd, 1976, hole of uniform size is arranged, and can be to diameter about 6
Or less than 6
Molecule carry out reversible adsorption.People such as R.W.Grose disclose a kind of polymorphic pure silicon dioxide in the United States Patent (USP) 4.061.724 on December 6th, 1977, be silicon zeolite (Silicalite), it has the performance of screening molecule, and has not both had the neutral backbone that positively charged ion does not have the positively charged ion lattice yet.
The oxide compound of having reported a class microporous compositions and first skeleton recently is not the synthesis of molecular sieve of silicon-dioxide, and this is that people's disclosed compositions in the United States Patent (USP) 4,310,440 in January 12 nineteen eighty-two such as Wilson are the phosphatic molecular sieve of crystalline aluminium.These molecular screen materials are by AlO
2And PO
2Tetrahedron constitutes, and as the silicon-dioxide polycrystal, it also has the electricity price neutral backbone.But different with SiO 2 molecular sieve, because existing, the silicon zeolite strides the positively charged ion of structure, so be hydrophobic; And the hydrophobicity of aluminophosphate molecular sieve is more moderate, and this obviously is because between aluminium and the phosphorus due to electronegative difference.Their intercrystalline pore volume and aperture and known zeolite are suitable with SiO 2 molecular sieve.
Application number at common unsettled and common transfer is 400, and the 438(applying date is July 26 nineteen eighty-two) application in, the microporous crystalline aluminate or phosphate of the silicon replacement of a class novelty has been described.This material has PO
+ 2, AlO
- 2And SiO
2The three-dimensional crystal formation skeleton of tetrahedron element, and except can exist or can non-existent basic metal or calcium, the empirical formula of the former synthetic attitude chemical composition of the moisture-free basis of this element is
mR∶（Si
XAl
YP
Z）O
2
Wherein " R " represents at least a organic formwork agent that is present in the crystallization inner duct system; " m " represents every mole of (Si
XAl
YP
Z) O
2In the mole number of " R ", " m " value is 0 to 0.3; Maximum value under each situation depends on effective pore volume in the actual seed crystal duct of the size of template molecule and aluminosilicophosphate; " X ", " Y " and " Z " represent the molar fraction of the silicon, aluminium and the phosphorus that exist with tetrahedral oxide respectively.Each minimum value of " X ", " Y ", " Z " is 0.01, is 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.This class aluminosilicophosphate has the feature physics and the chemical property of some aluminosilicate zeolites and aluminium phosphoric acid silicate.
March 31 nineteen eighty-three application, application number is in the patent application of 480.738 common unsettled and common transfer, described the new titaniferous molecular sieve of a class, the chemical composition of its former synthetic attitude anhydrous type can be with its unit empirical formula
mR∶（Ti
XAl
YP
Z）O
2
Represent at least a organic formwork agent that is present in the crystallization inner duct system of " R " representative in the formula; " m " represents every mole of (Ti
XAl
YP
Z) O
2In the mole number of " R ", " m " is worth between 0 to 5.0; " X ", " Y " and " Z " represent the molar fraction of the titanium, aluminium and the phosphorus that exist with tetrahedral oxide respectively.
July 15 nineteen eighty-three application, application number is in the patent application of 514,334 common unsettled and common transfer, described the new crystal metal aluminate or phosphate of a class, it has MO
2, AlO
2, PO
2The three-dimensional microporous framework structure of tetrahedron element, the chemical composition of its moisture-free basis is by empirical formula
mR∶（M
XAl
YP
Z）O
2
Expression, at least a organic formwork agent that is present in the crystallization inner duct system of " R " representative in the formula; " m " represents every mole of (M
XAl
YP
Z) O
2In the mole number of " R ", " m " value is 0 to 0.3; " M " represents at least a metal in this family of magnesium, manganese, zinc and cobalt; " X ", " Y " and " Z " represent the molar fraction of the metal " M ", aluminium and the phosphorus that exist with tetrahedral oxide respectively.
July 15 nineteen eighty-three application, application number is in the patent application of 514.335 common unsettled and common transfer, described the new crystallization iron aluminium phosphate of a class, it has FeO
2, AlO
2And PO
2The three-dimensional microporous framework structure of tetrahedron element, its moisture-free basis chemical composition is by empirical formula
mR∶（Fe
XAl
YP
Z）O
2
Expression, at least a organic formwork agent that is present in the crystallization inner duct system of " R " representative in the formula; " m " represents every mole of (Fe
XAl
YP
Z) O
2In the mole number of " R ", " m " value is 0 to 0.3; " X ", " Y " and " Z " represent the molar fraction of the iron, aluminium and the phosphorus that exist with tetrahedral oxide respectively.
The invention relates to and contain CoO
-2 2, AlO
- 2, PO
+ 2And SiO
2The novel molecular sieve of tetrahedral oxide skeleton.
Fig. 1 is the ternary Parameter Map of chemical composition of the present invention, and parameter is represented with molar fraction.
Fig. 2 is the ternary Parameter Map about the optimum chemical composition, and parameter is represented with molar fraction.
Fig. 3 is that parameter is represented with molar fraction about the ternary Parameter Map of the used reaction mixture of the preparation present composition.
The invention relates to the new molecular sieve of a class, it has CoO-2 2、AlO
- 2、PO
+ 2And SiO2The dimensional microporous crystal framework structure of tetrahedral oxide units. These new cobalt-al-p-silicon-oxide molecular sieves have the performance of ion-exchange, absorption, catalysis, therefore are widely used as adsorbent and catalyst. The component part of this class novel composition has CoO-2 2(and/or CoO-1 2）、AlO
- 2、PO
+ 2And SiO2The crystal framework structure of tetrahedron element, its moisture-free basis Chemical composition that is by empirical formula
mR∶（Co
WAl
XP
YSi
Z）O
2
Expression, at least a organic formwork agent that is present in the intracrystalline pore canal system of " R " representative in the formula; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2In the mole number of " R ", " m " value is about 0 to 0.3; " W ", " X ", " Y " and " Z " represent the molar fraction of the cobalt, aluminium, phosphorus and the silicon that exist with tetrahedral oxide respectively.The related above-mentioned ternary composition of molecular sieve of the present invention can demonstrate its feature from itself and the difference of several aspects of molecular sieves in the past.This molecular sieve is characterised in that the thermostability height of some kind, and strange kind has been appearred in binary, ternary molecular sieve.
Molecular sieve of the present invention represents that with the general abbreviation of quoting " CoAPSO " it is CoO
-2 2, AlO
- 2, PO
+ 2And SiO
2The crystalline framework of tetrahedral oxide units.Concrete structure type is to take the way of a numeral of this kind regulation is differentiated that promptly with " CoAPSO-i " expression, wherein " i " is integer.This number is arbitrarily specified, and it is not represented and be another kind of also with any structure relation is arranged between the digital material of distinguishing.
The invention relates to the new molecular sieve of a class, it has CoO
-2 2, AlO
- 2, PO
+ 2And SiO
2The dimensional microporous crystal framework structure of tetrahedral oxide units.Quote CoO herein
-2 2Also comprise CoO
-1 2, therefore can have CoO
-2 2And/or CoO
-1 2Tetrahedral oxide units.The molecular sieve that this class is new has ion-exchange, absorption and catalytic performance, thereby is widely used as sorbent material and catalyzer.
Molecular sieve of the present invention has the CoO of three-dimensional microporous framework structure
-2 2, AlO
- 2, PO
+ 2And SiO
2Tetrahedron element, its moisture-free basis chemical composition empirical formula
mR∶（Co
WAl
XP
YSi
Z）O
2
Expression, at least a organic formwork agent that is present in the intracrystalline pore canal system of " R " representative in the formula; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2In the mole number of " R ", " m " value is about 0 to 0.3; " W ", " X ", " Y " and " Z " represent the molar fraction of the cobalt, aluminium, phosphorus and the silicon that exist with tetrahedral oxide respectively.The molar fraction of " W ", " X ", " Y " and " Z " respectively is at least 0.01, be limited within the area of some determined pentagon composition of A among Fig. 1, B, C, D and E, " W " of said A, B, C, D and E each point, " X ", " Y " and " Z " have following numerical value
Molar fraction
Point X Y (Z+W)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In the CoAPSO molecular sieve in the preferable classification, the value of " W " in the above-mentioned empirical formula, " X ", " Y " and " Z " is within the area formed of the determined tetragon of a, b, c and d that is limited to Fig. 2." W " of this a, b, c and d each point, " X ", " Y " and " Z " have following numerical value.
Molar fraction
Point X Y (Z+W)
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c 0.10 0.55 0.35
d 0.55 0.10 0.35
CoAPSO of the present invention
SCan be used as sorbent material, catalyzer, ion-exchanger or the like, the form of use is the same with many forms of the aluminosilicate that adopted in the past, though the character of their chemistry and physical properties and observed aluminosilicate is not necessarily similar.
The CoAPSO composition is normally synthetic from the reaction mixture that contains the reactive behavior source by the hydrothermal crystallization process, this reaction source is cobalt, silicon, aluminium and phosphorus, also having organic formwork agent is the structure direction agent, and preferably the compound of a certain element of VA family in the periodictable can add basic metal in addition.This reaction mixture generally is placed in the pressurized vessel of sealing, the most handy inert plastics of container such as tetrafluoroethylene are made lining, be preferably in the autogenous pressure heating down of significant temp, this temperature is generally between 50 ℃ to 250 ℃, preferably 100 ℃ to 200 ℃, be generally several hours to several weeks to the working lipe that generates till the CoAPSO crystallized product.Effectively crystallisation process is generally about 2 hours to about 30 days, is typically about 4 hours to about 20 days.Product reclaims with traditional centrifugation or filtering method.
During synthetic CoAPSO composition of the present invention, reaction mixture preferably adopts the composition of being represented by following mol ratio:
aR∶（Co
WAl
XP
YSi
Z）O
2∶bH
2O
Wherein " R " is organic formwork agent; " a " is the molar weight of organic formwork agent " R ", and " a " value is about 0 to 6, and its significant quantity is preferably in greater than zero (0) to 6 scope; " b " value is that zero (0) is to about 500, preferably between 2 to 300; " W ", " X ", " Y " and " Z " represent the molar fraction of cobalt, aluminium, phosphorus and silicon respectively, each value at least 0.01.In concrete enforcement, preferably select such reaction mixture, the molar fraction of its " W ", " X ", " Y " and " Z " is limited within the area of being made up of some determined pentagon of E, F, G, H and I in Fig. 3 ternary diagram." W " of the E of Fig. 3, F, G, H and I each point, " X ", " Y " and " Z " are worth as follows:
Molar fraction
Point X Y (Z+W)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Do not understand why not be that each reaction mixture can both generate crystalline CoAPSO product at present as yet, find when whether this point has CoAPSO in x-ray analysis check reaction product.The reaction mixture that can generate crystallization CoAPSO product is put down in writing with the example of numerical markings in the following embodiments, and those are put down in writing with the example of alphabetic flag with the reaction mixture that X-ray procedure does not go out to have the CoAPSO product to exist.
Form in the statement in above-mentioned reaction, reagent is carried out stdn with respect to the summation of " W ", " Y " and " Z " so that (W+X+Y+Z)=1.00 mole, and in an embodiment, reaction mixture is explained with the mole oxide ratios, can be standardized into P
2O
5Mole number.Be accustomed to the use of with computing method and can be scaled preceding a kind of form to a kind of form in back at an easy rate, the mole number summation of the mole number of each component (comprising template and water), obtain the stdn molar fraction of the mole number summation of backbone said components divided by zinc, aluminium, phosphorus and silicon.
In the reaction mixture that generates molecular sieve of the present invention, organic formwork agent can be above-mentioned used any when synthetic traditional zeolite aluminosilicate, these compounds generally contain VA family element in the periodic table of elements, specifically nitrogen, phosphorus, arsenic, antimony, wherein nitrogen or phosphorus are preferable, and nitrogen is best.These compounds also contain an alkyl or aryl that 1 to 8 carbon atom is arranged at least.As the compound special recommendation of the template compound with amine, tetravalence phosphorus and quartemary ammonium, back two kinds of compounds are usually by formula R
4X
+Representative, X is nitrogen or phosphorus in the formula, each R is the alkyl or aryl that 1 to 8 carbon atom is arranged.Also can suitably adopt the polymeric quaternary ammonium salt, as ((C
14H
32H
2) (OH)
2)
X, " X " value is 2 at least herein.Primary amine, secondary amine or tertiary amine are more favourable, can use separately or be used in combination with quaternary ammonium compound or other template.The mixture of two or more template can generate desirable CoAPSOs mixture, perhaps stronger directed template.Can control the reaction process of it and other template.It mainly is the PH condition that is used for setting up the reaction gel body.Representational template includes: tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA ion; The four pentyl ammonium ion; Two-just-propyl group amine; Tripropylamine; Triethylamine; Trolamine;
Pyridine; Hexahydroaniline; The 2-picoline; N, the N-dimethyl benzylamine; N, the N-dimethylethanolamine; Chlorine; N, N '-dimethyl
Piperazine; 1,4-diazabicyclo (2,2,2) octane; N methyldiethanol amine, the N-Mono Methyl Ethanol Amine; The N-methyl
Pyridine; The 3-methyl
Pyridine; N-methylcyclohexylamine; The 3-picoline; The 4-picoline; Rubane; N, N '-dimethyl-1,4-diazacyclo (2,2,2) octane ion; Two-just-butylamine, neo-pentyl amine; Two-just-amylamine; Isopropylamine; Tert-butylamine; Ethylene diamine; Tetramethyleneimine; And 2-imidazolone.Be not the formation that every kind of template all can directionally be controlled each crystal seed of CoAPSO, it also is the proper handling reaction conditions, single template can directionally form several CoAPSO compositions, and a kind of given CoAPSO composition can produce with several different template.
Almost any reaction silicon source all can be utilized to form SiO then and there in reaction process
2Tetrahedral oxide units.This silicon source can be alkoxide, silicic acid or alkalimetal silicate of silicon-dioxide (silicon sol or vaporific particulate silica all can), active solid amorphous attitude precipitated silica, silica gel, silicon or the like.
Though it is phosphoric acid that preparation method of the present invention has been found only phosphorus source, find that organophosphate such as triethyl phosphine hydrochlorate also are satisfied phosphorus sources, also have the AlP in crystalline state or amorphous aluminate or phosphate such as the United States Patent (USP) 4,310,440
4Composition also is suitable for.Organo phosphorous compounds as tributyl phosphorus bromide, obviously can not be used as active phosphorus source, but these compounds can be made template usefulness.Common microcosmic salt such as metaphosphate have at least part to can be used as the phosphorus source, but are not best phosphorus sources.
The aluminium source is the alkoxide of aluminium preferably, as aluminium isopropoxide or pseudobochmite.Crystalline state or amorphous aluminate or phosphate are suitable phosphorus sources, also are suitable aluminium sources certainly.Other aluminium source of using when synthetic zeolite also can be used as hydrargillite, sodium aluminate and tri-chlorination sodium, but is not best aluminium source.
The cobalt source can enter reaction system with the form that generates the activated state cobalt then and there, and also promptly reaction generates CoO
-2 2The skeleton tetrahedron element.Adaptable cobalt compound has oxide compound, oxyhydroxide, alkoxide, carboxylate salt, vitriol, nitrate, halogenide or the like, comprises cobalt chloride hexahydrate, alpha-iodine cobalt, rose vitriol, Cobaltous diacetate, cobaltous bromide and cobalt chloride.
Though stir or suitably shake reaction mixture with other method, and/or in reaction mixture following crystallization seed (can with the seed crystal of identical aluminate or phosphate, aluminosilicate or combination of molecular sieve of the seed crystal that produces the CoAPSO crystal seed or configuration), to synthetic CoAPSO composition all is not main, but they play a driving role to crystallisation process.
CoAPSO product after the crystallization can separate, and preferably washes with water and at air drying.The CoAPSO of former synthetic attitude contains a kind of template used in its formation reaction usually at least in its inner duct.Modal is from organic formwork agent deutero-organic moiety (be at least a part), is cationic as balancing charge, as the situation of the synthetic aluminosilicate zeolites of self-contained organic reaction system.But may some or all organic moiety be the molecule kind of sorption in specific CoAPSO also.Common rule is, template and can not be freely by organic kind of sorption because volume is too big duct by the CoAPSO product, and must under 700 ℃, calcine at 200 ℃, the organic crystalline speciogenesis heat drop valency of CoAPSO is removed.Under a few cases, the CoAPSO product has enough big duct can allow template to pass through, if especially the latter's molecule is little, then just can as handle zeolite with traditional desorption method with they all or part of removing.One will understand that, do not comprise the sort of state of CoAPSO phase at this used " former synthetic state " this speech, the processing after the organic moiety that wherein occupies micropore system in the crystallization has been synthesized as the result of hydrothermal method crystallisation process eases down to be formed:
mR∶（Co
WAl
XP
YSi
Z）O
2
In the value of " m " less than 0.02.The meaning of other symbol is with above-mentioned identical in the formula.Use in the preparation process of alkoxide as cobalt, aluminium, phosphorus or silicon source at those, because the product that its corresponding alcohol is hydrolysis of alkoxide, so it certainly exists in reaction mixture.But can't determine whether these alcohol identify oneself with in the building-up process as template and go.But on the application's viewpoint, though this alcohol it be to be present among the CoAPSO of former synthetic state also can from the template class, be neglected arbitrarily.
Because CoAPSO composition of the present invention is by CoO
2, AlO
2, PO
2And SiO
2Tetrahedron element is formed, and this tetrahedron element has respectively-and 2(and/or-1) ,-1+1 and 0 net charge, so cation exchange capacity (CEC) is more more complicated than the situation of zeolite molecular sieve, in zeolite molecular sieve, AlO
- 2It between tetrahedron and the charge balance cation ideal stoichiometric relation.In composition of the present invention, AlO
- 2Tetrahedron can by with PO
+ 2Tetrahedron or simple positively charged ion such as alkali metal cation, the cobalt positively charged ion in reaction mixture combine, perhaps by with combine balancing charge from template deutero-organic cation.Equally, CoO
-2 2And/or CoO
-1 2Tetrahedron also can by with PO
+ 2Tetrahedron, cobalt positively charged ion, combine and reach electrobalance from template deutero-organic cation, the simple positively charged ion as alkali metal cation or other divalence of introducing from external ion source or multivalent metal cation.
People are hypothesis once also, AlO
- 2And PO
+ 2Non-conterminous paired tetrahedron, can use Na respectively
+And OH
-Come balance (Flanigen and Grose, molecular sieve zeolites-I, ACS, Washington, DC(1971)).
When CoAPSO composition of the present invention is analyzed with the used above-mentioned ion exchange technique of zeolite aluminosilicate, can find that it has cation exchange capacity (CEC), the inherent aperture has 3 at least in its lattice structure
About.The organic moiety that the CoAPSO composition is only generated when it is synthetic usually just has ion-exchange capacity after removing from the duct.Moisture content in former synthetic attitude CoAPSO composition generally just can be sloughed with method commonly used or take off a certain degree at least, and dehydration is not removed organic moiety, but does not have organic substance, and this is greatly favourable to absorption and desorption process.This class CoAPSO material has hydrothermal stability and thermostability in various degree, and in this respect, some is very outstanding.This material also has the function of making adsorbent of molecular sieve, and the function of making hydrocarbon conversion catalyst or catalyst backbone.
Must use stainless steel reactor in each embodiment, reactor will be used the inert plastic teflon lined, to avoid the pollution of reaction mixture.In general, making each CoAPSO composition form crystalline final reaction mixture should prepare like this, the summation of the reaction additives that will add in this mixture after promptly originally formed mixture is less than, this additive can be the intermediate blends of single reagent or two kinds, multiple reagent.In some cases, the reagent that is pre-mixed keeps the same performance of their intermediate blends, but the new reagent of chemical reaction generation is participated in other situation lower section or total overall reaction agent.Two kinds of situations are all used " mixture " this speech.In addition, except that particularly pointing out, each intermediate blend and final reaction mixture all should be stirred, till fully evenly.
X-ray powder diffraction technique with standard carries out x-ray analysis to reaction product, obtains X-ray pattern.Source of radiation is high-intensity, uses the copper target, 50 kilovolts of X-x ray tube operating voltage, 40 milliamperes of working currents.The diffraction pattern that is obtained by copper K-α radiation and graphite monochromator in time carries out record with scintillometer, pulsed height analyzer and the strip chart recorder of X-x ray spectrometer x.The powdered sample that flattens scans 2 ° (2 θ) with two seconds time constant per minutes.Obtain from the diffraction peak position of representing with 2 θ with
Be the spacing of unit, θ is an observed Bragg angle (Bragg angle) on rectangular record level herein.Intensity is determined " I by the height after the diffraction peak background correction
0" be the intensity at the strongest ray or peak, " I " is the intensity at other each peak.Another kind method is to obtain the X-ray diffraction style with computer scanning technology from copper K-α radiation, with be by (the Siemens Corporation.Cherry Hill of Siemens Company, New Jersey) Siemens D-500 type X-ray powder diffraction instrument of Chu Shouing and Siemens K-805 type X-ray source have suitable computer to connect.
Those skilled in the art be appreciated that parameter 2 θ determine comprising artificial and the comprehensive error of machine, to each its uncertainty value of 2 θ values be approximately ± 0.4 °.This uncertainty is worthwhile so also to be shown on the reading of the d-spacing of calculating from 2 θ.This out of true phenomenon is very general in the prior art, it be not enough to hinder differentiate crystalline material of the present invention each other and and prior art in difference between the said composition.In some X-ray patterns, the relative intensity of d-spacing VS, S, m, W and VW symbolic representation, these symbols are represented very strong, strong, medium, weak and very weak respectively.
In some cases, the purity of synthetic product can be identified according to X-ray powder diffraction style.Therefore, for example, if sample is pure, this only means that its X-ray pattern is not by the caused lines of impurity rather than owing to there not being the event of amorphous substance.
Molecular sieve of the present invention can characterize with their X-ray powder diffraction style.Table A represents all that to each table of M an X-ray pattern, these X-ray patterns all represent former synthetic attitude and burnt molecular sieve, remove have in addition dated.
Table A (CoAPSO-5)
2 θ d(
) relative intensity
7.3-7.5 12.11-11.79 m-VS
14.7-14.9 6.03-5.95 W-m
19.6-19.8 4.53-4.48 W-m
20.9-21.2 4.25-4.19 W-VS
22.3-22.4 3.99-3.97 m-VS
25.8-26.0 3.453-3.427 VW-m
Table B(CoAPSO-11)
2 θ d(
) relative intensity
7.9-8.1 11.19-10.92 m
9.3-9.5 9.51-9.31 m-S
21.0-21.3 4.23-4.17 VS
22.1-22.3 4.02-3.99 m
22.7-23.1 3.92-3.85 m
23.2-23.4 3.83-3.80 m
Table C(CoAPSO-16)
2 θ d(
) relative intensity
11.4-11.6 7.76-7.63 W-S
17.2-17.4 5.16-5.10 m
18.7-18.9 4.75-4.70 VW-m
21.9-22.1 4.06-4.02 VS
23.1-23.3 3.85-3.82 m
26.8-27.0 3.326-3.302 m
29.8-29.9 2.998-2.988 W-m
Table D(CoAPSO-20)
2 θ d(
) relative intensity
13.9-14.0 6.37-6.33 m
19.7-19.8 4.51-4.48 m
24.2-24.3 3.68-3.66 VS
28.0-28.1 3.187-3.175 W
31.4-31.5 2.849-2.840 W
34.5-34.6 2.600-2.592 W
Table E(CoAPSO-31)
2 θ d(
) relative intensity
8.5-8.6 10.40-10.28 m
20.2-20.3 4.40-4.37 m
22.0-22.1 4.04-4.02 m
22.6-22.7 3.93-3.92 VS
28.0-28.1 3.187-3.175 W
31.7-31.8 2.823-2.814 m
Table F(CoAPSO-34)
2 θ d(
) relative intensity
9.4-9.8 9.41-9.03 S-VS
12.86-13.06 6.86-6.76 W
14.08-14.30 6.28-6.19 W-m
15.90-16.20 5.57-5.47 VW-m
20.60-20.83 4.31-4.26 W-VS
30.50-30.80 2.931-2.903 W-m
Table G(CoAPSO-35)
2 θ d(
) relative intensity
10.9-11.0 8.12-8.04 m-VS
13.4-13.7 6.61-6.46 m-VS
17.3-17.4 5.13-5.10 m-S
20.9-21.2 4.25-4.19 m
21.9-22.3 4.06-3.99 m-VS
28.3-28.6 3.153-3.121 m
Table H(CoAPSO-36)
2 θ d(
) relative intensity
7.8-8.0 11.33-11.05 VS
8.2-8.3 10.78-10.65 m
16.4-16.6 5.40-5.34 m
19.0-19.3 4.67-4.60 m
20.7-21.0 4.29-4.23 m
22.3-22.6 3.99-3.93 W-m
Table J(CoAPSO-39)
2 θ d(
) relative intensity
9.4-9.5 9.41-9.31 m
13.3-13.4 6.66-6.61 m
18.1-18.2 4.90-4.87 W-m
21.0-21.2 4.23-4.19 VS
22.4-22.5 3.97-3.95 m-S
26.4-26.5 3.376-3.363 m
Table K(CoAPSO-44)
2 θ d(
) relative intensity
9.3-9.5 9.51-9.31 VS
16.0-16.3 5.54-5.44 W-m
20.5-20.8 4.33-4.27 m
24.3-25.1 3.66-3.548 W-m
25.8-26.2 3.453-3.401 W-m
30.7-31.1 2.912-2.876 VW-m
Table L(CoAPSO-46)
2 θ d(
) relative intensity
6.5-6.7 13.60-13.19 W
7.2-7.4 12.28-11.95 W
7.6-7.8 11.63-11.33 VS
21.6-21.7 4.11-4.10 W
27.8-27.9 3.209-3.198 W
Table M(CoAPSO-47)
2 θ d(
) relative intensity
9.4-9.6 9.41-9.21 VS
12.8-13.1 6.92-6.76 W-m
16.0-16.3 5.54-5.44 W-m
20.6-21.0 4.31-4.23 m-VS
25.5-25.9 3.493-3.440 W-m
30.6-31.1 2.921-2.876 W-m
Preparation reagent
In following example, the CoAPSO composition is to prepare with numerous reagent.List the reagent that all need below, represent with dummy suffix notation:
(a) Alipro: aluminium isopropoxide;
(b) CATAPAL:Condea company, the trade mark of pseudobochmite;
(c) LUDOX-LS:Dupont company, the SiO of 30 weight percentage
2Na with 0.1 weight percentage
2The trade mark of the aqueous solution of O;
(d) Co(Ac)
2: Cobaltous diacetate Co(C
2H
3O
2)
24H
2O;
(e) CoSO
4: rose vitriol (CoSO
47H
2O);
(f) H
3PO
4: the phosphoric acid of 85 weight percentage is in water;
(g) TBAOH: tetrabutylphosphoniuhydroxide hydroxide aluminium (25 weight % are in methyl alcohol);
(h) Pr
2NH: two-just-propyl group amine, (C
3H
7)
2NH;
(i) Pr
3N: three-just-propyl group amine, (C
3H
7)
3N;
(j) Quin: rubane (C
7H
13N);
(k) MQuin: methyl quinuclidine ring oxyhydroxide (C
7H
13NCH
3OH);
(l) C-hex; Hexahydroaniline;
(m) TEAOH: tetraethyl ammonium oxyhydroxide (40 weight % are in water);
(n) DEEA: diethanolamine;
(o) TPAOH: tetrapropyl ammonium oxyhydroxide (40 weight % are in water); With
(p) TMAOH: tetramethyl-ammonium oxyhydroxide (40 weight % are in water)
Preparation process
The CoAPSO preparation of compositions is to prepare reaction mixture earlier, and the mole of this mixture is formed with formula
eR∶fCoO∶hAl
2O
3∶iP
2O
5∶gSiO
2∶jH
2O
Expression.E, f, h, i, g and j represent template R, cobalt (oxide compound with it is represented), Al respectively in the formula
2O
3, P
2O
5(H
3PO
4With P
2O
5Expression), SiO
2And H
2The mole number of O.List in the preparation example that the value of this e, f, h, i, g and j is discussed below.
Use H
3PO
4Be made into the raw material reaction mixture with half water, come the preparation feedback mixture with it again.This mixture is stirred, and added aluminium source (Alipro or CATAPAL).The mixture that obtains thus in addition thorough mixing until presenting uniform mixture.Then LUDOX-LS is added in this mixture, this new blend of remix is until presenting uniform mixture.With cobalt source (CoCAc)
2, Co(SO
4) or their mixture) be dissolved in the remainder water, and merge with first mixture.The mixture of this merging is mixed until presenting uniform mixture.Organic formwork agent is added in this mixture, mixes about two to four minutes to presenting uniform mixture.This resulting mixture (last reaction mixture) is placed in the stainless steel pressure container of liner (tetrafluoroethylene), is heating following (150 ℃, 200 ℃ or 225 ℃) boiling for some time.Another kind method is, if boiling temperature is 100 ℃, then last reaction mixture is had in liner (tetrafluoroethylene), the screw-topped bottle at one and places for some time.Whole digestion carries out under autogenous pressure.Product shifts out from reaction vessel, and cooling is done later evaluation fully and used.
Propose following example and be in order to further specify the present invention, rather than will limit the present invention:
Example 1 to 31
Step according to above introduction prepares the CoAPSO molecular sieve, and the CoAPSO product is measured with x-ray analysis.I and II are shown in the results are shown in of example 1 to 31.Table I and II also comprise example
Table three (continuing)
The example temperature (℃) time (my god) product
1
53 150 10 CoAPSO-11;CoAPSO-46
54 200 4 CoAPSO-46;CoAPSO-11;CoAPSO-20
55 200 10 CoAPSO-46;CoAPSO-11;CoAPSO-20
56 150 4 CoAPSO-11
57 150 10 CoAPSO-11
58 200 4 CoAPSO-11
59 200 10 CoAPSO-11
60 150 4 CoAPSO-11
61 150 4 CoAPSO-11
F 100 4 -
G 100 11 -
H 150 4 -
I 150 4 -
1, these all are the main crystal seeds of being identified with the X-ray powder diffraction style of product, except identifying two or more crystal seeds, are to list in the table with their advantage orders in product."-" expression x-ray analysis does not show the CoAPSO product.
Example 62～83
Example 62～83 is carried out according to employed preparation process in the example 1～31, except each organic formwork agent is the TEAOH(tetraethylammonium hydroxide).Each reaction mixture of example 62～83 is: 1.0TEAOH: fCoO: 0.9Al
2O
3: 0.9P
2O
5: gSiO
2: 50H
2O wherein, " f " is 0.2, except f in example 78～79 be 0.1 and example 80～83 in f be 0.05; " g " is 0.2 in example 62～70, is 0.6 in example 71～83.A to E, wherein the mixed reaction product of x-ray analysis is not meant the CoAPSO product.
In table I and the II, reaction mixture is recently represented with the mole oxide compound:
eR∶fCoO∶0.9Al
2O
3∶0.9P
2O
5∶gSiO
2∶50H
2O
Wherein " e ", " R ", " f " and " g " are with as defined above the same.Have in addition the note in table I and II, the CoAPSO product of all examples is all with this reaction mixture preparation.The value of " e ", " f " and " g " provides in table one and table two.
Table one
Time
Example template e f g temperature (℃) (my god) product
1
1 Quin 1 0.2 0.2 150 4 CoAPSO-16;CoAPSO-35
2 Quin 1 0.2 0.2 150 10 CoAPSO-16;CoAPSO-35
3 Quin 1 0.2 0.2 200 4 CoAPSO-16;CoAPSO-35
4 Quin 1 0.2 0.2 200 10 CoAPSO-16;CoAPSO-35
5 Quin 1 0.2 0.2 100 4 CoAPSO-35;CoAPSO-16
6 Quin 1 0.2 0.2 100 10 CoAPSO-16;CoAPSO-35
7 MQuin 1 0.2 0.2 150 2 CoAPSO-35;CoAPSO-17
8 MQuin 1 0.2 0.2 150 7 CoAPSO-35
9 MQuin 1 0.2 0.2 200 2 CoAPSO-35
10 MQuin 1 0.2 0.2 200 7 CoAPSO-35
11
2、3TBAOH 2 0.4 0.4 200 4 CoAPSO-36;CoAPSO-5
12
2、3TBAOH 2 0.4 0.4 200 10 CoAPSO-36;CoAPSO-5
1, these all are the main crystal seeds of being identified with the X-ray powder diffraction style of product, except identifying two or more crystal seeds, are to list in the table with their advantage orders in product.
2, Al
2O
3Molar weight be 0.8 rather than 0.9.
3, adopted the CoAPSO-36 crystal seed in this example, as United States Patent (USP) S.N.
Table two (continuing)
Example template e f g temperature-time product
1
(℃) (my god)
A
＊TBAOH 2.0 0.4 0.4 150 4 -
B
＊TBAOH 2.0 0.4 0.4 150 10 -
C Pr
3N 1.0 0.2 0.2 100 4 -
D Pr
3N 1.0 0.2 0.2 100 11 -
E Pr
3N 1.0 0.2 0.2 200 21 -
1, these all are the main crystal seeds of being identified with the X-ray powder diffraction style of product, except identifying two or more crystal seeds, are to list in the table with their order of advantage in product.
"-" expression x-ray analysis does not show the CoAPSO product.
*, Al
2O
3Molar weight be 0.8 rather than 0.9.
Example 32 to 61
Used organic formwork agent is two-just-propyl group amine in example 32 to 61.The step of preparation is the same as previously described, but the preparation process of routine 39-45 and 53-61 has been done such improvement: Cobaltous diacetate is added in phosphoric acid and the water, then adds aluminium source, silicon source, add organic template again.Aluminium source in the example 32 to 45,60 and 61 is an aluminium isopropoxide, and the aluminium source in the example 46 to 59 is CATAPAL.The reaction mixture of example 32 to 61 is recently represented with the mole oxide compound:
ePr
2NH∶0.2CoO∶0.9Al
2O
3∶0.9P
2O
5∶0.2SiO
2∶50H
2O
Wherein " e " is template Pr
2The mole number of NH, " e " here is 1 to example 32 to 35,42 to 45,49 to 52,56 to 61, and is 2 to example 36 to 41,46 to 48,53 to 55.Example F, G, H and I are reaction mixtures, react 514 here, and 334(1983 applied for July 15) disclosed the same.
Table two
Temperature-time
Example template e f g (℃) (my god) product
1
13 C-hex 1.0 0.2 0.6 150 4 CoAPSO-44;CoAPSO-5
CoAPSO-13
14 C-hex 1.0 0.2 0.6 150 10 CoAPSO-44;CoAPSO-5
CoAPSO-13
15 C-hex 1.0 0.2 0.6 200 4 CoAPSO-44
16 C-hex 2.0 0.2 0.6 150 4 CoAPSO-44;CoAPSO-13
17 C-hex 2.0 0.2 0.6 150 10 CoAPSO-44;CoAPSO-13
18 C-hex 2.0 0.2 0.6 200 4 CoAPSO-44
19 C-hex 2.0 0.2 0.6 200 10 CoAPSO-44
20 Pr
3N 1.0 0.2 0.2 150 4 CoAPSO-5
21 Pr
3N 1.0 0.2 0.2 150 11 CoAPSO-5
22 Pr
3N 1.0 0.2 0.2 200 4 CoAPSO-5
23 Pr
3N 1.0 0.2 0.2 200 11 CoAPSO-5
24 Pr
3N 1.0 0.2 0.2 150 2 CoAPSO-5
25 Pr
3N 1.0 0.2 0.2 150 15 CoAPSO-5
26 Pr
3N 1.0 0.2 0.2 200 2 CoAPSO-5
27 Pr
3N 1.0 0.2 0.2 200 15 CoAPSO-5
28 Pr
3N 1.0 0.2 0.2 150 21 CoAPSO-5
29 Pr
3N 1.5 0.2 0.2 150 3 CoAPSO-5;CoAPSO-36
30 Pr
3N 1.5 0.2 0.2 150 10 CoAPSO-5;CoAPSO-36
31 Pr
3N 1.5 0.2 0.2 200 3 CoAPSO-5;CoAPSO-36
The x-ray analysis of product does not demonstrate the CoAPSO product.Example 32 to 61 and F, G, H and I list in table three.
Table three
The example temperature (℃) time (my god) product
1
32 150 4 CoAPSO-11;CoAPSO-39
33 150 11 CoAPSO-11;CoAPSO-46;CoAPSO-39
34 200 4 CoAPSO-11;CoAPSO-39;CoAPSO-46
35 200 11 CoAPSO-11;CoAPSO-39;CoAPSO-5
36 150 11 CoAPSO-46
37 200 4 CoAPSO-11;CoAPSO-5;CoAPSO-39
38 200 10 CoAPSO-11;CoAPSO-5
39 150 10 CoAPSO-46
40 200 4 CoAPSO-11;CoAPSO-5;CoAPSO-39;
CoAPSO-46
41 200 10 CoAPSO-11;CoAPSO-5;CoAPSO-39;
CoAPSO-46
42 150 4 CoAPSO-11
43 150 11 CoAPSO-11;CoAPSO-46
44 200 4 CoAPSO-11;CoAPSO-39
45 200 11 CoAPSO-11;CoAPSO-39
46 150 4 CoAPSO-46
47 150 10 CoAPSO-46;CoAPSO-11
48 200 4 CoAPSO-46;CoAPSO-11
49 150 10 CoAPSO-11
50 150 4 CoAPSO-11
51 200 10 CoAPSO-11
52 200 4 CoAPSO-11
The cobalt source of reaction is rose vitriol (II) in example 62～70, is Cobaltous diacetate (II) in example 71～83.
Now with the table four that the results are shown in of routine 63-83.
Table four
The example temperature (℃) time (fate) CoAPSO product
1
62 150 4 CoAPSO-34;CoAPSO-5
63 150 12 CoAPSO-34;CoAPSO-5
64 150 12 CoAPSO-34
65 200 4 CoAPSO-34;CoAPSO-5
66 200 12 CoAPSO-5;CoAPSO-34
67 200 12 CoAPSO-34
68 100 4 CoAPSO-34
69 100 12 CoAPSO-34
70 100 12 CoAPSO-34
71 100 2 CoAPSO-34
72 100 7 CoAPSO-34
73 150 2 CoAPSO-34;CoAPSO-5
74 150 13 CoAPSO-34;CoAPSO-5
75 200 2 CoAPSO-5;CoAPSO-34
76 200 7 CoAPSO-5;CoAPSO-34
77 100 14 CoAPSO-34
78 100 14 CoAPSO-34
79 100 28 CoAPSO-34
80 100 10 CoAPSO-34
81 100 20 CoAPSO-34
82 100 2 CoAPSO-34
83 100 4 CoAPSO-34
1. the principal item of being identified with the X-ray powder diffraction style of product.Except identifying two or more kinds, kind is to list by their advantage orders in product.
Example 84～106
Example 84～106 is carried out according to employed preparation process in the example 1～31, except each organic formwork agent press table five pointed.Each reaction mixture is:
eR∶fCo∶0.9Al
2O
3∶0.9P
2O
5∶0.6SiO
2∶50H
2O
Here except e in routine 94-97 be 1.5 and in example 94～97 e be 1.5 and be 2.0 that " e " is 1 in example 104, the existing table five that the results are shown in routine 84-106.
Table five
Example template e f temperature-time CoAPSO product
1
(℃) (fate)
84 TEAOH 1.0 0.025 125 3 CoAPSO-34;CoAPSO-18;
85 TEAOH 1.0 0.025 125 5 CoAPSO-34;CoAPSO-5;
86 TEAOH 1.0 0.025 100 5 CoAPSO-34;CoAPSO-5;
87 TEAOH 1.0 0.025 100 5 CoAPSO-34;
88 TEAOH 1.0 0.025 100 3 CoAPSO-34;
89 TEAOH 1.0 0.025 100 5 CoAPSO-34;
90 TEAOH 1.0 0.025 100 7 CoAPSO-34;
91 Quin 1.0 0.2 225 5 CoAPSO-35;CoAPSO-16
92 C-hex 1.0 0.2 225 5 CoAPSO-5;CoAPSO-44;
93
2Pr
3N 1.5 0.2 150 2 CoAPSO-36;
94
2Pr
3N 1.5 0.2 150 7 CoAPSO-36;
95
2Pr
3N 1.5 0.2 200 2 CoAPSO-36;CoAPSO-5;
96
2Pr
3N 1.5 0.2 200 7 CoAPSO-36;CoAPSO-5;
97
3Pr
2NH 1.0 0.2 150 4 CoAPSO-31;CoAPSO-11;
98
3Pr
2NH 1.0 0.2 150 10 CoAPSO-46;CoAPSO-31;
99
3Pr
2NH 1.0 0.2 200 4 CoAPSO-31;CoAPSO-11;
100
3Pr
2NH 1.0 0.2 200 10 CoAPSO-31;CoAPSO-11;
CoAPSO-5;CoAPSO-46
101
3Pr
2NH 1.0 0.2 150 2 CoAPSO-31
102
3Pr
2NH 1.0 0.2 150 3 CoAPSO-31
103
3Pr
2NH 1.0 0.2 200 2 CoAPSO-31;CoAPSO-46
104 DEEA 2.0 0.2 150 2 CoAPSO-47
105 TMAOH 1.0 0.2 150 4 CoAPSO-20
106 TMAOH 1.0 0.2 200 4 CoAPSO-20
1. the principal item of identifying according to the X-ray diffraction style of product, except two kinds or more kind, each crystal seed is to arrange by their shared advantage orders in the product.
2. used the CoAPSO-36 crystal seed, as No. 514334, the U.S. Patent application of July 15 nineteen eighty-three application is disclosed.
3. use AlPO
4No. 4310440 ,-31(United States Patent (USP)) crystal seed.
Example 107
The sample of various products is through chemical analysis.The chemical analysis of every kind of product is provided in down with the example of preparation CoAPSO, and instance number is labeled in the bracket behind the CoAPSO crystal seed trade mark.
(a) the CoAPSO-11(example 35) chemical analysis:
The composition weight percent
Al
2O
331.1
P
2O
546.1
CoO 6.4
SiO
23.5
Carbon 5.2
LOI
＊11.7
*LOI is a loss on ignition
Obtain representing that with mole oxide compound ratio (by no water meter) total product consists of from above-mentioned chemical analysis:
0.085CoO∶0.305Al
2O
3∶0.325P
2O
5∶0.058SiO
2，
And its chemical formula (by no water meter) is:
0.07R（Co
0.06Al
0.47P
0.46Si
0.04）O
2
(b) the CoAPSO-11(example 42) chemical analysis:
The composition weight percent
Al
2O
332.5
P
2O
544.7
CoO 4.4
SiO
21.4
Carbon 3.9
LOI
＊15.7
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, with mole oxide ratios (by no water meter) is:
0.059CoO∶0.319Al
2O
3∶0.315P
2O
5∶0.023SiO
2，
And its chemical formula (by no water meter) is:
0.05R（Co
0.04Al
0.47P
0.47Si
0.02）O
2
(c) the CoAPSO-20(example 106) chemical analysis:
The composition weight percent
Al
2O
327.7
P
2O
537.8
CoO 4.6
SiO
210.0
Carbon 9.4
LOI
＊18.4
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, with mole oxide ratios (by no water meter) is:
0.061CoO: 0.272Al
2O
3: 0.266P
2O
5: 0.166SiO
2; And its chemical formula is (by no water meter):
0.20R（Co
0.05Al
0.42P
0.41Si
0.13）O
2
(d) the CoAPSO-31(example 101) chemical analysis be:
The composition weight percent
Al
2O
332.3
P
2O
542.4
CoO 4.3
SiO
23.8
Carbon 2.8
LOI
＊16.6
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (calculating by the no water yield) is:
0.057CoO: 0.317Al
2O
3: 0.299P
2O
5: 0.063SiO
2; Its chemical formula (calculating by the no water yield) is:
0.04R（Co
0.04Al
0.47P
0.44Si
0.05）O
2
(e) the CoAPSO-34(example 69) chemical analysis:
The composition weight percent
Al
2O
328.2
P
2O
541.7
CoO 4.7
SiO
21.1
Carbon 5.9
LOI
＊23.6
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (by no water meter) is:
0.063CoO: 0.277Al
2O
3: 0.294P
2O
5: 0.018SiO
2; And its chemical formula (calculating by the no water yield) is:
0.06R（Co
0.05Al
0.45P
0.48Si
0.02）O
2
(f) the CoAPSO-34(example 72) chemical analysis be:
The composition weight percent
Al
2O
328.4
P
2O
540.6
CoO 4.6
SiO
22.2
Carbon 7.8
LOI
＊23.3
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (calculating by the no water yield) is:
0.061CoO: 0.279Al
2O
3: 0.282P
2O
5: 0.037SiO
2; Its chemical formula (calculating by the no water yield) is:
0.08R（Co
0.05Al
0.46P
0.46Si
0.03）O
2
(g) the CoAPSO-34(example 79) chemical analysis be:
The composition weight percent
Al
2O
331.7
P
2O
540.5
CoO 2.5
SiO
23.4
Carbon 8.4
LOI
＊20.8
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (calculating by the no water yield) is:
0.033CoO: 0.311Al
2O
3: 0.285P
2O
5: 0.057SiO
2; And its chemical formula (by no water meter) is:
0.09R（Co
0.03Al
0.49P
0.45Si
0.05）O
2
(h) the CoAPSO-34(example 81) chemical analysis be:
The composition weight percent
Al
2O
332.0
P
2O
539.6
CoO 1.2
SiO
22.7
Carbon 6.4
LOI
＊22.8
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound per-cent (by no water meter) is:
0.016CoO: 0.314Al
2O
3: 0.279P
2O
5: 0.045SiO
2And its chemical formula (by no water meter) is:
0.07R（Co
0.01Al
0.50P
0.45Si
0.04）O
2
(i) the CoAPSO-34(example 83) chemical analysis be:
The composition weight percent
Al
2O
333.8
P
2O
540.6
CoO 1.6
SiO
22.1
Carbon 6.6
LOI
＊21.7
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (calculating by the no water yield) is:
0.021CoO: 0.332Al
2O
3: 0.286P
2O
5: 0.035SiO
2; And its chemical formula (calculating by the no water yield) is:
0.07R（Co
0.02Al
0.53P
0.46Si
0.03）O
2
(j) the CoAPSO-34(example 77) chemical analysis results:
The composition weight percent
Al
2O
330.1
P
2O
541.7
CoO 4.8
SiO
22.6
Carbon 9.0
LOI
＊19.5
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, is expressed as with mole oxide ratios (calculating by the no water yield):
0.064CoO: 0.295Al
2O
3: 0.294P
2O
5: 0.043SiO
2; And its chemical formula (by no water meter) is:
0.09R（Co
0.05Al
0.46P
0.46Si
0.03）O
2
(k) the CoAPSO-34(example 89) chemical analysis be:
The composition weight percent
Al
2O
331.8
P
2O
538.8
CoO 0.71
SiO
22.2
Carbon 6.6
LOI
＊24.1
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, is expressed as with mole oxide ratios (by no water meter):
0.01CoO: 0.312Al
2O
3: 0.273P
2O
5: 0.037SiO
2; And its chemical formula (by no water meter) is:
0.07R（Co
0.01Al
0.51P
0.45Si
0.03）O
2;
Here the numerical value of cobalt is whole to 0.01 by 0.008 quiltization.
(l) the CoAPSO-34(example 90) chemical analysis be:
The composition weight percent
Al
2O
332.4
P
2O
539.3
CoO 0.66
SiO
23.5
Carbon 7.2
LOI
＊23.5
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (by no water meter) is:
0.009CoO: 0.318Al
2O
3: 0.277P
2O
5: 0.058SiO
2; Its chemical formula (by no water meter) is:
0.08R（Co
0.01Al
0.51P
0.44Si
0.05）O
2
Here the numerical value of cobalt is whole to 0.01 by 0.007 quiltization.
(m) the CoAPSO-35(example 10) chemical analysis be:
The composition weight percent
Al
2O
327.0
P
2O
541.6
CoO 4.3
SiO
24.3
Carbon 13.0
LOI
＊22.1
*LOI is a loss on ignition
Above-mentioned chemical analysis shows total product composition, represents that with mole oxide compound ratio (by no water meter) is:
0.057CoO: 0.265Al
2O
3: 0.290P
2O
5: 0.054SiO
2; Its chemical formula (by no water meter) is:
0.14R（Co
0.05Al
0.43P
0.48Si
0.04）O
2
(n) the CoAPSO-36(example 93) chemical analysis be:
The composition weight percent
Al
2O
329.5
P
2O
539.6
CoO 5.2
SiO
26.6
Carbon 3.3
LOI
＊18.5
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (by no water meter) is:
0.069CoO: 0.289Al
2O
3: 0.279P
2O
5: 0.110SiO
2; And its chemical formula (by no water meter) is:
0.03R（Co
0.05Al
0.44P
0.42Si
0.08）O
2
(o) the CoAPSO-44(example 19) chemical analysis be:
The composition weight percent
Al
2O
326.3
P
2O
536.3
CoO 4.5
SiO
210.0
Carbon 13.2
LOI
＊22.6
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, with mole oxide ratios (by no water meter) is:
0.06CoO: 0.258Al
2O
3: 0.256P
2O
5: 0.166SiO
2; And its chemical formula (by no water meter) is:
0.18R（Co
0.05Al
0.41P
0.41Si
0.13）O
2
(p) the CoAPSO-46(example 36) chemical analysis be:
The composition weight percent
Al
2O
331.4
P
2O
531.5
CoO 6.2
SiO
22.9
Carbon 4.2
LOI
＊27.5
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (by no water meter) is:
0.08CoO: 0.31Al
2O
3: 0.22P
2O
5: 0.05SiO
2; And its chemical formula (by no water meter) is:
0.06R（Co
0.07Al
0.52P
0.37Si
0.04）O
2
(q) the CoAPSO-47(example 104) chemical analysis be:
The composition weight percent
Al
2O
322.7
P
2O
539.8
CoO 8.2
SiO
22.9
Carbon 11.4
LOI
＊25.2
*LOI is a loss on ignition
Above-mentioned chemical analysis draws total product and forms, represents that with mole oxide compound ratio (by no water meter) is:
0.109CoO: 0.223Al
2O
3: 0.280P
2O
5: 0.048SiO
2; And its chemical formula (by no water meter) is:
0.16R（Co
0.09Al
0.38P
0.48Si
0.04）O
2
Example 108
Energy dispersion analysis (EDA) with the EDAX(X-ray) with the SEM coupling the clean crystalline substance of each CoAPSO product is carried out microprobe analysis.The crystalline analysis of each the CoAPSO component morphological feature that indicates having hereinafter obtains following analytical data based on relative peak height:
A) the CoAPSO-11(example 42):
The mean number of point probe
（Average of Spot Probes）
Co 1.0
Al 8.0
P 10.0
Si 1.0
B) the CoAPSO-20(example 10.6):
The mean number of point probe
（Average of Spot Probes）
Co 0.5
Al 8.0
P 7.5
Si 3.4
C) the CoAPSO-34(example 69):
The mean number of point probe
（Average of Spot Probes）
Co 0.5
Al 8.0
P 10.0
Si 1.0
D) the CoAPSO-35(example 10):
The mean number of point probe
（Average of Spot Probes）
Co 0.5
Al 9.0
P 7.5
Si 1.0
E) the CoAPSO-36(example 95):
The mean number of point probe
（Average of Spot Probes）
Co 0.6
Al 9.1
P 9.4
Si 2.2
F) the CoAPSO-44(example 16):
The mean number of point probe
（Average of Spot Probes）
Co 1.0
Al 8.0
P 8.0
Si 0.6
G) the CoAPSO-47(example 104):
The mean number of point probe
（Average of Spot Probes）
Co 0.7
Al 8.4
P 9.2
Si 2.8
Example 109
The sample of each CoAPSO product is done the loading capacity test.As hereinafter mentioning, to the evaluation of the loading capacity of CoAPSO product both can work as they when being in former synthetic form, also can be placed in air or the nitrogen calcining and make after with the template of removing part at them.The McBain-Baker of use standard (McBain-Bakr) gravimetric analysis absorption instrument is measured the loading capacity of sample after each calcination.Sample activates in 350 ℃ vacuum earlier before mensuration.The McBain-Baker instrument data of each the CoAPSO product after the aforesaid calcining are as follows:
A) the CoAPSO-11(example 61):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 106-183 6.9
Oxygen 3.46 744-183 12.1
Trimethylmethane 5.0 740 24.2 3.9
Hexanaphthene 6.0 82 23.9 13.5
Neopentane 6.2 741 25.3 3.6
Water 2.65 4.6 24.9 7.1
Water 2.65 19 24.8 21.0
*In 600 ℃ air, calcined one hour earlier before the activation.
Above-mentioned data show that the aperture of calcining after product is about 6.0
B) the CoAPSO-20(example 106):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 102-183 5
Oxygen 3.46 744-183 6.4
Water 2.65 4.6 23.3 10
Water 2.65 19 23.2 14
*In 500 ℃ air, calcined one hour earlier before the activation.
Above-mentioned data show that the aperture of calcining after product is about 3.0
C) the CoAPSO-31(example 102):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 105-183 6.9
Oxygen 3.46 741-183 12.8
Neopentane 6.2 739 23.5 5.8
Water 2.65 4.6 23.5 5.8
Water 2.65 20 24.0 15.9
*In 500 ℃ air, calcined 1.5 hours earlier before the activation.
Above-mentioned data show that the aperture of calcining after product is greater than 6.2
About.
D) the CoAPSO-34(example 78):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 103-183 15.9
Oxygen 3.46 731-183 28.2
Normal hexane 4.3 103 23.9 9.8
Trimethylmethane 5.0 741 23.3 1.8
Water 2.65 4.6 23.8 11.3
Water 2.65 18.5 24.0 28.9
*In 425 ℃ nitrogen, calcined 2 hours earlier before the activation.
Above-mentioned data indicate that the aperture of calcination after product is about 4.3
E) the CoAPSO-34(example 89):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 105-183 18.6
Oxygen 3.46 741-183 28.8
Trimethylmethane 5.0 108 23.9 9.9
Normal hexane 4.3 742 23.3 1.2
Water 2.65 4.6 23.8 10.7
Water 2.65 20.0 24.0 30.1
*In 600 ℃ air, calcined 1 hour earlier before the activation.
F) the CoAPSO-35(example 8):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 103-183 11.7
Oxygen 3.46 731-183 15.5
Trimethylmethane 5.0 741 24.5 0.6
Normal hexane 4.3 103 24.4 3.5
Water 2.65 4.6 24.4 14.3
Water 2.65 18.5 23.9 22.7
*In 500 ℃ nitrogen, calcined 2 hours earlier before the activation.
Above-mentioned data show that the aperture of calcining after product is about 4.3
G) the CoAPSO-44(example 19):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 103-183 24.8
Oxygen 3.46 731-183 31.4
Normal hexane 4.3 103 24.4 7.4
Trimethylmethane 5.0 741 24.5 0.3
Water 2.65 4.6 24.4 27.8
Water 2.65 18.5 23.9 35.1
*In 500 ℃ air, calcined 1.25 hours earlier before the activation.
Above-mentioned data show that the aperture of calcining after product is about 4.3
H) the CoAPSO-47(example 104):
Power diameter pressure temperature
Adsorbate
(holder) (℃) absorption weight percent
*
Oxygen 3.46 102-183 4.1
Oxygen 3.46 744-183 4.9
Trimethylmethane 5.0 746 24.1 0.6
Normal hexane 4.3 95 23.6 1.3
Water 2.65 4.6 23.3 9.6
Water 2.65 19 23.2 14.3
*In 500 ℃ of air, calcined 1.5 hours earlier before the activation.
Above-mentioned data show that the aperture of calcining after product is about 4.3
Example 110
(a) CoAPSO-5 of the former synthetic form of usefulness x-ray analysis example 76.The CoAPSO-5 product has the characteristics of the X-ray powder diffraction style of following table seven:
Table seven
2ν d.（
） 100×I/I
0
7.4 11.95 100
9.6
＊9.21 65
12.9
＊＊6.86 19
14.1
＊6.28 10
14.9 5.95 26
16.0
＊5.54 32
17.8
＊4.98 13
19.8 4.48 61
20.5
＊4.33 55
21.1 4.21 74
22.4
＊＊3.97 94
23.0
＊3.87 10
24.8 3.59 16
25.2
＊3.53 16
26.0
＊＊3.427 42
27.4
＊3.255 13
28.2
＊3.164 10
29.1 3.069 19
29.5
＊3.028 10
30.1 2.969 29
30.6
＊2.921 23
31.1
＊2.876 19
33.7
＊＊2.660 10
34.5
＊＊2.600 19
37.0 2.430 7
37.7 2.386 16
41.5 2.176 7
42.2 2.141 8
43.7 2.071 7
44.9
＊＊2.019 7
47.8
＊＊1.903 10
48.9
＊1.863 10
55.8 1.647 10
*The peak value that obtains from CoAPSO-34
*The peak value that obtains from CoAPSO-34 and CoAPSO-5
(b) in 600 ℃ air with the CoAPSO-5 of example 21 calcining 4 hours.The calcining after product has the characteristic of the X-ray powder diffraction style of following table eight:
Table eight
2ν d.（
） I/I
0×100
7.4 11.95 100
12.9 6.86 22
14.8 5.99 13
19.7 4.51 39
20.3
＊4.37 83
21.0 4.23 74
21.4
＊4.15 99
22.4 3.97 74
22.9
＊3.88 35
24.4 3.65 13
25.9 3.440 30
27.1
＊＊3.290 17
28.1
＊3.175 26
29.0 3.079 26
30.1 2.969 30
33.7 2.660 13
34.6 2.592 22
35.6
＊2.522 26
37.0 2.430 13
37.8 2.380 13
42.8 2.113 13
43.8 2.067 9
47.8 1.903 9
55.8 1.647 9
*The peak value of tridymite (tridymite) (release notes, original text is that tridynite is wrong)
*The peak value of impurity
(c) alleged here each crystal seed of CoAPSO-5 has CoO
2, AlO
2, PO
2And SiO
2The skeleton structure of dimensional microporous crystal of tetrahedron element, and the chemical constitution that sees service, by the following chemical formulation of no water meter:
mR∶（Co
WAl
XP
YSi
Z）O
2
Here " R " representative deposit in the micropore system in the crystal, be at least and be a kind of organic formwork agent; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", its value is about 0～0.3; " W ", " X ", " Y " and " Z " are according to each 1 or 2 each molar fraction as top defined; And no matter all have distinctive X-ray powder diffraction style, include d-spacing listed in the table nine at least in former synthetic form or in the calcining form:
Table nine
2 ν d.(
) relative intensity
7.3～7.5 12.11～11.79 m-VS
14.7～14.9 6.03～5.95 W-m
19.6～19.8 4.53～4.48 W-m
20.9～21.2 4.25～4.19 W-VS
22.3～22.4 3.99～3.97 m-VS
25.8～26.0 3.453～3.427 VW-m
(d) each the CoAPSO-5 composition that has obtained the X-powder diffraction pattern so far all has the characteristics that the X-of table ten ray pattern is arranged:
Table ten
2ν d，（
） I/I
0×100
7.3～7.5 12.11～11.79 32～100
12.7～12.9 6.97～6.86 2～22
14.7～14.9 6.03～5.95 10～26
19.6～19.8 4.53～4.48 7～39
20.9～21.2 4.25～4.19 19～100
22.3～22.4 3.99～3.97 25～94
24.4～24.8 3.65～3.59 2～16
25.8～26.0 3.453～3.427 6～41
29.0～29.1 3.079～3.069 3～26
29.9～30.1 2.988～2.969 3～30
33.5～33.7 2.667～2.660 2～13
34.4～34.6 2.607～2.592 4～22
36.8～37.0 2.442～2.430 2～13
37.5～37.8 2.398～2.380 3～16
41.4～41.5 2.181～2.176 1～7
42.2～42.8 2.141～2.113 1～13
43.7～43.8 2.071～2.067 0～9
44.9～45.0 2.019～2.014 1～7
47.5～47.8 1.914～1.903 3～10
55.6～55.8 1.653～1.647 1～10
Example 111
(a) CoAPSO-11 of the former synthetic form of usefulness x-ray analysis example 42.CoAPSO-11 has the characteristics of the X-ray powder diffraction style of following table 11:
Table ten one
2ν d，（
） 100×I/I
0
7.9 11.19 32
9.3 9.51 72
12.3
＊7.20 16
13.1 6.76 24
15.6 5.68 32
16.2 5.47 12
18.2 4.87 16
18.9 4.70 12
20.3 4.37 40
21.0 4.23 100
22.1 4.02 56
22.5 3.95 60
22.7 3.92 72
23.1 3.85 68
24.6 3.62 20
26.3 3.389 28
28.2 3.164 16
28.5 3.132 24
29.4 3.038 20
29.6 3.018 16
29.9 2.988 16
31.3 2.858 16
32.6 2.747 24
34.0 2.637 16
36.3 2.475 12
37.6 2.392 20
39.3 2.292 12
42.8 2.113 8
44.8 2.023 8
50.5 1.807 12
54.4 1.687 12
*Peak value may include impurity
(b) CoAPSO-11 of example 42 is placed in 600 ℃ of air and calcined 1.5 hours.Calcinate has the characteristics as the X-ray powder diffraction style of following table 12:
Table ten two
2ν d，（
） 100×I/I
0
8.1 10.92 70
9.5 9.31 83
13.1 6.76 26
13.5 6.56 30
15.8 5.61 56
18.5 4.80 17
19.2 4.62 13
20.2 4.40 Sh
20.3 4.37 35
21.3 4.17 100
22.3 3.99 61
22.5 3.95 Sh
23.0 3.87 65
23.4 3.80 52
24.3 3.66 17
25.1 3.548 17
26.5 3.363 30
26.6 3.351 Sh
28.2 3.164 13
28.9 3.089 26
29.5 3.028 17
30.1 2.969 13
30.5 2.931 17
31.8 2.814 17
32.9 2.722 22
34.7 2.585 13
36.2 2.481 13
37.9 2.374 17
38.3 2.350 17
39.5 2.281 9
*Peak value may include impurity
(c) alleged here CoAPSO-11 crystal seed has CoO
2, AlO
2, PO
2And SiO
2The skeleton structure of the dimensional microporous crystal of tetrahedron element, and the chemical constitution that sees service, with no water meter with chemical formulation down:
mR（Co
WAl
XP
YSi
Z）O
2
Here " R " representative be present in the crystal in the micropore system, be at least a kind of organic formwork agent; " m " represents every mole of (C
OWAl
XP
YSi
Z) O
2The mole number of " R ", its value is about 0～0.3; " W ", " X ", " Y " and " Z " are according to Fig. 1 or 2 each molar fraction as above-mentioned defined; No matter be all have in former synthetic form or in the calcining form distinctive, include d-spacing listed in the table ten three at least:
Table ten three
2 θ d, (
) relative intensity
7.9～8.1 11.19～10.92 m
9.3～9.5 9.51～9.31 m-S
21.0～21.3 4.23～4.17 VS
22.1～22.3 4.02～3.99 m
22.7～23.1 3.92～3.85 m
22.2～23.4 3.83～3.80 m
(d) each the CoAPSO-11 composition that has obtained the X-powder diffraction pattern so far all has the characteristics that the X-of table ten four ray pattern is arranged:
Table ten four
2θ d，（
） 100×I/I
0
7.9～8.1 11.19～10.92 32～70
9.3～9.5 9.51～9.31 72～83
12.3
＊7.20 16
13.1～13.2 6.76～6.71 16～26
13.5～13.6 6.56～6.51 30
15.6～15.8 5.68～5.61 32～56
16.2～16.3 5.47～5.44 8～12
18.2～18.5 4.87～4.80 16～17
18.9～19.2 4.70～4.62 12～13
19.7～20.2 4.51～4.40 Sh
20.3 4.37 35-40
21.0～21.3 4.23～4.17 100
22.1～22.3 4.02～3.99 56～61
22.4～22.6 3.97～3.93 Sh～60
22.7～23.1 3.92～3.85 65～72
23.2～23.4 3.83～3.80 52～68
24.3～24.6 3.66～3.62 17～20
25.1 3.548 17
26.3～26.5 3.389～3.363 28～30
26.6 3.351 Sh
28.1～28.2 3.175～3.164 13～16
28.5～28.9 3.132～3.089 24～26
29.4～29.5 3.038～3.028 17～20
29.6～30.5 3.018～2.931 13～17
31.3～31.8 2.858～2.814 16～17
32.6～32.9 2.747～2.722 22～24
34.0～34.7 2.637～2.585 13～16
36.2～36.3 2.481～2.475 12～13
36.7～37.9 2.392～2.374 17～20
38.3～38.4 2.350～2.344 17～18
39.3～39.5 2.292～2.281 9～12
42.8～42.9 2.113～2.108 8～9
44.7～44.8 2.027～2.023 8～9
50.5～50.6 1.807～1.804 9～12
54.4～54.6 1.687～1.681 9～12
*Peak value may contain impurity
Example 112
(a) CoAPSO-16 of the former synthetic form of usefulness x-ray analysis example 4.The CoAPSO-16 product has the characteristics of the X～ray powder diffraction style of following table 15:
Table ten five
2ν d，（
） 100×I/I
0
8.7
＊10.16 17
11.0
＊8.04 40
11.5 7.69 32
13.0
＊6.81 15
15.9
＊5.57 13
17.3
＊5.13 55
17.9
＊4.96 13
18.8 4.72 23
20.8
＊4.27 （Sh）
21.2
＊4.19 40
22.0
＊＊4.04 100
23.2
＊＊3.83 21
23.8
＊3.74 11
25.1
＊3.548 9
26.9
＊＊3.314 23
28.6
＊3.121 26
28.8
＊3.100 26
29.0 3.079 15
29.6 3.018 11
29.9 2.988 15
32.2
＊2.780 34
32.8 2.730 9
34.6
＊＊2.592 13
35.8
＊2.508 11
37.9 2.374 9
40.1 2.249 9
42.2
＊2.141 11
43.0
＊2.103 9
44.5 2.036 9
48.6
＊＊1.873 13
49.6 1.838 11
51.6 1.771 11
52.6 1.740 6
55.0 1.670 6
55.4
＊1.658 11
*The peak value that obtains from CoAPSO-35
The peak value that obtains from CoAPSO-16 and CoAPSO-35
(b) alleged here CoAPSO-16 crystal seed has CoO
2, AlO
2, PO
2And SiO
2The skeleton structure of the dimensional microporous crystal of tetrahedron element, and the chemical constitution that sees service, with the following chemical formulation of no water meter:
mR（Co
WAl
XP
YSi
Z）O
2
Here " R " representative is present in a kind of organic formwork agent that is at least in the interior micropore of the crystal system; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", its value is about 0～0.3; " W ", " X ", " Y " and " Z " are according to Fig. 1 or 2 each molar fraction as above-mentioned defined; No matter be former synthetic form or calcining all have in the form distinctive, include d-spacing listed in the table ten six at least:
Table ten six
2 ν d.(
) relative intensity
11.4～11.6 7.76～7.63 W-S
17.2～17.4 5.16～5.10 m
18.7～18.9 4.75～4.70 VW-m
21.9～22.1 4.06～4.02 VS
23.1～23.3 3.85～3.82 m
26.8～27.0 3.326～3.302 m
29.8～29.9 2.998～2.988 W-m
(c) each the CoAPSO-16 composition that has obtained each case of X-ray powder diffraction so far all has the characteristics that each case of the X-of table ten seven ray is arranged:
Table ten seven
2ν d，（
） 100×I/I
0
11.4～11.6 7.76～7.63 11～79
17.2～17.4 5.16～5.10 66～80
18.7～18.9 4.75～4.70 7～53
21.9～22.1 4.06～4.02 100
23.1～23.3 3.85～3.82 21～24
26.8～27.0 3.326～3.302 23～28
29.0 3.079 14～18
29.5～29.7 3.028～3.008 4～15
29.8～29.9 2.998～2.988 15～29
32.7～32.9 2.739～2.722 3～9
34.5～34.7 2.600～2.585 9～13
37.8～38.0 2.380～2.368 6～9
40.0～40.2 2.534～2.243 1～9
44.3～44.6 2.045～2.032 2～9
48.5～48.7 1.877～1.870 8～13
49.5～49.7 1.841～1.834 8～11
51.5～51.7 1.774～1.768 6～11
52.5～52.7 1.743～1.737 6～7
54.9～55.1 1.672～1.667 1～6
Example 113
(a) CoAPSO-20 of the former synthetic form of usefulness x-ray analysis example 106.The CoAPSO-20 product has the characteristics of the X-ray powder diffraction style of following table 18.
Table ten eight
2ν d.（
） 100×I/I
0
10.293 8.5942 7
12.078 7.3278 1
13.925 6.3595 46
14.376 6.1609 2
18.773 4.7268 2
19.738 4.4977 42
20.507 4.3307 3
22.093 4.0233 3
24.227 3.6735 100
26.363 3.3806 3
26.941 3.3094 3
28.052 3.1808 11
31.442 2.8451 11
31.759 2.8175 2
31.980 2.7985 2
34.523 2.5980 16
37.426 2.4029 1
40.075 2.2499 4
42.614 2.1215 4
47.3 1.922 4
51.8 1.765 8
(b) CoAPSO-20 of example 106 was calcined 1 hour in 500 ℃ air.Calcinate has the characteristics of the X-ray powder diffraction style of following table 19:
Table ten nine
2ν d.（
） 100×I/I
0
10.6
＊8.39 7
21.1
＊7.30 3
12.2
＊7.24 2
14.0 6.33 75
14.8
＊6.01 3
16.1
＊5.51 2
19.8 4.48 38
22.2 4.01 4
24.3 3.66 100
26.7
＊3.344 3
27.6
＊3.227 2
28.1 3.173 14
31.5 2.839 13
32.2
＊2.781 2
32.4
＊2.764 2
34.6 2.593 18
40.2 2.244 3
42.5 2.127 4
47.3 1.922 4
51.8 1.765 8
*The impurity peak value
(c) alleged here CoAPSO-20 crystal seed has CoO
2, AlO
2, PO
2And SiO
2The skeleton structure of dimensional microporous crystal of tetrahedron element, and the chemical constitution that sees service, by the following chemical formulation of no water meter:
mR∶（Co
WAl
XP
YSi
Z）O
2
Here " R " representative is present in a kind of organic formwork agent that is at least in the intracrystalline micropore system; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", its value is about 0～0.3; " W ", " X ", " Y " and " Z " are according to Fig. 1 or 2 each molar fraction as top defined; And no matter former synthetic form still the calcining form all have distinctive, include the listed d-spacing of table two ten at least:
Table two ten
2 θ d.(
) relative intensity
13.9～14.0 6.37～6.33 m
19.7～19.8 4.51～4.48 m
24.2～24.3 3.68～3.66 VS
28.0～28.1 3.187～3.175 W
31.4～31.5 2.849～2.840 W
34.5～34.6 2.600～2.592 W
(d) each the CoAPSO-20 composition that has obtained X-ray powder diffraction style so far all has the X-ray pattern characteristic of table two 11:
Table two 11
2θ d.（
） 100×I/I
0
13.9～14.0 6.37～6.33 44～75
19.7～19.8 4.51～4.48 38～42
22.1～22.2 4.02～4.00 3～4
24.2～24.3 3.68～3.66 100
28.0～28.1 3.187～3.175 11～14
31.4～31.5 2.849～2.840 11～12
34.5～34.6 2.600～2.592 16～18
40.1～40.2 2.249～2.243 3～4
42.5～42.6 2.127～2.122 3～4
47.3～47.4 1.922～1.918 4～5
51.8～51.9 1.765～1.762 8～9
Example 114
(a) use the nothing of x-ray analysis example 101 to synthesize the CoAPSO-31 of form.CoAPSO-31 has the X-ray powder diffraction style of following table 22:
Table two 12
2ν d.（
） 100×I/I
0
8.5 10.35 58
17.1 5.19 5
18.4 4.82 2
20.3 4.38 42
21.1 4.20 4
22.1 4.03 28
22.7 3.93 100
23.2 3.83 2
25.2 3.537 4
25.7 3.464 3
28.0 3.187 12
29.8 3.000 6
31.8 2.816 20
35.2 2.549 9
36.2 2.482 2
37.2 2.417 2
37.7 2.386 2
38.3 2.352 2
39.4 2.288 3
39.7 2.271 2
40.3 2.239 2
45.3 2.002 2
46.8 1.943 2
48.7 1.869 2
51.7 1.768 4
(b) (a) partial C oAPSO-31 calcined 1.5 hours in 500 ℃ air.Calcinate has the characteristics as the X-powder diffraction pattern of following table 23:
Table two 13
2ν d，（
） 100×I/I
0
8.5 10.36 73
14.8 5.99 4
17.1 5.19 10
18.4 4.81 4
20.3 4.37 56
21.4 4.15 3
22.1 4.03 47
22.7 3.93 100
23.4 3.80 3
25.2 3.530 6
25.7 3.464 7
28.0 3.184 15
29.8 2.300 10
31.0 2.885 2
31.8 2.813 31
35.2 2.548 10
36.3 2.476 5
37.3 2.409 3
37.7 2.385 3
38.3 2.348 3
39.4 2.287 4
39.7 2.270 3
40.3 2.237 3
46.7 1.944 5
47.6 1.910 3
48.7 1.868 3
49.3 1.849 2
51.7 1.768 6
(c) alleged here CoAPSO-31 crystal seed has CoO
2, AlO
2, PO
2And SiO
2The skeleton structure of the dimensional microporous crystal of tetrahedron element, and the chemical constitution that sees service, with no water meter with chemical formulation down:
mR（Co
WAl
XP
YSi
Z）O
2
Here " R " representative is present in a kind of organic formwork agent that is at least in the intracrystalline micropore system; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", its value is about 0～0.3; " W ", " X ", " Y " and " Z " are according to Fig. 1 or 2 each molar fraction as above-mentioned defined; And no matter be all have in former synthetic form or in the calcining form distinctive, include the listed d-spacing of table two 14 at least:
Table two 14
2 ν d.(
) relative intensity
8.5～8.6 10.40～10.28 m
20.2～20.3 4.40～4.37 m
22.0～22.1 4.04～4.02 m
22.6～22.7 3.93～3.92 VS
28.0～28.1 3.187～3.175 W
31.7～31.8 2.823～2.814 m
(d) each the CoAPSO-31 composition that had obtained the X-powder diffraction pattern so far already all has the characteristics of the X-ray pattern of table two 15:
Table two 15
2ν d，（
） 100×I/I
0
8.5～8.6 10.40～10.28 58～73
14.7～14.8 6.03～5.99 2～4
17.0～17.2 5.22～5.16 5～10
18.4～18.5 4.82～4.80 2～4
20.2～20.3 4.40～4.37 42～56
21.1～21.4 4.21～4.15 3～4
22.0～22.1 4.04～4.02 28～47
22.6～22.7 3.93～3.92 100
23.2～23.4 3.83～3.80 2～3
25.1～25.2 3.548～3.534 4～6
25.7～25.8 3.466～3.453 3～7
28.0～28.1 3.187～3.175 12～15
29.7～29.8 3.008～2.998 6～10
31.0～31.1 2.885～2.876 2～4
31.7～31.8 2.823～2.814 20～31
35.2～35.3 2.550～2.543 9～10
36.2～36.3 2.481～2.475 2～5
37.2～37.3 2.417～2.411 2～3
37.7～37.8 2.386～2.380 2～3
38.2～38.4 2.356～2.344 2～3
39.3～39.4 2.292～2.287 3～4
39.6～39.7 2.276～2.270 2～3
40.2～40.3 2.243～2.238 2～3
45.2～45.3 2.006～2.002 1～2
46.7～46.8 1.945～1.941 2～5
47.5～47.6 1.914～1.910 2～3
48.7～48.8 1.870～1.866 2～3
49.2～49.3 1.852～1.848 1～2
51.6～51.7 1.771～1.768 4～6
Example 115
(a) utilize the CoAPSO-34 of x-ray analysis example 90 former synthetic attitudes.The feature that the CoAPSO-34 product is represented by the X-ray powder diffraction style of following table 26:
Table two 16
2ν d，（
） 100×I/I
0
9.6 9.22 100
12.9 6.84 11
14.2 6.26 10
16.1 5.51 35
18.1 4.92 15
20.7 4.29 62
22.3 3.98 3
23.2 3.84 4
25.3 3.522 17
26.0 3.430 14
27.7 3.217 2
28.5 3.136 3
29.7 3.010 4
30.7 2.914 25
31.3 2.855 16
31.8 2.817 3
34.5 2.597 6
36.3 2.473 3
39.8 2.263 3
43.3 2.090 3
43.6 2.075 3
47.6 1.911 2
47.8 1.904 3
49.2 1.853 5
51.1 1.786 3
53.4 1.716 3
54.7 1.678 2
(b) CoAPSO-34 of example 90 temperature with 600 ℃ in air was calcined one hour.The feature that calcination product is represented by the X-ray powder diffraction style of following table 27:
Table two 17
2ν d，（
） 100×I/I
0
9.6 9.20 100
10.1 8.77 6
13.0 6.80 14
16.2 5.46 8
17.9 4.97 4
18.0 4.94 3
19.3 4.60 4
20.5 4.34 3
20.8 4.27 14
21.4 4.15 4
23.3 3.82 2
24.3 3.67 3
25.1 3.543 3
25.3 3.524 3
25.7 3.464 2
26.2 3.402 5
31.0 2.831 10
31.6 2.835 5
31.8 2.815 3
(c) sample such as the CoAPSO-34 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes, and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic model agent that is present in the intracrystalline pore canal system at least; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", " Z " represent molar fraction, with reference to figure 1 or Fig. 2, above-mentioned " W " " X " " Y " " Z " has been defined, and has the characteristic x-ra-diation powder diffraction pattern in former synthetic attitude or calcining and attitude, comprises the d-spacing that table two 18 is illustrated at least:
Table two 18
2 ν d.(
) relative intensity
9.4-9.8 6.41-9.03 S-VS
12.86-13.06 6.86-6.76 W
14.08-14.30 5.28-6.19 W-m
15.90-16.20 4.57-5.47 VW-m
20.60-20.83 2.31-4.26 W-VS
30.50-30.80 2.931-2.903 W-m
(d) hereto, the X-ray powder diffraction style of each CoAPSO-34 composition obtains, and has represented feature by the X-ray powder diffraction style of table two 19:
Table two 19
2ν d，（
） 100×I/I
0
9.4-9.8 9.41-9.03 87-100
10.09-10.14 8.77-8.72 1-6
12.86-13.06 6.86-6.76 11-18
14.08-14.30 6.28-6.19 10-24
15.90-16.24 5.57-5.47 8-35
17.85-18.05 4.97-4.92 3-15
19.13-19.48 4.65-4.55 1-4
20.48-20.56 4.34-4.33 Sh-3
20.60-20.83 4.31-4.26 14-100
21.41-22.35 4.15-3.98 3-4
23.18-23.31 3.84-3.82 2-3
24.25-24.53 3.67-3.63 0-3
25.13-25.29 3.543-3.520 3-17
25.72-25.98 3.464-3.430 3-14
26.06-26.19 3.414-3.402 5-9
27.73-27.80 3.217-3.209 2-16
28.30-28.46 3.153-3.136 3-9
29.50-29.68 3.028-3.010 4-14
30.50-30.80 2.931-2.903 12-25
31.04-31.33 2.881-2.855 7-16
31.60-31.79 2.831-2.815 3-5
34.40-34.53 2.607-2.597 5-6
36.20-36.32 2.481-2.473 3-8
38.40-38.60 2.344-2.332 3-5
39.70-39.83 2.270-2.263 3-4
43.10-43.28 2.099-2.090 Sh-6
43.40-43.61 2.045-2.075 3-10
47.40-47.59 1.918-1.911 Sh-2
47.77-47.80 1.904-1.903 3-10
49.17-49.20 1.853-1.852 5-10
49.90-50.40 1.828-1.809 0-11
51.13-51.20 1.786-1.784 3-10
53.20-53.39 1.722-1.716 3-10
54.60-54.70 1.681-1.678 2-7
55.80-55.90 1.647-1.645 2-10
Example 116
(a) utilize the CoAPSO-35 of X light analysis example 10 former synthetic attitudes.The feature that the CoAPSO-35 product is represented by the X-ray powder diffraction style of following table 30:
Table three ten
2ν d，（
） 100×I/I
0
7.9
＊11.19 8
8.6 10.28 18
10.9 8.12 45
11.6 7.63 8
13.4 6.61 30
15.9 5.57 15
17.3 5.13 83
17.8 4.98 20
20.9 4.25 58
21.9 4.06 100
22.7 3.92 13
23.3 3.82 38
24.9 3.58 13
25.6 3.480 8
26.9 3.314 28
28.3 3.153 45
29.1 3.069 13
31.4
＊2.849 10
32.2 2.780 40
34.3 2.614 10
35.2
＊2.550 8
35.9 2.501 8
37.8 2.380 5
39.4 2.287 5
41.9 2.156 8
42.6 2.122 10
44.6 2.032 8
47.8 1.903 8
48.6 1.873 8
49.8 1.831 10
51.2 1.784 10
55.7 1.650 8
*The peak value of impurity
(b) CoAPSO-35 of example 10 temperature lower calcination two hours of 600 ℃ in air.The feature that calcination product is represented by the X-ray powder diffraction style of following table hentriaconta-
The table hentriaconta-
2ν d.（
） 100×I/I
0
8.7 10.16 26
11.0 8.04 90
11.8 7.50 21
13.7 6.46 100
16.2 5.47 16
17.4 5.10 26
17.6 5.04 37
21.2 4.19 42
22.3 3.99 58
23.2 3.83 26
23.7 3.75 37
25.1 3.548 26
25.3 3.520 32
26.3 3.389 26
27.5 3.243 42
28.6 3.121 53
28.8 3.100 53
29.6 3.018 32
31.9
＊2.805 26
32.8 2.730 42
34.5 2.600 21
35.0 2.564 21
35.8 2.508 16
*The impurity peak value
(c) sample such as the CoAPSO-35 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes, and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic formwork agent that is present in the intracrystalline pore canal system at least; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", " Z " represent molar fraction, and with reference to figure 1 or Fig. 2, above-mentioned " W ", " X ", " Y ", " Z " have been defined; And in former synthetic attitude or calcined state, have X-ray powder diffraction style feature, comprise the d-spacing that table three 12 is illustrated at least:
Table three 12
2 ν d.(
) relative intensity
10.9-11.0 8.12-8.04 m-VS
13.4-13.7 6.61-6.46 m-VS
17.3-17.4 5.13-5.10 m-S
20.9-21.2 4.25-4.19 m
21.9-22.3 4.06-3.99 m-VS
28.3-28.6 3.153-3.121 m
(d) hereto, the X light powder diffraction style of CoAPSO-35 composition obtains, and the feature of being represented by the X-ray powder diffraction style of table three 13:
Table three 13
2ν d，（
） 100×I/I
0
7.9
＊11.19 8
8.6-8.7 10.28-10.16 18-26
10.9-11.0 8.12-8.04 45-90
11.6-11.8 7.63-7.50 8-21
13.4-13.7 6.61-6.46 30-100
15.9-16.2 5.57-5.47 15-16
17.3-17.4 5.13-5.10 26-83
17.6-17.8 5.04-5.98 20-37
20.9-21.2 4.25-4.19 42-58
21.9-22.3 4.06-3.99 58-10
22.7-23.2 3.92-3.83 13-26
23.3-23.7 3.83-3.75 37-38
24.9-25.1 3.58-3.548 13-26
25.3 3.520 32
25.6-26.3 3.480-3.389 8-26
26.9-27.5 3.314-3.243 28-42
28.3-28.6 3.153-3.121 45-53
28.8-29.6 3.100-3.018 13-53
31.4-31.9 2.849-2.805 10-26
32.2-32.8 2.780-2.730 40-42
34.3-34.5 2.614-2.600 10-21
35.0-35.2
＊2.564-2.550 8-21
35.8-35.9 2.508-2.501 8-16
37.8-37.9 2.380-2.374 5
39.4-39.5 2.287-2.281 5
41.9-42.0 2.156-2.151 8
42.6-42.7 2.122-2.118 10
44.6-44.7 2.032-2.027 8
47.8-47.9 1.903-1.900 8
48.6-48.7 1.873-1.870 8
49.8-49.9 1.831-1.828 10
51.2-51.3 1.784-1.781 10
55.6-55.7 1.653-1.650 8
Example 117
(a) utilize the CoAPSO-36 of X light analysis example 93 former synthetic attitudes.The CoAPSO-36 product has the feature of being represented by following table 34 X-ray powder diffraction styles:
Table three 14
2ν d.（
） 100×I/I
0
7.3 12.11 7
8.0 11.12 100
8.2 10.74 29
9.2 9.65 4
12.9 6.86 5
13.6 6.52 8
13.7 6.48 8
15.9 5.57 14
16.5 5.38 42
18.4 4.83 6
19.1 4.64 37
20.8 4.27 49
21.6 4.12 7
21.8 4.09 22
22.1 4.03 28
22.6 3.94 29
23.0 3.86 9
24.0 3.71 9
27.3 3.267 20
27.7 3.226 7
28.4 3.148 13
28.7 3.116 5
29.2 3.063 12
30.4 2.940 7
32.1 2.792 12
34.9 2.571 12
(b) CoAPSO-36 of example 93 temperature with 500 ℃ in air was calcined one hour.Calcination product has by the X-ray powder diffraction style of following table 35 has represented feature:
Table three 15
2ν d（
） 100×I/I
0
7.4 12.00 8
8.0 11.10 100
8.3 10.69 33
13.6 6.52 13
15.9 5.58 8
16.6 5.36 32
19.3 4.59 29
20.8 4.27 26
21.5 4.14 8
21.8 4.07 11
22.3 3.98 19
22.7 3.92 17
24.0 3.71 7
27.3 3.266 19
27.8 3.215 10
28.3 3.154 12
28.4 3.145 13
28.5 3.131 10
29.2 3.062 13
32.0 2.797 10
(c) sample such as the CoAPSO-36 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic formwork agent that is present in the intracrystalline pore canal system at least; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", " Z " expression molar fraction are with reference to figure 1 or Fig. 2, and above-mentioned " W " " X " " Y " " Z " has been defined; And in former synthetic attitude or calcined state, have X light powder diffraction style feature: comprise the d-spacing that table three 16 is illustrated at least:
Table three 16
2 ν d(
) relative intensity
7.8-8.0 11.33-11.05 VS
8.2-8.3 10.78-10.65 m
16.4-16.6 5.40-5.34 m
19.0-19.3 4.67-4.60 m
20.7-21.0 4.29-4.23 m
22.3-22.6 3.99-3.93 W-m
(d) hereto, the X light powder diffraction style of CoAPSO-36 composition obtains, and has represented feature by the X-ray powder diffraction style of table three 17:
Table three 17
2ν d（
） 100×I/I
0
7.3-7.5 12.11-11.79 7-8
7.8-8.0 11.33-11.05 100
8.2-8.3 10.78-10.65 29-33
9.2-9.3 9.61-9.51 4-5
12.9-13.0 6.86-6.81 4-5
13.5-13.6 6.56-6.51 8-13
13.7 6.46 7-8
15.8-16.0 5.61-5.54 8-14
16.4-16.6 5.40-5.34 32-42
18.4 4.82 4-6
19.0-19.3 4.67-4.60 29-36
20.7-21.0 4.29-4.23 26-49
21.5-21.7 4.13-4.10 7-8
21.8-22.0 4.08-4.04 11-22
22.3-22.6 3.99-3.93 17-29
22.9-23.0 3.88-3.87 5-9
23.9-24.0 3.72-3.71 7-9
27.2-27.3 3.278-3.267 19-20
27.6-27.8 3.232-3.209 7-10
28.3-28.4 3.153-3.143 12-13
28.5-28.7 3.132-3.110 5-10
29.0-29.2 3.079-3.058 12-13
30.3-30.4 2.950-2.940 5-7
32.0-32.1 2.797-2.788 10-12
34.7-34.9 2.585-2.571 10-12
Example 118
(a) utilize the CoAPSO-39 of the former synthetic attitude of X light analysis example 45.The CoAPSO-39 product has been represented feature by the X-ray powder diffraction style of following table 38:
Table three 18
2ν d（
） 100×I/I
0
8.0
＊11.05 31
9.4
＊＊9.41 47
13.1
＊6.76 22
13.3 6.66 16
14.8
＊5.99 9
15.6
＊5.68 31
16.2
＊5.47 6
18.1 4.90 16
19.0 4.67 9
20.2
＊4.40 41
21.0
＊＊4.23 100
22.1
＊4.02 53
22.4
＊＊3.97 53
22.6
＊3.93 69
23.1
＊3.85 66
24.7
＊3.60 13
26.4
＊＊3.376 28
26.9 3.314 13
27.7
＊3.220 13
28.1 3.175 13
28.6
＊＊3.121 25
29.4 3.038 13
30.2 2.959 13
31.4
＊2.849 13
32.7
＊＊2.739 22
34.2
＊＊2.622 16
34.6 2.592 6
36.2 2.481 6
37.6 2.392 16
37.8
＊＊2.380 16
39.4
＊＊2.287 9
42.9
＊＊2.108 9
44.6
＊＊2.032 9
48.6 1.873 6
50.6
＊1.804 6
51.4 1.778 6
54.5
＊＊1.684 9
55.6
＊＊1.653 6
*The peak value that causes by CoAPSO-11
*The peak value that causes by CoAPSO-11 and CoAPSO-39
(b) sample such as the CoAPSO-39 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes, and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic formwork agent that is present in the intracrystalline pore canal system at least, and " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", " Z " represent molar fraction, and with reference to figure 1 or Fig. 2, above-mentioned " W " " X " " Y " " Z " has been defined; In former synthetic attitude or calcined state, have X-ray powder diffraction style feature: comprise the d-spacing that table three 19 is illustrated at least:
Table three 19
2 ν d(
) relative intensity
9.4-9.5 9.41-9.31 m
13.3-13.4 6.66-6.61 m
18.1-18.2 4.90-4.87 W-m
21.0-21.2 4.23-4.19 VS
22.4-22.5 3.97-3.95 m-S
26.4-26.5 3.376-3.363 m
(c) hereto, the X-ray powder diffraction style of CoAPSO-39 composition obtains, and has represented feature by the X-ray powder diffraction style of table four ten:
Table four ten
2ν d（
） 100×I/I
0
9.4-9.5 9.41-9.31 31-43
13.3-13.4 6.66-6.61 22-30
18.1-18.2 4.90-4.87 16-31
21.0-21.2 4.23-4.19 100
22.4-22.5 3.97-3.95 53-80
26.4-26.5 3.376-3.363 28-29
26.9-27.0 3.314-3.302 6-13
28.1-28.2 3.175-3.164 13-15
28.6-28.7 3.121-3.110 10-25
29.4-29.5 3.038-3.028 13-18
30.2 2.959 13-15
32.7-32.8 2.739-2.730 17-22
34.2-34.3 2.622-2.614 12-16
34.5-34.6 2.617-2.592 6-10
36.2-36.3 2.481-2.475 6-8
37.6-37.9 2.392-2.374 16-17
39.4-39.5 2.287-2.281 9-11
42.9-43.0 2.108-2.103 8-9
44.6-44.8 2.032-2.023 6-9
48.5-48.6 1.877-1.873 5-6
51.4-51.6 1.778-1.771 5-6
54.5-54.6 1.684-1.681 9-10
55.4-55.6 1.658-1.653 5-6
Example 119
(a) utilize the CoAPSO-44 of x-ray analysis example 19 former synthetic attitudes.The CoAPSO-44 product has been represented feature by the X-ray powder diffraction style of following table 41:
Table four 11
2ν d（
） 100×I/I
0
4.8
＊18.41 8
9.4 9.41 100
13.1 6.76 22
13.9 6.37 5
15.9 5.57 （Sh）
16.2 5.47 37
17.4 5.10 5
19.0 4.67 9
20.8 4.27 72
21.8 4.08 17
22.7 3.92 9
23.1 3.85 9
24.4 3.65 49
26.2 3.401 31
27.8 3.209 11
29.0 3.079 Sh
29.7 3.008 8
30.1 2.969 20
30.8 2.903 49
31.6 2.831 3
32.5 2.755 6
32.9 2.722 6
34.8 2.578 5
35.5 2.529 9
38.6 2.332 5
39.3 2.292 3
39.8 2.265 Sh
40.0 2.254 6
42.2 2.141 5
42.6 2.122 5
43.7 2.071 3
44.4 2.040 3
46.2 1.965 3
47.3 1.922 3
48.2 1.888 12
48.7 1.870 8
50.3 1.814 15
55.0 1.759 5
53.8 1.704 9
54.8 1.675 3
(b) CoAPSO-44 of example 19 temperature with 500 ℃ in air was calcined 1.25 hours.Calcination product has been represented feature by the X-ray powder diffraction style of following table 42:
Table four 12
2ν d（
） 100×I/I
0
8.9 9.94 20
9.3 9.51 100
12.9 6.86 24
14.0 6.33 5
15.8 5.61 Sh
16.0 5.54 14
17.8 4.98 18
19.1 4.65 4
20.5 4.33 40
22.1 4.02 4
22.3 3.99 4
23.0 3.87 7
25.1 3.548 12
25.8 3.453 13
27.6 3.232 3
28.2 3.164 4
29.5 3.028 3
30.6 2.921 21
31.1 2.876 14
31.7 2.823 4
32.2 2.780 2
33.4 2.683 3
33.7 2.660 4
34.5 2.600 8
36.2 2.481 5
38.2 2.356 2
38.7 2.327 3
39.2 2.298 2
39.8 2.265 3
42.9 2.108 3
43.4 2.085 4
47.6 1.910 3
49.0 1.859 5
49.8 1.831 3
50.6 1.804 3
51.0 1.791 4
53.2 1.722 3
54.7 1.678 2
(c) sample such as the CoAPSO-44 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes, and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic formwork agent that is present in the intracrystalline pore canal system at least; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", each molar fraction of " Z " expression expression, with reference to figure 1 or Fig. 2, above-mentioned " W " " X " " Y " " Z " has been defined; In former synthetic attitude or calcined state, have X-ray powder diffraction style feature: comprise the d-spacing that table four 13 is illustrated at least:
Table four 13
2 ν d(
) relative intensity
9.3-9.5 9.51-9.31 VS
16.0-16.3 5.54-5.44 W-m
20.5-20.8 4.33-4.27 m
24.3-25.1 3.66-3.548 W-m
25.8-26.2 3.453-3.401 W-m
30.7-31.1 2.912-2.876 VW-m
(d) hereto, the X light powder diffraction style of CoAPSO-44 composition obtains, and the feature of being represented by the X-ray powder diffraction style of table four 14:
Table four 14
2ν d（
） 100×I/I
0
4.8
＊18.41 8
8.9 9.94 20
9.3-9.5 9.51-9.31 100
12.9-13.1 6.86-6.76 22-24
13.7-14.0 6.46-6.33 5-6
15.8-15.9 5.61-5.57 Sh
16.0-16.3 5.54-5.44 14-37
17.4-17.8 5.10-4.98 5-18
18.9-19.1 4.70-4.65 4-9
20.5-20.8 4.33-4.27 40-72
21.8-22.1 4.08-4.02 4-17
22.3-22.7 3.99-3.92 4-9
23.0-23.1 3.87-3.85 7-9
24.3-25.1 3.66-3.548 12-49
25.8-26.2 3.453-3.401 13-31
27.6-27.8 3.232-3.209 3-11
28.2 3.164 4
29.0-29.5 3.079-3.028 Sh-3
29.7-30.6 3.008-2.921 8-21
30.7-31.1 2.912-2.876 4-49
31.6-31.7 2.831-3.823 3-4
32.2 2.780 2
32.5-33.7 2.755-2.660 3-6
34.5-34.8 2.600-2.578 5-8
35.4-36.2 2.536-2.481 5-9
38.2-38.6 2.356-2.332 2-5
38.7-39.3 2.327-2.292 2-3
39.8-40.0 2.265-2.254 Sh-3
42.2-42.9 2.141-2.108 3-5
43.4-43.7 2.085-2.071 3-4
44.4-46.2 2.040-1.965 3
47.3-47.6 1.922-1.910 3
48.1-49.0 1.892-1.859 5-12
49.8-50.3 1.831-1.814 3-15
50.6 1.804 3
51.0-52.0 1.791-1.759 4-5
53.2-53.8 1.722-1.704 3-9
54.7-54.8 1.678-1.675 2-3
Example 120
(a) utilize the CoAPSO-46 of x-ray analysis example 36 former synthetic attitudes.The CoAPSO-46 product has been represented feature by the X-ray powder diffraction style of following table 45:
Table four 15
2ν d（
） 100×I/I
0
6.6 13.39 11
6.9 12.81 7
7.2 12.28 12
7.7 11.48 100
12.5 7.08 7
13.1 6.76 5
13.3 6.66 6
13.5 6.56 4
15.0 5.91 4
15.4 5.75 5
16.1 5.51 3
16.8 5.28 6
17.4 5.10 4
17.5 5.07 5
19.9 4.46 5
20.6 4.31 5
21.0 4.23 4
21.4 4.15 Sh
21.7 4.10 13
22.2 4.00 3
22.9 3.88 7
23.8 3.74 4
24.3 3.66 5
26.3 3.389 3
26.9 3.314 7
27.8 3.209 10
28.3 3.153 5
28.8 3.010 6
29.9 2.988 4
30.2 2.959 4
30.7 2.912 4
30.9 2.894 4
31.2 2.867 5
31.8 2.814 3
33.0 2.714 4
34.2 2.622 3
36.0 2.495 5
36.6 2.455 3
44.0 2.058 3
(b) sample such as the CoAPSO-46 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes, and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic formwork agent that is present in the intracrystalline pore canal system at least, and " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", " Z " represent molar fraction, and with reference to figure 1 or Fig. 2, above-mentioned " W " " X " " Y " " Z " has been defined; In former synthetic attitude or calcined state, have X-ray powder diffraction style feature: comprise the d-spacing that table four 16 is illustrated at least:
Table four 16
2 ν d(
) relative intensity
6.5-6.7 13.60-13.19 W
7.2-7.4 12.28-11.95 W
7.6-7.8 11.63-11.33 VS
21.6-21.7 4.11-4.10 W
27.8-27.9 3.209-3.198 W
(c) hereto, the X light powder diffraction style of CoAPSO-46 composition obtains, and has represented feature by the X-ray powder diffraction style of table four 17:
Table four 17
2ν d（
） 100×I/I
0
6.5-6.7 13.60-13.19 11
6.9-7.0 12.81-12.63 7
7.2-7.4 12.28-11.95 12
7.6-7.8 11.63-11.33 100
12.5-12.6 7.08-7.03 7
13.1-13.3 6.76-6.66 5
13.5-13.9 6.56-6.37 4
15.0-15.1 5.91-5.87 4
15.4 5.75 5
16.1 5.51 3
16.7-16.8 5.31-5.28 6
17.4-17.5 5.10-5.07 4
19.9-20.0 4.46-4.44 5
20.5-20.6 4.33-4.31 5
21.0 4.23 4
21.4 4.15 Sh
21.6-21.7 4.11-4.10 13
22.1-22.2 4.02-4.00 3
22.8-22.9 3.90-3.88 7
23.8 3.74 4
24.2-24.3 3.68-3.66 5
26.3-26.4 3.389-3.376 3
26.8-26.9 3.326-3.314 7
27.8-27.9 3.209-3.198 10
28.3-28.4 3.153-3.143 5
28.8-28.9 3.010-3.089 6
29.8-29.9 2.998-2.988 4
30.2 2.959 4
30.7 2.912 4
30.9-31.0 2.894-2885 4
31.2-31.3 2.867-2.858 5
31.8-31.9 2.814-2.805 3
32.8-33.0 2.730-2.714 4
34.2-34.3 2.622-2.614 3
35.9-36.0 2.510-2.495 5
36.5-36.6 2.462-2.455 3
44.0-44.1 2.058-2.053 3
Example 121
(a) utilize the CoAPSO-47 of x-ray analysis example 104 former synthetic attitudes.The CoAPSO-47 product has been represented feature by the X-ray powder diffraction style of following table 48
Table four 18
2ν d（
） 100×I/I
0
9.4 9.37 94
12.9 6.88 16
13.8 6.40 9
16.0 5.55 40
17.5 5.06 14
18.9 4.69 6
20.6 4.32 100
21.8 4.08 11
22.4 3.97 4
23.0 3.87 12
24.6 3.62 38
25.9 3.443 22
27.6 3.230 11
29.5 3.030 6
30.6 2.926 42
31.5 2.844 3
33.1 2.707 3
34.5 2.602 9
35.7 2.518 7
38.4 2.345 4
39.6 2.275 4
42.5 2.128 4
47.6 1.910 4
48.5 1.877 11
50.3 1.815 7
52.3 1.749 2
53.2 1.721 5
53.9 1.700 3
54.3 1.690 3
(b) CoAPSO-47 of example 104 temperature with 500 ℃ in air was calcined 1.5 hours.Calcination product has been represented feature by the X-ray powder diffraction style of following table 49:
Table four 19
2ν d（
） 100×I/I
0
9.6 9.18 100
3.1 6.77 26
14.2 6.23 3
16.3 5.44 10
18.1 4.90 16
19.4 4.58 3
21.0 4.24 26
22.5 3.96 3
23.5 3.79 3
25.5 3.499 11
26.4 3.381 9
28.7 3.113 4
31.2 2.868 14
31.7 2.824 6
(c) sample such as the CoAPSO-47 in this name has one by CoO
2, AlO
2, PO
2And SiO
2Three-dimensional many microporous crystals skeleton structure that tetrahedron element constitutes, and the experience chemical composition of a moisture-free basis is arranged, express by following formula:
mR∶（Co
WAl
XP
YSi
Z）O
2
Wherein, " R " represents a kind of organic formwork agent that is present in the intracrystalline pore canal system at least; " m " represents every mole of (Co
WAl
XP
YSi
Z) O
2The mole number of " R ", it is worth approximately by 0 to 0.3; " W ", " X ", " Y ", " Z " represent molar fraction, with reference to figure 1 or Fig. 2, above-mentioned " W " " X " " Y " " Z " has been defined, and has X light powder diffraction style feature in former synthetic attitude or calcined state: comprise the d-spacing that table six 11 is illustrated at least:
Table six 11
2 θ d(
) relative intensity
9.4-9.6 9.41-9.21 VS
12.8-13.1 6.92-6.76 W-m
16.0-16.3 5.54-5.44 W-m
20.6-21.0 4.31-4.23 m-VS
25.5-25.9 3.493-3.440 W-m
30.6-31.1 2.921-2.876 W-m
(d) hereto, the X-ray powder diffraction style of CoAPSO-47 composition obtains, and has represented feature by the X-ray powder diffraction style of table six 12:
Table six 12
2θ d（
） 100×I/I
0
9.4-9.6 9.41-9.21 94-100
12.8-13.1 6.92-6.76 16-26
13.8-14.2 6.42-6.24 3-9
16.0-16.3 5.54-5.44 10-40
17.5-18.1 5.07-4.90 14-16
18.9-19.4 4.70-4.58 3-6
20.6-21.0 4.31-4.23 26-100
21.8 4.08 11
22.4-22.5 3.97-3.95 3-4
23.0-23.5 3.87-3.79 3-12
24.6 3.62 38
25.5-25.9 3.493-3.440 11-22
26.4 3.376 9
27.6 3.232 11
28.7 3.110 4
29.5 3.028 6
30.6-31.1 2.921-2.876 13-42
31.5-31.7 2.840-2.823 3-6
33.1 2.706 3
34.5 2.600 9
35.7 2.515 7
38.4 2.344 4
39.6 2.276 4
42.5 2.127 4
47.6 1.910 4
48.5 1.877 11
50.3 1.814 7
52.3 1.749 2
53.2 1.722 5
53.9 1.701 3
54.3 1.689 3
Example 122
In order to confirm the catalytic activity of CoAPSO composition, just doing-the cracking catalyst test of butane cracking with CoAPSO composition calcining sample.
Utilize mini-reactor just carrying out-butane cracking.Reactor is the Cylinder silica tube of long 254mm, internal diameter 10.3mm.Pack into the CoAPSO particle of 20-40 order (USS) of each test, reactor, weight is 0.5 to 5 gram, the selection of amount be under test conditions, just make-transformation efficiency of butane is at 5%-90%.In most of the cases, CoAPS calcining in advance in air to remove the organic substance in the microcellular system, activates 1 hour then in 500 ℃ helium flow in reactor.In some instances, sample is an incinerating in reactor, and former material is helium-just-butane mixture, wherein contain 0.02 mole just-butane, and pass through reactor with the speed of 50 milliliters of per minutes.Utilize gas chromatographic technique commonly used that reactor effluent and raw material are analyzed.Flowing out 10 minutes post analysis reactor effluents.
Calculated pseudo-first-order reaction velocity constant (K
A) determined the catalytic activity of CoAPSO composition, the K of the CoAPSO composition of acquisition
AValue (Cm
3/ gmin) be listed in the table below:
CoAPSO instance number velocity constant (K
A)
CoAPSO-11(example 50) 1.0
CoAPSO-11(example 42)
*2.0
CoAPSO-11(example 42) 1.9
CoAPSO-11(example 61) 1.4
CoAPSO-31(example 102) 2.1
CoAPSO-34(example 89)
*1.5
CoAPSO-34(example 89) 8.7
CoAPSO-34(example 90) 11.8
CoAPSO-34(example 83) 28.1
CoAPSO-34(example 77)
*11.1
CoAPSO-35(example 10)
*1.0
CoAPSO-44(example 19) 18.1
CoAPSO-46(example 36) 2.4
CoAPSO-47(example 104) 2.4
CoAPSO-44(example 19)
*2.7
CoAPSO-36(example 93)
*1.0
CoAPSO-34(example 83)
*4.1
CoAPSO-34(example 69)
*9.4
CoAPSO-34(example 79)
*5.2
CoAPSO-34(example 78)
*4.6
CoAPSO-34(example 81)
*3.3
*In helium, under 500 ℃ temperature, in reactor, calcined 2 hours before the activation.
Process application
In general, CoAPSO composition of the present invention has hydrophily and adsorbed water preferentially than the molecule of common hydrocarbon such as alkane, alkene and aromatic hydrocarbons (such as benzene, dimethylbenzene and isopropylbenzene). Therefore, CoAPSO (such as the drying of natural gas, drying of cracked gas) in adsorbing separation/purification process is a kind of useful drier. Water is adsorbed prior to so-called permanent gas (such as carbon dioxide, nitrogen, oxygen and hydrogen). Therefore, CoAPSO is applicable to drying, the oxygen of reburner hydrogen stream, the drying of nitrogen, perhaps the drying of air before the liquefaction.
CoAPSO composition of the present invention has also shown some surperficial selectivity characteristics, and these characteristics make them become useful as catalyst or catalyst base when some hydrocarbon conversion reactions and oxidizing fire react. The CoAPSO composition can have the metal of catalytic activity with method dipping well known in the art or load, and is used for the producing as basic catalyst composition take silica or aluminium oxide. In general type, when using as catalyst, be preferably the aperture greater than 4
Kind.
With the hydrocarbon conversion reactions of CoAPSO catalysis the alkylation of cracking, hydrocrack, fragrance and isoparaffin class is arranged, comprise isomerization, polymerization, reformation, hydrogenation, transalkylation, dealkylation, the hydrogenated ring-opened and dehydrocyclization of dimethylbenzene isomery.
When using the CoAPSO composition of containing hydrogenated promoter such as platinum or palladium, the raw material of heavy crude residue, ring-type raw material and other hydrogenatable cracking can be in 400 °F to 825 °F temperature range hydrocrack, the hydrogen that uses and the mol ratio of hydrocarbon are between 2 and 80, and pressure is (pound/inch between 10 and 3500 gauge pressures2), liquid hourly space velocity (LHSV) (LHSV) preferably selects 1.0 to 10 between 0.1 to 20.
The CoAPSO carbon monoxide-olefin polymeric that uses in hydrocrack also is applicable to reforming process, and in this process, hydrocarbon material contacts with catalyst in about 700 °F to 1000 °F temperature, hydrogen pressure from 100 to 500 gauge pressure (pound/inch2), the liquid hourly space velocity (LHSV) value is in 0.1 to 10 scope, and the mol ratio of hydrogen and hydrocarbon is preferably between 4 and 12 in 1 to 20 scope.
Same catalyst namely contains the catalyst of hydrogenation promoter, equally also is useful in hydroisomerization process, and in this process, raw material such as normal paraffin hydrocarbons are converted into saturated branched chain isomer. Carry out the temperature of hydrogenation isomerization about 200 °F to 600 °F, be preferably between 300 °F to 550 °F, liquid hourly space velocity (LHSV) value approximately from 0.2 to 1.0. Be used in the mol ratio (hydrogen is than hydrocarbon) of the interior hydrogen that mixes of reactor and hydrocarbon material between 1 and 5.
In slightly high temperature, for example, from 650 °F to 1000 °F, preferably select 850 °F to 950 ℃, usually at low-pressure slightly, in about 15 to 50 gauge pressure (pound/inch) scopes, same carbon monoxide-olefin polymeric is used for the isomerization normal paraffin hydrocarbons, preferably selects to contain the normal paraffin hydrocarbons of 7-20 carbon atom as paraffinic feed. Usually be short the time of contact of raw material and catalyst, and to avoid undesirable side reaction such as olefin polymerization and alkane cracking, the liquid hourly space velocity (LHSV) value exists 0.1 to 10 scope, preferably select 1.0 to 6.0.
The space of the unique crystal structures of CoAPSO catalyst of the present invention and fully alkali metal-free filling helps to utilize the conversion at alkyl aromatic, is particularly conducive to toluene, ethene, trimethylbenzene, the catalytic disproportionation of durol etc. In dismutation, isomerization and transalkylation also can take place simultaneously. Select separately the 8th noble metal that belongs to or select such as tungsten, molybdenum and chromium together with the 6th subgroup metal, its content accounts for the 3%-15%(percetage by weight of carbon monoxide-olefin polymeric total amount). Can add the hydrogen (but not needing) that adds at conversion zone, the temperature of conversion zone remains on 400 to 750 °F approximately, and pressure is in 100 to 2000 gauge pressure (pound/inch) scopes, and the liquid hourly space velocity (LHSV) value is in 0.1 to 15 scope. Utilize CoAPSO composition (depitching natural oil etc. is very desirable product with gasoline for the raw material of utilization such as gas-oil, heavy crude) optionally to carry out catalytic pyrolysis. Temperature is between 850 to 1100 °F, and the liquid hourly space velocity (LHSV) value is between 0.5 to 10, and pressure is between 0 to 50 gauge pressure (pound/inch).
The alkane hydrocarbon material has been used in the dehydrocyclization reaction, preferably selects the normal paraffin hydrocarbons more than 6 carbon atoms, utilizes with the essentially identical reaction condition reaction of catalytic pyrolysis and has formed benzene, two-toluene, toluene etc. For these reactions, together with the 8th noble metal anion that belongs to such as cobalt and nickel choice for use the CoAPSO catalyst.
In the catalytic dealkylation reaction, alkane side chain on the aromatic rings of wishing to split, and main be not the hydrogenated aromatic ring structure. The relevant temperature of using is between 800 °-1000 °F, and the hydrogen pressure of appropriateness is between 300-1000 gauge pressure (pound/inch), and other reaction condition is similar to the reaction condition of above-mentioned catalytic pyrolysis. What the catalyst of selecting and above-mentioned catalytic dehydrogenation reaction were used is identical. Especially desirable desirable dealkylation comprising, methyl naphthalene becomes the conversion of naphthalene, toluene and/or two-toluene become the conversion of benzene.
In Hydrobon, initial target is the selection that promotes the hydrocrack of in raw material organic sulfur and/or nitrogen. And therein main be not to affect hydrocarbon molecules. In order to reach this purpose, the choice for use condition identical with above-mentioned catalytic pyrolysis usually, and usually select with The identical catalyst of the dehydrocyclization character of operation of foregoing description. Raw material comprises gasoline fraction, kerosene, airborne vehicle fuel fraction, and the automotive fuel cut, light diesel and heavy diesel, depitching natural oil etc., wherein any raw material all can contain the sulphur of about weight percentage 5% and 3% nitrogen at the most.
Can use similar condition to reach hydrorefined purpose, for example, organic nitrogen and the organic sulfur of the more hydrocarbon material that comprises organic nitrogen and organosulfur compound ratio. It has been generally acknowledged that the more existence of this composition has suppressed the effect of hydrocracking catalyst significantly. Thereby when wishing that organic nitrogen raw material per pass obtains to utilize the desired hydrocrack transforming degree of nitrogen-containing compound raw material still less identical, operation is essential under very rare condition. So, under this condition, denitrogenation, desulfurization and/or hydrocrack can the most promptly be finished, and the characteristic of raw material must determine the operating condition that provides. The concentration of organic nitrogen in the raw material particularly. Because the result of organonitrogen compound hydrogenolytic cleavage, be best suited for as can be known the condition of the denitrogenation of the high raw material of organic nitrogen content, may not be worthless, and MIN hydrocrack also can be selected, make and contain lower hydrocrack when remaking raw material and suppress the concentration that forms. For example, organonitrogen compound. Therefore, on the basis of primary screening test, special catalyst and the supply of raw material quantitative also are in contact with one another, and each condition of setting up has in this article become reality.
Utilize acid slightly big catalyst, carried out isomerization reaction under the condition of above-mentioned reformation being similar to. Alkene is preferably in 500 °-900 °F and carries out isomerization, and alkane, cycloalkane and alkyl aromatic carry out isomery at 700 °-1000 °F and turn to. Especially desirable desirable isomerization reaction comprising: just-heptene and/or just-octane becomes different-heptene, the conversion of different-octane. Butane becomes different-butane, methyl cyclopentane becomes cyclohexane ,-dimethylbenzene and/or ortho-xylene become right-dimethylbenzene, and the 1-butylene becomes 2-butylene and/or isobutene, just-and hexene becomes different-hexene, and cyclohexene becomes methyl cyclopentene etc. Better the form of catalyst is polyvalent metal compounds (such as the sulfide) combination the metal of CoAPSO and second main group and second subgroup and rare metal. For alkylation and dealkylation, selected to have at least 5
The CoAPSO composition of micropore. When being used for the dealkylation of alkyl aromatic, temperature Usually be controlled at 350 °F and the temperature when mainly being raw material or conversion product generation cracking, usually approximately high to 700 °F. Preferably select temperature at 450 °F to the critical-temperature that is not more than the compound that carries out dealkylation. The pressure condition of using will make aroamtic hydrocarbon raw material exist with liquid state at least. Can be low to moderate 250 °F if alkyl replaces temperature, but preferably select to be not less than 350 °F. At benzene, in the alkylated reaction of toluene and dimethylbenzene, alkylating agent is alkene such as ethene and propylene preferably.
Claims (9)
1, a kind of preparation method of crystal form molecular sieve, this crystal form molecular sieve has CoO
2, AlO
2,
PO
2And SiO
2The three-dimensional micropore framework structure of tetrahedron element, the chemical constitution empirical formula of its anhydrous state is:
mR：(Co
wAl
xP
ySi
z)O
2
" R " representative at least one organic formwork agent in the micropore system in crystal in the formula; " m " represents every mole of (Co
wAl
xP
ySi
z) O
2In the molar weight of " R ", its value is 0 to 0.3;
" w ", " x ", " y " and " z " represent the molar fraction of cobalt, aluminium, phosphorus and silicon respectively and represent with the tetrahedral oxide form, said molar fraction is within the area formed of the pentagon that limited by A, B, C, D and E each point in accompanying drawing 1, it is characterized in that this method comprises heated under 50-250 ℃ temperature 2 hours to 30 days containing the reaction mixture that the reaction source of cobalt, aluminium, phosphorus and silicon and one or more organic formwork agents form, through hydrothermal crystallization, to produce the crystal form molecular sieve; Reaction mixture (representing) composed as follows with oxide mol ratio:
aR：(Co
wAl
xP
ySi
z)∶bH
2O
" R " is organic formwork agent in the formula; A is the amount of " R ", and its value is by greater than 0 to 6; The value of b is about 2 to 300; " w ", " x ", " y " and " z " represent (Co respectively
wAl
xP
ySi
z) O
2The molar fraction of the cobalt in the composition, aluminium, phosphorus and silicon, its value are within the area formed of the pentagon that limited by F, G, H, I and J each point in accompanying drawing 3.
2, the described method of claim 1, wherein the source of the phosphorus in the reaction mixture is ortho-phosphoric acid.
3, the described method of claim 1, wherein the source of phosphorus is an at least a compound in the compound at least a this group of alkoxide that is selected from pseudobochmite and aluminium for the source of ortho-phosphoric acid aluminium in the reaction mixture.
4, the described method of claim 3, wherein the alkoxide of aluminium is an aluminium isopropoxide.
5, the described method of claim 1, wherein the source of silicon is a silicon-dioxide.
6, the described method of claim 1, wherein cobalt salt is Cobaltous diacetate (II) or rose vitriol (II).
7, the described method of claim 1, wherein organic formwork agent is quaternary ammonium or quaternary compound, its chemical formula is:
R
4X
+
X wherein is nitrogen or phosphorus, and each R is the alkyl or aryl that contains 1 to 8 carbon atom simultaneously.
8, the described method of claim 1, organic formwork agent wherein is a kind of amine.
9, claim 1 or 2 described methods, organic formwork agent wherein is selected from the compound group by following material, the tetrapropyl ammonium ion, the tetraethyl ammonium ion, tripropyl amine, triethylamine, trolamine, piperidines, hexahydroaniline, the 2-picoline, N, N-diformazan benzylamine, N, the N-dimethylethanolamine, choline, N, the 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, 1, tetramethyleneimine, 2-imidazolone and polyquaternium [(C
14H
32N
2) (OH)
2]
x(value of x is at least 2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103238 CN1011222B (en) | 1985-04-27 | 1985-04-27 | Cobalt-aluminium-phosphorus-silicon-oxide molecular sieve composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103238 CN1011222B (en) | 1985-04-27 | 1985-04-27 | Cobalt-aluminium-phosphorus-silicon-oxide molecular sieve composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103238A CN85103238A (en) | 1986-10-29 |
| CN1011222B true CN1011222B (en) | 1991-01-16 |
Family
ID=4793053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103238 Expired CN1011222B (en) | 1985-04-27 | 1985-04-27 | Cobalt-aluminium-phosphorus-silicon-oxide molecular sieve composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011222B (en) |
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| WO2014085279A1 (en) * | 2012-11-30 | 2014-06-05 | Uop Llc | Metallophosphate molecular sieves, method of preparation and use |
| GB2551623A (en) * | 2016-04-22 | 2017-12-27 | Johnson Matthey Plc | Methods of producing SAPO-56, an AFX-containing molecular sieve |
| CN117342572B (en) * | 2023-12-05 | 2024-02-13 | 内蒙古工业大学 | Preparation method and application of magnetic cobalt phosphate molecular sieve |
-
1985
- 1985-04-27 CN CN 85103238 patent/CN1011222B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85103238A (en) | 1986-10-29 |
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