# US 2018/0021728 A1 · Pervaporation and Vapor-Permeation Separation of Gas-Liquid Mixtures and Liquid Mistures by SAPO-34 Molecular Sieve Membrane Prepared in Dry-Gel Process

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- Number: US 2018/0021728 A1
- Document ID: US20180021728A1
- Status: Published application
- Kind: A1
- Application number: 15/547,923
- Filed: 2016-02-02
- Published: 2018-01-25
- Earliest claimed: 2015-02-03
- Assignees: Shanghai Advanced Research Institute, Chinese Academy of Sciences
- Applicants: Shanghai Advanced Research Institute, Chinese Academy of Sciences; Shanxi Lu'An Enviromental Protection & Energy Development Co., Ltd.; Total Raffinage Chimie
- Inventors: Daniel Curulla-Ferre; Yuhan Sun; Zhiqiang Sun; Yanfeng Zhang
- Web page: https://patentgrep.com/patent/US20180021728A1

## CPC

- B01D 61/362: {Pervaporation}
- B01D 19/0031: {by filtration}
- B01D 53/228: {characterised by specific membranes}
- B01D 67/0051: {by controlled crystallisation, e,.g. hydrothermal growth}
- B01D 69/04: Tubular membranes
- B01D 69/105: {Support pretreatment}
- B01D 71/028: {Molecular sieves (carbon B01D71/021)}
- C01B 37/08: Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO}
- C01B 39/026: {After-treatment}
- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- C07C 68/08: Purification; Separation; Stabilisation
- B01D 2323/24: Use of template or surface directing agents [SDA]
- B01D 2323/46: Impregnation
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The invention discloses a method for the pervaporation and vapor-permeation separation of a gas-liquid mixture or a liquid mixture by a SAPO-34 molecular sieve membrane prepared in a dry gel process, comprising: 1) synthesis of SAPO-34 molecular sieve seeds; 2) coating the SAPO-34 seeds on a porous support; 3) preparation of a mother liquor for dry gel synthesis of SAPO-34 molecular sieve membrane; 4) supporting the mother liquor for dry gel synthesis on the porous support coated with SAPO molecular sieve seeds and drying; 5) placing the porous support prepared in step 4) into a reaction vessel, adding a solvent, performing crystallization of the dry gel; 6) calcining; 7) using the SAPO-34 molecular sieve membrane obtained from step 6) to perform separation of a gas-liquid mixture or a liquid mixture by a process of pervaporation separation or vapor-permeation separation. The invention has the advantages of very high methanol selectivity and permeation flux, lowering synthesis cost of molecular sieve membrane and lowering environment pollution.

## Claims

### Claim 1

A method for the pervaporation or vapor-permeation separation of a gas-liquid mixture or a liquid mixture by a SAPO-34 molecular sieve membrane prepared in a dry gel process, characterized in that the method comprises the following steps;
1) mixing and dissolving an Al source, tetraethylammonium hydroxide (TEAOH), water, a Si source and a P source to make a reaction liquor for seeds, which is then subjected to crystallization for 2-72 h by heating at 120-230 ±C, then centrifuging, washing and drying to get SAPO-34 molecular sieve seeds;
wherein the molar ratio of the Al source, P source, Si source, tetraethylammonium hydroxide and all water in the reaction liquor for seeds is 1 Al2O3: 1-2 P2O5: 0.3-0.6 SiO2: 1-3 TEAOH: 55-150 H2O;
2) coating the SAPO-34 molecular sieve seeds on a porous ceramic support;
3) uniformly mixing an Al source, a P source, a Si source, tetraethyl ammonium hydroxide (TEAOH) and water to form a mother liquor for dry gel synthesis of SAPO-34 molecular sieve membrane;
wherein the molar ratio of the Al source, P source, Si source, tetraethyl ammonium hydroxide and all water in the mother liquor for dry gel synthesis is: 1 Al2O3: 1-2 P2O5: 0.1-0.6 SiO2: 1-8 TEAOH:30-1000 H2O;
4) supporting the mother liquor for dry gel synthesis on the porous support coated with SAPO-34 molecular sieve seeds prepared in step 2), and drying, to form a porous support having a dry gel layer;
5) placing the porous support prepared in step 4) into a reaction vessel, adding a solvent, performing crystallization of the dry gel;
6) calcining at 400-600° C. for 4-8 h to obtain a SAPO-34 molecular sieve membrane;
7) using the SAPO-34 molecular sieve membrane obtained in step 6) to perform the separation of a liquid mixture by a process of pervaporation separation or vapor-permeation separation;
wherein the liquid mixtures is a mixture of methanol and a liquid other than methanol, wherein said liquid other than methanol is selected from one of dimethyl carbonate, ethanol, methyl tert-butyl ether;

### Claim 2 (depends on 1)

The method according to claim 1 characterized in that in step 1), the procedure for making the reaction liquor for seeds comprises adding the Al source to the tetraethyl ammonium hydroxide solution, and after hydrolysis, adding the Si source and the P source, and stirring for 12-24 h to form the reaction liquor for seeds; wherein the heating is microwave heating; and the size of the SAPO-34 molecular sieve seeds is 50-1000 nm.

### Claim 3 (depends on 1)

The method according to claim 1 characterized in that in steps 1) and 3), the Al source is selected from one or more of aluminium isopropoxide, aluminium hydroxide, elemental aluminium, an aluminium salt, alumina, and hydrated alumina; wherein the aluminium salt is selected from one or more of aluminium nitrate, aluminium chloride, alumimium sulfate, aluminium phosphate;
the Si source is selected from one or more of silica sol, silicate ester, silica aerosol and sodium silicate;
the P source is phosphoric acid.

### Claim 4 (depends on 1)

The method according to claim 1 characterized in that in step 2), the shapes of the porous support are selected from single-channel tube, multi-channel tube, flat plate, hollow fiber tube; the pore size of the porous support is 5-2000 nm; and the coating method is selected from brush coating, dip-coating, spray coating or spin coating.

### Claim 5 (depends on 4)

The method according to claim 4 characterized in that the coating method is dip-coating and the process comprises uniformly coating a 0.01-1 wt % solution of the SAPO-34 molecular sieve seeds in ethanol on the porous support.

### Claim 6 (depends on 1)

The method according to claim 1 characterized in that in step 3), the procedure of forming the mother liquor for dry gel synthesis of SAPO-34 molecular sieve membrane comprises adding the Al source to the P source and after full hydrolysis, adding the Si source and tetra-ethyl ammonium hydroxide and stirring for 12-24 h, to obtain the mother liquor for dry gel synthesis of SAPO-34 molecular sieve membrane.

### Claim 7 (depends on 1)

The method according to claim 1 characterized in that in step 4), the supporting method is selected from dip-coating, spray coating or spin coating; and the molar composition of the dry gel layer is 1.0 Al2O3: 1-2.0 P2O5: 0.1-0.6 SiO2: 1-8 TEAOH: 1-300 H2O.

### Claim 8 (depends on 7)

The method according to claim 7 characterized in that the supporting method is dip-coating and its procedure comprises immersing the porous support coated with SAPO-34 molecular sieve seeds in the mother liquor for dry gel synthesis for 1 s to 24 h, and then drying for 1 min to 48 h at room temperature to 120° C.

### Claim 9 (depends on 1)

The method according to claim 1 characterized in that in step 5), the solvent is selected from one or more of water, ammonia water, the mother liquor for dry gel synthesis, an organic solvent; and the solvent is used in an amount of 0.001˜0.1 g per mL volume of the reaction vessel; and the temperature for crystallization of the dry gel is 120-230° C. and the crystallization time is 2-72 h.

### Claim 10 (depends on 9)

The method according to claim 9 characterized in that the crystallization time is 4-7 h.

### Claim 11 (depends on 1)

The method according to claim 1 characterized in that in step 6), the atmosphere for calcination is selected from inert gas, vacuum, air, oxygen gas, or diluted oxygen gas in any ratio; in the calcination, the temperature increasing rate and the temperature decreasing rate are not higher than 2 K/min; and the membrane thickness of the SAPO-34 molecular sieve membrane is 1-2 microns.

### Claim 12 (depends on 1)

The method according to claim 1 characterized in that in step 7), the conditions for the process of pervaporation separation or vapor-permeation separation comprises: a methanol concentration of the feed ranging from 1-99 wt %, a feed flow rate ranging from 1-500 mL/min, a separation operation temperature ranging from 20° C. to 150° C., and a pressure on the permeate side ranging from 0.06 Pa to 300 Pa;
wherein in step 7), the inert gas contains N2;
the gaseous hydrocarbon contains methane;
the alcohol contains methanol, ethanol, or propanol;
the ketone contains acetone or butanone;
the aromatics contain benzene.