CN100418880C - Molecular sieve with AWO structure and its synthesizing process - Google Patents

Molecular sieve with AWO structure and its synthesizing process Download PDF

Info

Publication number
CN100418880C
CN100418880C CNB2004100693340A CN200410069334A CN100418880C CN 100418880 C CN100418880 C CN 100418880C CN B2004100693340 A CNB2004100693340 A CN B2004100693340A CN 200410069334 A CN200410069334 A CN 200410069334A CN 100418880 C CN100418880 C CN 100418880C
Authority
CN
China
Prior art keywords
molecular sieve
template
crystallization
diethanolamine
source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CNB2004100693340A
Other languages
Chinese (zh)
Other versions
CN1724357A (en
Inventor
方文秀
张凤美
罗一斌
舒兴田
何鸣元
荆世梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CNB2004100693340A priority Critical patent/CN100418880C/en
Publication of CN1724357A publication Critical patent/CN1724357A/en
Application granted granted Critical
Publication of CN100418880C publication Critical patent/CN100418880C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention relates to a molecular sieve with AWO structure. An anhydrous chemical composition formula represented by the mole ratio of oxide is aR: Al2O3: bP2O5: cSiO2, wherein R is a template agent of ethanolamine and/or diethanolamine, a=0.01-0.25, b=0.6-1.0, and c=0-1.1. A method for synthesizing the molecular sieve comprises: an aluminum source, a phosphorus source, a silicon source and water are formed into gel at 0 to 80 DEG C in the presence of the template agent of ethanolamine and/or diethanolamine, the gel is crystallized under autogenous pressure and at 120 to 220 DEG C for 4 to 60 hours, and crystallized products are filtered, washed and dried. After the molecular sieve is calcined to remove amine, a molecular sieve with ATV structure can be obtained. The method for synthesizing the molecular sieve has the characteristics of convenience, low cost of raw material and high yield.

Description

A kind of molecular sieve and synthetic method thereof with AWO structure
Technical field
The invention relates to a kind of molecular sieve and synthetic method thereof of aluminum phosphate class.Specifically, the invention relates to AlPO with AWO structure 4-21, SAPO-21 molecular sieve and their synthetic method.
Technical background
Aluminium phosphate molecular sieve is after al silicate molecular sieve, and the class novel molecular sieve that U.S. UCC company develops at early eighties (USP 4,310, and 440; USP 4,385, and 994).The characteristics of this molecular sieve analog are that its skeleton alternately is formed by connecting by phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, because framework of molecular sieve is electric neutrality, therefore do not have cation exchange property and catalytic perfomance.
AlPO 4-21 and SAPO-21 be the typical case representative that does not contain the heteroatomic AWO of having structure molecular screen.The former skeleton is AlO 4Tetrahedron and PO 4The octatomic ring duct that tetrahedron is formed; The latter's skeleton then is AlO 4Tetrahedron, PO 4Tetrahedron and SiO 4The octatomic ring duct that tetrahedron is formed because they have identical skeleton structure, thereby has essentially identical XRD spectra.On the other hand, owing to have template in the AWO molecular sieve structure, thereby diffraction peak position and the diffracted intensity in the resulting XRD spectra all can change when adopting different template synthetic, promptly can obtain different XRD spectra this moment.Table 1 has been listed at USP 4,310,440 and USP 4,385,994 in that provide is template synthetic AlPO with the tetramethyleneimine 4The XRD spectra of-21 molecular sieves.Table 2 has been listed CA 2,104,052 and JP 6,171,926 in what provide is the XRD spectra of template synthetic SAPO-21 molecular sieve with the tetramethyleneimine.
Has the AWO structure molecular screen just can obtain having the ATV structure after roasting molecular sieve.AlPO 4-21 and SAPO 4-21 can to obtain the aperture respectively after amine is taken off in roasting be 3.0 * 4.9
Figure C20041006933400041
AlPO 4-25 and the SAPO-25 molecular sieve.Table 3 has been listed at USP 4,310,440 and USP 4,385,994 in the AlPO that provides 4The typical XRD spectra of-25 molecular sieves.Owing to do not have template in the ATV structure molecular screen, so its XRD spectra is subjected to when synthetic the influence of template used dose of kind less relatively.
AlPO among table 1 USP 4,385,994 4-21 XRD spectra data
Figure C20041006933400051
Figure C20041006933400061
The XRD spectra data of SAPO-21 among table 2 CA 2,104,052 and the JP 6,171,926
AlPO among table 3 USP 4,385,994 4-25 typical XRD spectra data
USP 4,385, the AlPO of report in 994 4The hydrothermal crystallizing synthesis method of-21 molecular sieves, wherein the template of Cai Yonging is tetramethyleneimine, Trimethylamine, 1,4-lupetazin, 3-di-n-butyl amido-propylamine, N, N, N ', N '-tetramethyl--1,3-propylene diamine, N, N-dimethylethanolamine, Tri N-Propyl Amine, N, N, N ', N '-Tetramethyl Ethylene Diamine, Mono Methyl Ethanol Amine or their mixture, these template exist problems such as price height, toxicity are big, contaminate environment.
Reported with the trolamine to be that template synthesizes the AlPO with AWO structure in petroleum journal (refining of petroleum) the 5th volume, the 3rd phase 114-121 page or leaf 4-21 molecular sieves, but because this template all has guidance quality to multiple differing molecular sieve, so the AlPO that synthesizes 4-21 molecular sieves have numerous Al PO 4The association phase of-5 molecular sieves.
J.Chem.Soc., Chem.Commun., 10, reported AlPO among the 783-784 4The anhydrous synthetic method of-21 molecular sieves is to be template, to be the organic solvent synthetic with ethylene glycol, butanols with dimethylamine or ethamine.The organic amine that this method is used is too much, cost is high, pollution is big.
J.Mater.Chem.8 (12) has reported AlPO among the 2827-2830 4The synthetic method of-21 molecular sieves, the template of use is a Tri N-Propyl Amine.This method exists cost height, heavy-polluted problem equally.
Up to now, at synthetic AlPO with AWO structure 4-21, in the method for SAPO-21 molecular sieve, never seeing has the report that adopts the template that other is cheap, toxicity is little.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art, to provide a kind of molecular sieve that contains the different templates agent, and use the method for cheap amine as synthetic this molecular sieve of template with AWO structure.
The anhydrous chemical constitution formula that the molecular sieve of the AWO of having structure provided by the invention is represented with the molar fraction of oxide compound is:
aR∶Al 2O 3∶bP 2O 5∶cSiO 2
In the formula: R is template thanomin and/or the diethanolamine that is present in the molecular sieve crystal duct, and a is the molar fraction of template R, a=0.01～0.25; B and c are respectively P 2O 5And SiO 2Molar fraction, b=0.6～1.0, c=0～1.1.
This molecular sieve has XRD spectra as shown in table 4.
The table 4 XRD spectra data with AWO structure molecular screen provided by the invention
Figure C20041006933400091
*vs：＞90～100％；s：70～90％；m：20～70％；w：10～20％
In method provided by the invention, will be with AlPO 4-21, SAPO-21 is the synthetic method of typical case's representative explanation AWO structure molecular screen.
The synthetic method of the AWO of having structure molecular screen provided by the invention comprises: make aluminium source, phosphorus source, silicon source, water in the presence of thanomin and/or diethanolamine template, form gel down at 0～80 ℃; Autogenous pressure, 120～220 ℃ of following crystallization 4～60 hours; Crystallization product after filtration, washing and dry.
Specifically, the synthetic method of the molecular sieve of the AWO of having structure provided by the invention may further comprise the steps:
(a) become glue: aluminium source, phosphorus source, template, silicon source and water are mixed, form gel down at 0～80 ℃, the mixture gel has the following composition of expressing by the oxide molar mark:
aR∶Al 2O 3∶bP 2O 5∶cSiO 2∶dH 2O
Wherein R is the organic formwork agent that is selected from thanomin and/or diethanolamine, and a is the molar fraction of template R, and the value of a is with respect to every mole of Al 2O 3Be 0.2～2.0, preferred value is 0.3～1.5, and more preferably value is 0.5～1.0.
Aluminium source wherein is selected from pseudo-boehmite or aluminum isopropylate.
Phosphorus source wherein is a phosphoric acid, and b is the molar fraction in phosphorus source, and it is worth with respect to every mole of Al 2O 3Be advisable with 0.6～1.4, preferred value is 0.8～1.1, and more preferably value is 0.9～1.0.
Silicon source wherein is inorganic silicon colloidal sol or organic silicone grease, and c is the molar fraction in silicon source, and its value is 0～1.1, and preferred value is 0～0.8, and more preferably value is 0～0.6.
The molar fraction value d of water is with respect to every mole of Al 2O 3Be 15～80, preferred value is 20～70, and more preferably value is 22～65.
The addition sequence of each raw material can be any when becoming glue, for example: aluminium source, template, silicon source can be added phosphate aqueous solution successively; Perhaps, add template, silicon source more successively earlier with behind aluminium source and the phosphate aqueous solution thorough mixing; Perhaps, add silicon source, template more successively earlier with behind aluminium source and the phosphate aqueous solution thorough mixing; Perhaps, add the silicon source and continue thorough mixing, add template at last more earlier with behind aluminium source and the phosphate aqueous solution thorough mixing; After perhaps aluminium source, silicon source, template and phosphoric acid solution being mixed into glue, add entry at last again.
In becoming the glue process, water both can add separately, also portion water can be mixed with some kinds of raw materials in advance.
Becoming the glue temperature is 0～80 ℃, preferred 5～70 ℃, and more preferably 10～60 ℃
(b) crystallization: the said mixture gel is placed in the crystallizing kettle, and crystallization is 4～60 hours under autogenous pressure, and crystallization temperature is 120～220 ℃, and preferred 130～210 ℃, more preferably 140～200 ℃.
(c) crystallization product after filtration, washing, drying, promptly obtain having the molecular sieve of AWO structure.
Promptly change AWO structure molecular screen provided by the invention crystalline phase after amine is taken off in roasting into the ATV structure, specifically, have the AlPO of AWO structure 4-21 and SAPO 4-21 molecular sieves just can correspondingly obtain having the AlPO of ATV structure after roasting 4-25 and the SAPO-25 molecular sieve.Roasting can be carried out under 450～650 ℃, preferred 500～600 ℃ 1～5 hour, preferred 2～3 hours.
It is the molecular sieve of the synthetic AWO structure of template that method provided by the invention has adopted cheap, avirulent thanomin and/or diethanolamine, and simple synthetic method, raw materials cost is low, yield is high.
Embodiment
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Used in an embodiment all ingredients and chemical specification are as follows:
Phosphoric acid: analytical pure or chemical pure, H 3PO 4Content 85.0%, the Beijing Chemical Plant produces.
Hydrated aluminum oxide: Industrial products, Al 2O 3Content is more than 73.2%, and Chang Ling, Hunan catalyst plant is produced.
Aluminum isopropylate: analytical pure, content 〉=99.5%, east, Beijing ring amalgamation plant produced.
Silicon sol: Industrial products, SiO 2Content 25%, Haiyang Chemical Plant, Qingdao produces.
Tetraethoxysilance: analytical pure, SiO 2Content 〉=28.8%.
Thanomin: analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces.
Diethanolamine: analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces.
Trolamine: analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces.
Embodiment 1
The present embodiment explanation is the synthetic SAPO-21 molecular sieve with AWO structure provided by the invention of template with the thanomin.
With 46.2 gram phosphoric acid (H 3PO 4Content 85%) and 144.0 gram deionized waters join and be placed in 30 ℃ of colloid generating kettles in the water-bath, add 27.9 gram pseudo-boehmite (Al after the mixing and stirring 2O 3Content 73.2%), mix, 12.2 gram thanomins are joined in the colloid generating kettle again, the back of waiting to stir adds 14.4 gram silicon sol (SiO 2Content 25.0%), fully gel is made in stirring.The composition of the gel that makes is expressed as with oxide form:
1.0R∶1.0Al 2O 3∶1.0P 2O 5∶0.3SiO 2∶50H 2O
R is the organic formwork agent thanomin in the formula.
The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 20 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.21R: Al 2O 3: 0.88P 2O 5: 0.28SiO 2
The X-ray powder diffraction of this crystallization product the results are shown in table 5, and it meets table 4 column data.
Table 5
Figure C20041006933400121
Figure C20041006933400131
Embodiment 2
The present embodiment explanation is the synthetic SAPO-21 molecular sieve with AWO structure provided by the invention of template with the thanomin.
With 462 gram phosphoric acid (H 3PO 4Content 85%) and 1440 gram deionized waters join and be placed in 30 ℃ of colloid generating kettles in the water-bath, add 279 gram pseudo-boehmite (Al after the mixing and stirring 2O 3Content 73.2%), mix, 122 gram thanomins are joined in the colloid generating kettle, the back of waiting to stir adds 192 gram silicon sol (SiO 2Content 25.0%), fully gel is made in stirring.The composition of the gel that makes is expressed as with oxide form:
1.0R∶1.0Al 2O 3∶1.0P 2O 5∶0.4SiO 2∶50H 2O
Wherein R is the organic formwork agent thanomin.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 30 hours under 165 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.19R: Al 2O 3: 0.84P 2O 5: 0.37SiO 2
The X-ray powder diffraction result of this crystallization product meets table 4 column data.
Embodiment 3
The present embodiment explanation is the synthetic SAPO-21 molecular sieve with AWO structure provided by the invention of template with the thanomin.
With 36.9 gram phosphoric acid (H 3PO 4Content 85%) and 110 gram deionized waters join and be placed in 70 ℃ of colloid generating kettles in the water-bath, add 27.9 gram pseudo-boehmite (Al after the mixing and stirring 2O 3Content 73.2%), mix, add 57 gram deionized water and stirring again and mix, 9.8 gram thanomins are joined in the colloid generating kettle, the back of waiting to stir adds 8.57 gram tetraethoxy (SiO 2Content 28.0%), fully gel is made in stirring.The composition of the gel that makes is expressed as with oxide form:
0.8R∶1.0Al 2O 3∶0.8P 2O 5∶0.2SiO 2∶50H 2O
Wherein R is the organic formwork agent thanomin.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 170 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.16R: Al 2O 3: 0.78P 2O 5: 0.19SiO 2
The X-ray powder diffraction result of this crystallization product meets table 4 column data.
Embodiment 4
The present embodiment explanation is the synthetic SAPO-21 molecular sieve with AWO structure provided by the invention of template with the thanomin.
With 46.2 gram phosphoric acid (H 3PO 4Content 85%), 115.8 gram deionized waters, 90.8 gram aluminum isopropylates, 12.2 gram thanomins, 19.2 gram silicon sol (SiO 2Content 25.0%) join together and be placed in 0 ℃ of colloid generating kettle in the ice-water bath, mix and fully stir and make gel.The composition of the gel that makes is expressed as with oxide form:
1.0R∶1.0Al 2O 3∶1.0P 2O 5∶0.4SiO 2∶40H 2O
Wherein R is the organic formwork agent thanomin.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 48 hours under 150 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.25R: Al 2O 3: 0.78P 2O 5: 0.38SiO 2
The X-ray powder diffraction result of this crystallization product meets table 4 column data.
Embodiment 5
The present embodiment explanation is the synthetic AlPO with AWO structure provided by the invention of template with the thanomin 4-21 molecular sieves.
With 46.2 gram phosphoric acid (H 3PO 4Content 85%) and 147.7 gram deionized waters join and be placed in 35 ℃ of colloid generating kettles in the water-bath, add 27.9 gram pseudo-boehmite (Al after the mixing and stirring 2O 3Content 73.2%), mix, again 12.2 gram thanomins are joined in the colloid generating kettle, fully stir and make gel.The composition of the gel that makes is expressed as with oxide form:
1.0R∶1.0Al 2O 3∶1.0P 2O 5∶45H 2O
Wherein R is the organic formwork agent thanomin.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 16 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.19R: Al 2O 3: 0.99P 2O 5
The X-ray powder diffraction of this crystallization product the results are shown in table 6, and it meets table 4 column data.
Table 6
Figure C20041006933400151
Comparative Examples 1
This Comparative Examples explanation according to the immediate prior art of the present invention, promptly be the synthetic AlPO of template with AWO structure with the trolamine 4The situation of-21 molecular sieves.
Synthetic according to method described in petroleum journal (refining of petroleum) the 5th volume, the 3rd phase 114-121 page or leaf:
With 46.2 gram phosphoric acid (H 3PO 4Content 85%) and 129.6 gram deionized waters join in the colloid generating kettle and to add 27.9 gram hydrated aluminum oxide (Al after the mixing and stirring 2O 3Content 73.2%), mix.Again 29.8 gram trolamines are joined fully to stir in the colloid generating kettle and make gel.The composition of the gel that makes is expressed as with oxide form: 1.0R: 1.0Al 2O 3: 1.0P 2O 5: 40H 2O
R in the formula is the organic formwork agent trolamine.
The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 48 hours under 150 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
The X-ray powder diffraction result of this crystallization product had not both met the listed AlPO of table 1 4-21 data are compared with table 4, table 6 column data simultaneously and are also existed tangible difference, wherein exist a large amount of AlPO 4-5 association phases.
Embodiment 6
The present embodiment explanation is the synthetic SAPO-21 molecular sieve with AWO structure provided by the invention of template with the diethanolamine.
With 27.8 gram phosphoric acid (H 3PO 4Content 85%) and 100 gram deionized waters join in the colloid generating kettle under the room temperature, add 27.9 gram pseudo-boehmite (Al after the mixing and stirring 2O 3Content 73.2%), mix, 14.7 gram diethanolamine are joined in the colloid generating kettle again, the back of waiting to stir adds 19.2 gram silicon sol (SiO 2Content 25.0%), fully gel is made in stirring.The composition of the gel that makes is expressed as with oxide form:
0.7R∶1.0Al 2O 3∶0.6P 2O 5∶0.4SiO 2∶35H 2O
Wherein R is the organic formwork agent diethanolamine.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 20 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.20R: Al 2O 3: 0.57P 2O 5: 0.33SiO 2
The X-ray powder diffraction result of this crystallization product meets the listed effect certificate of table 4.
Embodiment 7
The present embodiment explanation is the synthetic SAPO-21 molecular sieve with AWO structure provided by the invention of template with thanomin-diethanolamine mixture.
With 46.2 gram phosphoric acid (H 3PO 4Content 85%) and 108.4 gram deionized waters join and be placed in 35 ℃ of colloid generating kettles in the water-bath, add 27.9 gram pseudo-boehmite (Al after the mixing and stirring 2O 3Content 73.2%), mix, again 6.1 gram thanomins, 10.5 gram diethanolamine are joined in the colloid generating kettle and stir, at last with 19.2 gram silicon sol (SiO 2Content 25.0%) join in the colloid generating kettle and to mix and fully stir and make gel.The composition of the gel that makes is expressed as with oxide form:
1.0R∶1.0Al 2O 3∶1.0P 2O 5∶0.4SiO 2∶40H 2O
Wherein R is the mixture of organic formwork agent thanomin and diethanolamine.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get zeolite product.
Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.12R: Al 2O 3: 0.74P 2O 5: 0.37SiO 2
The X-ray powder diffraction result of this crystallization product meets table 4 column data.
Embodiment 8～14
These embodiment illustrate that the molecular sieve of the AWO of having structure provided by the invention can obtain having the molecular sieve of ATV structure after roasting.
With the 570 ℃ of following roastings 2 hours in air atmosphere of the AWO molecular sieve of embodiment 1～7 gained, obtain the molecular sieve behind the removed template method.
Record the anhydrous chemical constitution formula that the molar fraction with oxide compound of these molecular sieves represents with the X-ray fluorescent method and list in table 7.
Table 7
Figure C20041006933400181
Figure C20041006933400191
The BET specific surface that is recorded them by low-temperature nitrogen adsorption method is 170～190m2/g, and total pore volume is 0.28～0.35ml/g.
List in table 8 by the XRD structure spectral data that takes off the amine molecule sieve that each embodiment obtains.This result conforms to institute's column data in the table 3, illustrates that the gained molecular sieve has the ATV structure.
Table 8
Embodiment 15
The catalytic activity that the molecular sieve of the present embodiment explanation AWO of having structure provided by the invention obtains after roasting with ATV structure molecular screen.
With the 570 ℃ of following roastings 2 hours in air atmosphere of the AWO molecular sieve of embodiment 2 gained, obtain the molecular sieve behind the removed template method, through compressing tablet, fragmentation, make 20～40 order particles.With methyl alcohol is probe, and hydrogen is carrier gas, and through the pulse micro anti-evaluation, its transformation efficiency is 68.1% under 500 ℃, ethylene selectivity 16.0%, and propylene selectivity 28.1%, dme selectivity are 12.5%.

Claims (10)

1. molecular sieve with AWO structure, the anhydrous chemical constitution formula of representing with the molar fraction of oxide compound is: aR:Al 2O 3: bP 2O 5: cSiO 2In the formula: R is thanomin and/or diethanolamine template, a=0.01～0.25, b=0.6～1.0, c=0～1.1.
2. according to the molecular sieve of claim 1, it has following x-ray diffraction spectra:
3. the synthetic method of claim 1 molecular sieve comprises: make aluminium source, phosphorus source, silicon source, water in the presence of thanomin and/or diethanolamine template, form gel down at 0～80 ℃; Autogenous pressure, 120～220 ℃ of following crystallization 4～60 hours; Crystallization product after filtration, washing and dry.
4. according to the method for claim 3, wherein gel mixture has the following composition of expressing by the oxide molar mark: aR:Al 2O 3: bP 2O 5: cSiO 2: dH 2R is the organic formwork agent that is selected from thanomin and/or diethanolamine in the O formula, a=0.2～2.0; The aluminium source is selected from pseudo-boehmite or aluminum isopropylate; The phosphorus source is a phosphoric acid, b=0.6～1.4; The silicon source is inorganic silicon colloidal sol or organic silicone grease, c=0～1.1; Molar fraction value d=15～80 of water.
5. according to the method for claim 4, the molar fraction a=0.3 of said each component～1.5 wherein; B=0.8～1.1; C=0～0.8; D=20～70.
6. according to the method for claim 5, the molar fraction a=0.5 of said each component～1.0 wherein; B=0.9～1.0; C=0～0.6; D=22～65.
7. according to the method for claim 3, wherein said one-tenth glue carries out under 5～70 ℃.
8. according to the method for claim 7, wherein said one-tenth glue carries out under 10～60 ℃.
9. according to the method for claim 3, wherein said crystallization is carried out under 130～210 ℃.
10. according to the method for claim 9, wherein said crystallization is carried out under 140～200 ℃.
CNB2004100693340A 2004-07-19 2004-07-19 Molecular sieve with AWO structure and its synthesizing process Active CN100418880C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100693340A CN100418880C (en) 2004-07-19 2004-07-19 Molecular sieve with AWO structure and its synthesizing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100693340A CN100418880C (en) 2004-07-19 2004-07-19 Molecular sieve with AWO structure and its synthesizing process

Publications (2)

Publication Number Publication Date
CN1724357A CN1724357A (en) 2006-01-25
CN100418880C true CN100418880C (en) 2008-09-17

Family

ID=35924013

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100693340A Active CN100418880C (en) 2004-07-19 2004-07-19 Molecular sieve with AWO structure and its synthesizing process

Country Status (1)

Country Link
CN (1) CN100418880C (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
CN1308019A (en) * 1999-12-30 2001-08-15 中国科学院大连化学物理研究所 Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process
US6620983B1 (en) * 2002-06-12 2003-09-16 Exxonmobil Chemical Patents Inc. Synthesis of aluminophosphates and silicoaluminophosphates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
CN1308019A (en) * 1999-12-30 2001-08-15 中国科学院大连化学物理研究所 Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process
US6620983B1 (en) * 2002-06-12 2003-09-16 Exxonmobil Chemical Patents Inc. Synthesis of aluminophosphates and silicoaluminophosphates

Also Published As

Publication number Publication date
CN1724357A (en) 2006-01-25

Similar Documents

Publication Publication Date Title
JP6517001B2 (en) Titanium silicate molecular sieve and its synthesis
EP2753579B1 (en) Synthesis of zeolitic materials using n,n-dimethyl organotemplates
CN103025658B (en) The manufacture method of zeolite
JP6591740B2 (en) Complete Si molecular sieve and synthesis method thereof
FR2918050A1 (en) IZM-2 CRYSTALLIZED SOLID AND PROCESS FOR PREPARING THE SAME
WO2012071889A1 (en) Method for synthesizing sapo-34 molecular sieve with low silicon content
US20060147364A1 (en) Process for synthesising porous crystalline aluminophosphate molecular sieves
CN109626394B (en) Method for preparing SAPO-35 molecular sieve by using N-methylpiperidine as template agent
JPH10507730A (en) Synthesis of new molecular sieve using metal complex as template
Davis et al. Synthesis of aluminophosphate and element substituted aluminophosphate VPI-5
EP1683761B1 (en) Novel method for the synthesis of zeolite ZBM-30 from a mixture of amine compounds
WO2016145619A1 (en) Method for preparation of, and application of, mordenite having mesopores and micropores
CN100418880C (en) Molecular sieve with AWO structure and its synthesizing process
de Araujo et al. Hydrothermal synthesis of cerium aluminophosphate
EP2174911A1 (en) Method for preparing a zeolite with MTW-type structure
EP1980531B1 (en) Method for preparing a zeolite having MEL structure
US7037874B2 (en) Process for the preparation of porous crystalline silicoaluminophosphate molecular sieves
WO2012056118A1 (en) Izm-4 crystallized solid and process for preparing same
CN111099605B (en) Phosphate molecular sieve with AFX structure and preparation method thereof
CN111099637B (en) Silicon-phosphorus-aluminum molecular sieve and preparation method thereof
CN111099631A (en) Transition metal phosphorus aluminium molecular sieve and its preparation method
FR2953509A1 (en) Preparing crystallized solid metallophosphate having AFI structure type comprises mixing phosphate anion-, trivalent element- and fluoride anion source with ionic liquid having 1-butyl-3-methylimidazolium salt and ionothermally treating
JPH0234512A (en) Novel mtt structure zeolite and synthesis thereof
CN111099635B (en) SCM-19 metal phosphoaluminate and preparation method thereof
Yuan et al. Synthesis of mesostructured lamellar aluminophosphates in the presence of alkylpyridinium cationic surfactant

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant