WO2014089739A1

WO2014089739A1 - Sapo-35 zeolite and synthesis method therefor

Info

Publication number: WO2014089739A1
Application number: PCT/CN2012/086279
Authority: WO
Inventors: 王德花; 田鹏; 刘中民; 樊栋; 张莹; 杨越
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2012-12-10
Filing date: 2012-12-10
Publication date: 2014-06-19

Abstract

Provided in the present invention is a SAPO-35 zeolite. The anhydrous chemical composition of same is: mR₁·nCh⁺·(Si_xAl_yP_z)O₂, where R₁ is an alkanolamine, Ch⁺ is a choline cation distributed in zeolite cages and pores, m is the number of moles of the alkanolamine per mole of (Si_xAl_yP_z)O₂, n is the number of moles f the choline cation per mole of (Si_xAl_yP_z)O₂, m = 0-0.03, n = 0.05-0.25, and x, y, and z respectively express the mole fractions of Si, Al, and P, respectively ranged as x = 0.01-0.30, y = 0.35-0.55, and z = 0.25-0.49, while x + y + z = 1. The synthesized SAPO-35 zeolite of the present invention can be used as a catalyst in an acid-catalyzed reaction, such as a methanol-to-olefin reaction. The present invention also relates to applications of the SAPO-35 zeolite in terms of adsorption and isolation of CH₄, CO₂, and N₂.

Description

SAPO-35 molecular sieve and synthesis method thereof

The invention belongs to the field of SAPO molecular sieves, and particularly relates to a SAPO-35 molecular sieve and a synthetic method thereof. Background technique

The aluminum phosphate molecular sieve is a new generation molecular sieve (US4310440) invented by UCC in the early 1980s after the silica-alumina molecular sieve. The skeleton of the molecular sieve is formed by alternating the phosphorus-oxygen tetrahedron and the aluminum-oxygen tetrahedron. Since the molecular sieve skeleton is electrically neutral, there is no cation exchange performance and catalytic reaction performance.

When silicon is introduced into the framework of the aluminum phosphate molecular sieve, it is a silicoaluminophosphate molecular sieve, that is, a SAPO series molecular sieve (US4440871), and the molecular sieve skeleton is composed of a phosphorus-oxygen tetrahedron, an aluminoxytetrahedron and a silicon tetrahedron, and the skeleton has a negative charge. There are equilibrium cations outside the backbone and therefore have cation exchange properties. When the extra-framework cation is H÷, the molecular sieve has an acidic center and will possess acid-catalyzed reaction properties. SAPO molecular sieves as active components of catalysts are likely to be used in refining and petrochemical industries such as catalytic cracking, hydrocracking, isomerization, aromatic alkylation, and oxidant-containing conversion.

SAPO-35 is a delta-zeolite type (LEV) molecular sieve with intersecting eight-membered ring channels with a pore size of 3.6 X 4.8A, which is a small pore molecular sieve. The skeleton of SAPO-35 is a LEV cage connected by a single six-membered ring and a double six-membered ring. There are two different T atom positions in the skeleton, one in the double six-membered ring and the other in the single six-membered ring. The distribution ratio of these two positions is 2:1.

The SAPO-35 molecular sieve is generally carried out by hydrothermal or alcoholic synthesis using water or an alcohol as a solvent in a closed autoclave. The synthetic components include an aluminum source, a silicon source, a phosphorus source, a structure directing agent, and deionized water. Optional silicon source is silica sol, fumed silica, aluminum source is activated alumina, aluminum isopropoxide, pseudoboehmite and alkyl aluminum oxide. Phosphorus source is generally 85% phosphoric acid. The choice of structure-directing agent will have a certain influence on the microstructure, element composition and morphology of the synthetic molecular sieve, which will affect its catalytic performance.

In 1984, US 440871 first disclosed a synthesis using quinuclidine as a template. The method of SAPO-35 molecular sieve. In 1999, CN1299776A discloses a method for synthesizing SAPO-35 using hexamethyleneimine (HMI) and hexamethylenediamine (HDA) as a template. In 2005, US 2005/0090390 discloses a method for synthesizing a highly crystalline, strongly acidic SAPO-35 molecular sieve using hexamethyleneimine as a template in an alcoholic heat system.

The invention adopts the amine thermal method for the first time to synthesize pure phase SAPO-35 molecular sieve under the condition of amine heat with choline cation as structure directing agent and alcohol amine as solvent. The prepared SAPO-35 molecular sieve exhibits excellent catalytic performance and gas adsorption separation performance in the catalytic reaction. Summary of the invention

The object of the present invention is to provide a SAPO-35 molecular sieve whose anhydrous chemical composition is: ^^.!^!^ (Si _x Al _y P _z )0 ₂ , where: is an alcoholamine, Ch ⁺ is a choline cation, distributed in a molecular sieve cage and a channel; m is per mole (Si _x Al _y P _z The number of moles of the alcohol amine in 0 ₂ , m = 0 to 0.03; n is the number of moles of choline cation per mole (81 _{? {} 8 1 ^ 0 ₂ , n = 0.05 to 0.25; x, y, z respectively represent The molar fractions of Si, Al and P are respectively x=0.01~0.30, y=0.35~0.55, z=0.25-0.49, and x+y+z=l; the preferred range is x=0.05~0.20, y =0.38-0.52 ,

And x+y+z=l. The alcoholamine is any one or any of hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-diethylethanolamine, triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, diglycolamine. A mixture of several. The molecular sieve X-ray diffraction analysis results include at least diffraction peaks as shown in the following table:

Another object of the present invention is to provide a method for synthesizing SAPO-35 molecular sieve.

A further object of the present invention is to provide an SAPO-35 molecular sieve synthesized by the above method and an acid catalytic reaction catalyst and a gas adsorbent prepared therefrom.

The technical problem to be solved by the invention is that the choline cation is used as a structure-directing agent, and the phosphorus source, the silicon source and the aluminum source used in the synthesis of the conventional molecular sieve are used as raw materials, and the amine thermal condition using the alcohol amine as a solvent The pure phase SAPO-35 molecular sieve was synthesized.

The present invention is characterized in that the preparation process is as follows - a) mixing an alcohol amine, an aluminum source, a silicon source, a phosphorus source, a compound containing a choline cation, and deionized water in a certain ratio to obtain an initial coagulation having the following molar ratio. Glue mixture:

Si0 ₂ /Al ₂ 0 ₃ =0.01 -1 .5;

Ρ ₂ Ο ₅ /Α1 ₂ Ο ₃ = 0.5 ~ 3;

H ₂ 0/A1 ₂ 0 ₃ = 3- 20;

Ch ⁺ /Al ₂ 0 ₃ = 0.01 ~ 3, wherein Ch ⁺ is a choline cation;

3⁄4/Α1 ₂ Ο ₃ = 3 ~ 30 , where is an alcoholamine;

b) The initial gel mixture obtained in step a) is charged into a high pressure synthesis kettle, sealed, and heated to

Crystallization at 150-220 ° C under autogenous pressure for 5 to 120 hours;

c) After the crystallization is completed, the solid product is centrifuged, washed with deionized water to neutrality, and dried to obtain SAPO-35 molecular sieve.

The step a) the silicon source in the initial gel mixture is a mixture of one or a combination of silica sol, active silica, orthosilicate, metakaolin; aluminum source is aluminum salt, activated alumina, a mixture of one or any of alkoxyaluminum, metakaolin; a phosphorus source of one or a mixture of any of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphide or phosphorus oxide . The alcoholamine is any one or any of hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-diethylethanolamine, triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, diglycolamine. a mixture of several; the choline cation Ch ⁺ -containing compound is a choline inorganic salt and / or a choline organic salt.

The step a) the compound containing the choline cation Ch ⁺ in the initial gel mixture is a mixture of any one or any one of choline chloride, phosphorylcholine, choline choline and choline hydroxide. a) The molar ratio of Si0 ₂ /Al ₂ 0 ₃ in the initial gel mixture is preferably from 0.1 to 1.0. The molar ratio of P ₂ 0 ₅ /A1 ₂ _{3 3} in the initial gel mixture in the step a) is preferably from 0.7 to 2.0. The molar ratio of H ₂ 0/A1 ₂ 0 ₃ in the initial gel mixture in the step a) is preferably from 8 to 17. The molar ratio of Ch ⁺ /Al ₂ 〇 ₃ in the initial gel mixture in the step a) is preferably from 0.42 to 2.0. The molar ratio of the alcoholamine/A1 ₂ 0 ₃ in the initial gel mixture in the step a) is preferably 6.0 to 15. The crystallization process in step b) can be carried out either statically or dynamically. The present invention also relates to a catalyst for acid-catalyzed reaction which is obtained by calcining in an air of 400 to 700 ° C by the SAPO-35 molecular sieve described above or the SAPO-35 molecular sieve synthesized according to the above method.

The present invention also relates to a catalyst for the conversion of an oxygen-containing compound to an olefin, which is obtained by calcining the above-mentioned SAPO-35 molecular sieve or SAPO-35 molecular sieve synthesized according to the above method through 400 to 70 (TC air).

The invention also relates to an adsorbent for CH ₄ /C〇 ₂ and N ₂ /C〇 ₂ separation, which is passed through the above SAPO-35 molecular sieve or the SAPO-35 molecular sieve synthesized according to the above method through 400 ~ 70 ( It is obtained by calcination in TC air.

The beneficial effects that can be produced by the present invention include:

(1) A SAPO-35 molecular sieve having a choline cation as a template was obtained.

(2) For the first time, SAPO-35 molecular sieve was obtained by amine thermal method, which opened up a new system for the preparation of SAPO-35 molecular sieve.

(3) The prepared SAPO-35 molecular sieve can be used as a catalyst for acid catalytic reaction and oxygenate conversion to exhibit good catalytic performance in the olefin reaction.

(4) The prepared SAPO-35 molecular sieve can be used as an adsorbent for CH ₄ /CO ₂ and N ₂ /CO ₂ separation. DRAWINGS

Figure 1 Detailed Description - Elemental composition using Philips' Magix 2424 X-ray fluorescence analyzer (XRF)

X-ray powder diffraction phase analysis (XRD) was carried out by XNaert PROX ray diffractometer from PANalytical, Netherlands, Cu target, Κα radiation source (λ = 0.15418 nm), voltage 40 KV, current 40 mA.

The SEM morphology analysis was performed using a KYKY-AMRAY-1000B scanning electron microscope from the Scientific Instrument Factory of the Chinese Academy of Sciences.

Carbon magnetic resonance ( ¹³ CMASNM ) analysis using Infinity plus from Vanan, USA 400WB solid nuclear magnetic spectrum analyzer, using BBO MAS probe, the operating magnetic field strength is 9.4T.

The CHN elemental analysis was carried out using a Vario EL Cube elemental analyzer made in Germany.

The invention is described in detail below by way of examples, but the invention is not limited to the examples. Example 1

The molar ratio of each raw material and the crystallization conditions are shown in Table 1. The specific batching process is as follows, mixing pseudo-boehmite (A1 ₂ 0 ₃ mass percentage 72.5%) and hydrazine, hydrazine-diethylethanolamine (mass percentage 99%), and then adding silica sol (Si0 ₂ The mass percentage is 30.04%), stir evenly, then add phosphoric acid (H ₃ P0 ₄ mass% 85%) dropwise, stir evenly, then add water, finally add choline chloride, stir to form a gel. , Transfer the gel to the stainless steel reactor. After the reactor was placed in an oven, the temperature was programmed to crystallization for 48 h at 200 ° C. After the crystallization was completed, the solid product was centrifuged, washed, and dried in 10 CTC of air to obtain a raw powder. The sample was subjected to XRD analysis, and the results showed that the synthesized product had the characteristics of SAPO-35 structure, and the XRD data are shown in Table 2. Table 1 Molecular sieve synthesis ingredients and crystallization conditions table *

The solid alcohol amine and the aluminum source and the phosphorus source and the silicon source and the H ₂ 0 contain choline crystallized crystallization amount of A1 ₂ 0 ₃ p ₂ o ₅ moles containing 0 ₂ cations. Molar number of compounds and

Molar number

1 Ν,Ν-二乙拟薄水水铝正phosphoric acid silica sol 1.54mol choline chloride 200°C 48h base ethanolamine stone 0.10 O. l Omol 0.04mol 0.05mol

0.8mol mol

2 Ν,Ν-diethyl aluminum isopropoxide orthophosphoric acid silica sol 1.2mol choline chloride 220°C 12h ethanolamine 0.1 mol O. l Omol O.OOlmol 0.005mol

0.60mol

3 Ν,Ν-二乙拟薄水水铝 orthophosphoric acid silica sol 2.0mol gasification choline 200°C 24h base ethanolamine stone 0.1 mol 0.15mol 0.15mol 0.3mol

1.2mol

4 Ν,Ν-二乙 Y alumina orthophosphoric acid silica sol 0.9mol gasification choline 200°C 24h base ethanolamine 0.1 mol O. l Omol O. l Omol 0.042mol

0.88mol

5 triethanolamine sulfuric acid orthophosphoric acid active dioxin l. lmol phosphorylcholine 190 ° C 48 h 0.6 mol 0.1 mol 0.05 mol silicon oxide 0.2 mol

0.03mol

6 triethanolamine aluminum chloride 0.1 orthophosphoric acid tetraethyl orthosilicate 0.3mol 200 ° C 24h 0.3mol mol O. l Omol ester 0.08mol alkali

O.OOlmol Ν,Ν-二乙拟薄水铝铝phosphoric acid silica sol 1.8mol Phosphocholine 200°C 24h-based ethanolamine 0.1 mol 0.09mol 0.15mol 0.25mol

l .Omol

Triethanolamine pseudo-thin aluminum orthophosphate silica sol 1.54mol gasification choline 200°C 48h 0.8mol stone 0.1 mol O. l Omol 0.04mol 0.05mol

Ν,Ν-二乙拟薄水水 Ammonia hydrogen phosphate sol 1.8mol citric acid bile 220°C 12h basal ethanolamine stone 0.1 mol O. l Omol 0.01 mol alkali 0.2mol

1.6mol

Diisopropyl alcohol Quasi-thin aluminum hydroxide Hydrogen phosphate diamine Active dioxane 1.6mol Choline chloride 200°C 24h Amine 1.5mol Stone 0.1 mol O. l Omol Siliconized 0.3mol

0.06mol

Ν,Ν-Diethyl sulphate S Hydrogen phosphate diamine Silica sol 1.6mol 200°C 18h Ethylethanolamine 0.1 mol 0.15mol 0.07mol Base 0.08mol

2.0mol

N-methyldiphosphorus thin aluminum hydroxide orthophosphoric acid silica sol 1.6mol choline chloride 180°C 96h ethanolamine stone 0.1 mol 0.12 mol 0.12 mol 0.2 mol

0.8mol

N-methyldiphosphoric acid aluminum hydroxide phosphoric acid active dioxane 1.8mol phosphorylcholine 210°C l Oh ethanol amine stone 0.1 mol 0.13mol silicon 0.18mol

1.4mol 0.03mol

Ν,Ν-二乙拟薄水水铝正phosphoric acid silica sol l .Omol gasification choline 190°C 12h-based ethanolamine stone 0.1 mol O. l Omol 0.03mol 0.28mol

l .Omol

Diisopropyl alcohol pseudo-thin aluminum orthophosphate orthophosphoric acid 1.7 mol choline chloride 150 ° C 120 h amine 1.5 mol stone 0.1 mol O. l Omol ester 0.03 mol 0.25 mol

Ν,Ν-二乙拟薄水水铝 Trimethylphosphorus silica sol 1.7mol 210°C 12h-based ethanolamine stone 0.1 mol O. l Omol 0.03mol alkali 0.3mol

1.5mol

Triethanolamine pseudo-thin aluminum triethylphosphide silica sol 1.5mol gasification choline 170°C 96h 1.7mol stone 0.1 mol O. l Omol 0.03mol 0.19mol

Ν,Ν-二乙拟薄水水铝正phosphoric acid silica sol 2.0mol phosphorylcholine 220°C 5h basal ethanolamine stone 0.1 mol 0.20mol 0.075mol 0.28mol

1.8mol

Ν,Ν-二乙拟薄水水铝 orthophosphoric acid silica sol 2.0mol choline chloride 200°C 24h basal ethanolamine stone 0.1 mol 0.30mol 0.06mol 0.3mol

3.00mol Table 2 XRD results of the sample of Example 1

No. 2Θ d(A) 100x1/1°

1 8.6317 10.24437 14.26

2 10.9414 8.08649 62.8

3 1 1.6544 7.59327 7.1

4 13.3789 6.61 816 35. 16

5 15.9398 5.5602 7.21

6 17.3168 5.12104 67.47

7 17.7816 4.9882 12.08

8 20.9872 4.233 59.3

9 21.9518 4.04913 100

10 22.6986 3.91756 4.17

Π 23.2826 3.82061 29.23

12 24.9802 3.56468 1 1.47

13 25.8324 3.44899 2.89

14 26.966 3.30652 18.95

15 28.5264 3.1291 43.82

16 29. 1684 3.06167 7.16

17 31.6272 2.82904 8.6

18 32.234 2.77715 36.52

19 34.487 2.60071 1 1.55

20 35.0524 2.56004 3.43

21 35.5046 2.52847 3.04

22 35.9207 2.50013 4.91

23 37.7786 2.38134 1.37

24 39.5783 2.2771 1 1.17

25 40.9423 2.20434 1.71

26 42.0343 2.14957 3.35

27 44.8294 2.02183 2.33 28 47.9661 1.89668 4.34

29 49.7191 1.83384 3.7

30 51.4118 1.77737 8.42

31 55.296 1.66137 3.32

32 58.7295 1.57216 2.27 Example 2-19

The specific proportion of ingredients and crystallization conditions are shown in Table 1. The specific batching process is the same as in Example 1. The synthesized samples were subjected to XRD analysis, and the data results were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensity of the peaks fluctuated within ±10% according to the synthesis conditions, indicating that the synthesized product has the characteristics of the SAPO-35 structure.

¹³ C MAS NMR analysis of the original powder samples of Examples 1-7, by comparison with the ¹³ C MAS NMR standard spectrum of choline cations and alcohol amines, it was found that the sample contained both choline cations and corresponding alcohol amines, according to The NMR peaks with unique non-coincidence were quantitatively analyzed to determine the ratio of the two.

The CHN elemental analysis of the original powder samples of Examples 1-7 was carried out by XF analysis of the bulk elemental composition of the molecular sieve product. Based on the results of CHN elemental analysis, XRF and ¹³ C MAS NMR analysis, the composition of the molecular sieve raw powder was obtained as follows -

Ο.ΟΙΝ,Ν-Diethylethanolamine O.10Ch ⁺ .(Si.. ₁₂ Al.. ₄₉ P.. ₃₉ )O ₂

0.02N, N-diethylethanolamine. 0.08Ch ⁺ . (Si ₀ . ₀₇ Al ₀ . ₅₃ P ₀ . ₄₀ )O ₂ ,

0.03N, N-diethylethanolamine. 0.05Ch+. (Si ₀ . ₁₇ Al ₀ . ₄₆ P ₀ . ₃₇ )O ₂ ,

0.013N, N-diethylethanolamine. 0.17Ch ⁺ . (Si _i4 Al ₄₇ P ₃₉ )O ₂ ,

0.005 triethanolamine O.19Ch ⁺ .(Si _il Al ₀ . ₅₀ P ₃₉ )O ₂ ,

0.008 triethanolamine. 0.23Ch ⁺ . (Si.. ₁₃ Al.. ₄₆ P.. ₄₁ )O ₂ ,

0.014N, N-Diethylethanolamine. 0.19Ch ⁺ . (Si.. ₁₅ Al.. ₄₇ P.. ₃₈ )O ₂ .

Example 20

The specific proportion of ingredients and crystallization conditions are shown in Table 1, and the specific batching process is the same as in Example 1. Only hydrazine, hydrazine-diethylethanolamine was replaced with triethanolamine. The XRD analysis of the synthesized samples showed that the XRD results of the synthesized products were close to those of Table 2, that is, the peak positions and shapes were the same, and the relative peak intensities of the peaks were ±10%. Fluctuations within the range indicate that the synthesized product has the characteristics of the SAPO-35 structure.

The ¹³ C MAS NMR analysis of the original powder sample showed that it contained only the characteristic resonance peak of choline. Example 21

3 g of the synthetic sample of Example 1-20 was separately placed in a plastic beaker, and 3 ml of a 40% hydrofluoric acid solution was added to dissolve the molecular sieve skeleton in an ice water bath, and then 15 ml of carbon tetrachloride was added to dissolve the organic matter therein. The organic matter was analyzed by ICS-3000 ion chromatography and the cation column type was CS12A, and the composition was analyzed to show that both contained choline cations. Comparative Example 1 (no choline cationization in the synthesis system)

Bu

The specific proportion of ingredients, the batching process and the crystallization conditions were the same as in Example 1. No choline chloride was added to the synthetic gel. The XD analysis of the synthesized sample showed that the XRD result of the synthesized product was the characteristic peak of SAPO-34. Example 22

The sample obtained in Example 1 was subjected to air baking at 60 CTC for 4 hours, and then tableted and crushed to 20 to 40 mesh. The l.Og sample was weighed into a fixed bed reactor for MTO reaction evaluation. The reaction was carried out by activating nitrogen gas at 550 ° C for 1 hour and then cooling to 400 ° C. Methanol was carried by nitrogen, nitrogen flow rate was 40 ml/mm, methanol weight space velocity was 4.0 h - the reaction product was analyzed by on-line gas chromatography (Vanan 3800, FID detector, capillary column PoraPLOT Q-HT). The results are shown in Table 3.

Table 3 sample methanol conversion to olefin' hydrocarbon reaction results

Life selectivity (% by mass) *

Sample

(min) CH ₄ C2H C ₂ H6 C3H6 C3H8 C4+ c ₅ ⁺ C2H +C3H6

100 4.05 42.16 0.84 3.87 80.23 Example 1 Example 23

The sample obtained in Example 4 was used as a CO ₂ adsorbent. The adsorption isotherm of the sample is in the United States The measurement was performed on ASAP2020 by Micromeritics. The adsorbed gases are C〇 ₂ (99.99%), CH ₄ (99.99%), and N ₂ (99.99%). In order to avoid the influence of the physically adsorbed water on the adsorption test in the molecular sieve, the sample was air-fired at 600 °C for 4 hours before the isotherm test, and then further processed in ASAP2020 under the condition that it was extremely low. Under vacuum (5x10-3 mmHg), it was raised to 350 °C at a heating rate of rC/min for 8 hours. The temperature of the gas adsorption was controlled by a constant temperature water bath (accuracy: plus or minus 0.05 ^Q C), and the adsorption temperature was 298 K. The adsorption amounts of the samples for C0 ₂ , CH ₄ and N ₂ were 3.79, 0.36 and 0.28 mmol/g, respectively (at a pressure of 10 kPa). The adsorption selectivity calculated therefrom was CO ₂ /CH ₄ = 10.5, and C 〇 ₂ /N ₂ = 13.5. The sample after the adsorption experiment was subjected to vacuum adsorption treatment at room temperature for 30 mm on an ASAP2020 apparatus, and then subjected to adsorption adsorption isotherm measurement. The adsorption amounts of the sample to C〇 ₂ and CH n N ₂ were 3.78, 0.38 and 0.30 mmol/g, respectively. lOlkPa), indicating that the sample has good regeneration performance and can be regenerated under very mild conditions.

Claims

Rights request

A SAPO-35 molecular sieve characterized in that the molecular sieve has the following anhydrous chemical composition: ΐΉ3⁄4 .η(:ΐι ⁺ . (Si _x Al _y P _z )0 ₂ , wherein:

1 is an alkanolamine, m is the number of moles of alkanolamine per mole of (Si _x Al _y P _z ) 0 ₂ , m = 0 to 0.03; Ch ⁺ is a choline cation, and n is per mole (S _lx Al _y P _z ) the number of moles of choline cation in 0 ₂ , n=0.05~0.25 _;

x, y, and z represent the molar fractions of Si, Al, and P, respectively, and the ranges are x = 0.01 to 0.30, y = 0.35 to 0.55, z = 0.25 to 0.49, and x + y + z = 1.

2. The SAPO-35 molecular sieve according to claim 1, wherein the X-ray diffraction pattern has a diffraction peak at the following position:

The SAPO-35 molecular sieve according to claim 1, wherein the alcohol amine is hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-diethylethanolamine, triethanolamine, diethanolamine, triisopropyl Any one or a mixture of any of alkanoamine, diisopropanolamine, and diglycolamine.

4. A method of synthesizing the SAPO-35 molecular sieve according to claim 1, wherein the step of synthesizing is carried out by an amine thermal method as follows: a) an alcohol amine, an aluminum source, a silicon source, a phosphorus source, and a choline cation The compound and deionized water are uniformly mixed in a certain ratio to obtain an initial gel mixture having the following molar ratio:

Si0 ₂ /Al ₂ 0 ₃ =0.01~1.5 ;

Ρ ₂ Ο ₅ /Α1 ₂ Ο ₃ = 0.5~ 3 ;

H ₂ 0/A1 ₂ 0 ₃ = 3~ 20;

Ch ⁺ /Al ₂ 0 ₃ = 0.01 〜 3, wherein Ch ⁺ is a choline cation; ΐνΑ1 ₂ Ο ₃ = ₃ ~30, wherein 1^ is an alcoholamine;

Crystallization at 150-220 ° C under autogenous pressure for 5 to 120 hours;

c) After the crystallization is completed, the solid product is separated, washed with deionized water to neutrality, and dried to obtain SAPO-35 molecular sieve.

The method according to claim 4, wherein the step a) the silicon source in the initial gel mixture is one or any of silica sol, active silica, orthosilicate, metakaolin. a mixture of aluminum; aluminum source, activated alumina, alkoxy aluminum, metakaolin or a mixture of any of the following; phosphorus source is orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphide Or a mixture of one or any of several phosphorus oxides; the alcohol amine is hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-diethylethanolamine, triethanolamine, diethanolamine, triisopropanolamine, diiso Any one or a mixture of any one of propanolamine and diglycolamine; the compound containing a choline cation Ch ⁺ is a choline inorganic salt and/or a choline organic salt.

The method according to claim 4, wherein the step a) the compound containing the choline cation Ch ⁺ in the initial gel mixture is choline chloride, phosphorylcholine, choline citrate, and choline hydroxide. Any one or a mixture of any of the bases.

The method according to claim 4, characterized in that the crystallization process in the step b) is carried out under static or dynamic conditions.

The method according to claim 4, wherein said step a) is in the initial gel mixture, Ch ⁺ /Al ₂ 〇 ₃ = 0.42 to 2.0.

The method according to claim 4, wherein said step a) the initial gel mixture has an alkamine Α _{1 2} 〇 ₃ = 6.0 to 15.

A catalyst for acid-catalyzed reaction, characterized in that the SAPO-35 molecular sieve according to any one of claims 1 to 3 or the SAPO-35 molecular sieve synthesized according to any one of claims 4 to 9 is subjected to 400 ~ It is obtained by calcination in air at 700 °C.

A catalyst for the conversion of an oxygenate to an olefin, characterized in that the SAPO-35 molecular sieve according to any one of claims 1 to 3 or the SAPO synthesized according to any of the methods of claims 4-9 -35 molecular sieves are obtained by calcination in air at 400 ~ 700 °C. , an adsorbent for (: 11 ₄ / ( 0 ₂ and ] ^ ₂ / (0 ₂ separated), characterized by The SAPO-35 molecular sieve according to any one of claims 1 to 3 or the SAPO-35 molecular sieve synthesized according to any one of claims 4 to 9 is obtained by calcination in air at 400 to 700 °C.