CN111359446B - Preparation method and application of acid-resistant PSQ composite film - Google Patents
Preparation method and application of acid-resistant PSQ composite film Download PDFInfo
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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Abstract
The invention discloses a preparation method and application of an acid-resistant PSQ composite membrane, and belongs to the technical field of membrane separation preparation. The preparation method comprises the following steps: (1) dissolving the PSQ precursor in an alcohol solvent, and sequentially adding hydrochloric acid, ammonia water and hydrochloric acid to perform acid-base-acid alternative catalytic reaction to obtain the PSQ sol. (2) A silica-zirconia sol is applied to a ceramic support to form a transition layer. (3) Coating PSQ sol on the surface of the transition layer as a separation layer, and dipping and pulling to obtain the PSQ composite membrane with the structure of the support layer, the transition layer and the separation layer. The PSQ composite membrane provided by the invention has good acid resistance, high flux and high selectivity, meets the current industrial requirements and expectations, and is widely applicable to organic solvent dehydration and organic solvent separation of an acidic system.
Description
Technical Field
The invention belongs to the field of membrane separation preparation, and particularly relates to a preparation method and application of an acid-resistant PSQ composite membrane.
Background
In the fields of petrochemical industry, fine chemical industry, pharmaceutical chemical industry, food and the like, an anhydrous organic solvent is indispensable, so that the anhydrous organic solvent is obtained by separating a small amount of or trace amount of water in the organic solvent. The traditional organic solvent dehydration technologies such as extractive distillation, azeotropic distillation, molecular sieve adsorption and the like have the defects of high energy consumption, complex process, high operation cost, environmental pollution and the like, so the fields face the challenges of energy conservation and emission reduction. Membrane separation technology has the advantages of high efficiency, low energy consumption, easy control, small occupied area and the like, and is generally considered to play a crucial role in the transition to sustainable chemical industry.
In the existing membrane separation technology, organic matter dehydration is a research hotspot in the field of pervaporation separation, and is particularly suitable for separating liquid mixtures with azeotropy or similar boiling points. Most of membranes used in pervaporation technology are high molecular organic membranes, such as polyvinyl alcohol, polyimide and polydimethylsiloxane, which are easy to form and have good selectivity to organic matters, but because the high molecular organic membranes have poor acid and alkali resistance and thermal stability, swelling is easily generated during use, performance attenuation is very large, and the defects cause that the high molecular organic membranes are greatly limited in application of dehydration at high temperature (more than 60 ℃) and in acid systems. Therefore, currently, inorganic pervaporation commercial membranes (such as zeolite membranes) are mostly selected for dehydration in an acidic system. However, the zeolite membrane has the problems of complex film forming mechanism, high preparation difficulty, high requirement on a carrier, need of an expensive template and the like, so that the zeolite membrane is difficult to expand and apply. And zeolite membranes (such as zeolite a, mordenite) exhibit some acid resistance, but the acid resistance is only limited to weak acid conditions (such as acetic acid) in the literature, and its performance decreases with increasing weak acid concentration, and the overall performance fluctuates greatly in strong acid (such as nitric acid) systems. Therefore, in order to realize wider application of the pervaporation technology, an acid-resistant polymer separation layer is prepared for the pervaporation membrane. The invention provides a preparation method of an acid-resistant pervaporation composite membrane and application of solvent dehydration in an acid system.
Disclosure of Invention
Aiming at the technical problems, the invention selects to prepare a silica-zirconia transition layer with good acid resistance in advance on an inorganic ceramic support body, prepares a separation layer by performing acid-base-acid alternative catalytic hydrolysis polymerization on a Polysilsesquioxane (PSQ) precursor, and finally prepares the acid-resistant PSQ composite membrane with excellent performance.
The preparation method comprises the following steps:
(1) dissolving a PSQ precursor in an alcohol solvent according to the mass fraction of 5 wt%, and adding hydrochloric acid and water to perform hydrolysis reaction, wherein the molar ratio of the PSQ precursor to the water to the hydrochloric acid is 1: 30-240: 0.1, the acid catalysis reaction time is 10-60 min, and the reaction temperature is 40-60 ℃. And (2) adding ammonia water for alkali catalytic reaction after the acid catalytic reaction, wherein the molar ratio of the ammonia water to the hydrochloric acid is 2-10: 1, the reaction time is 5-90 min, and the reaction temperature is 40-60 ℃. And finally, adding hydrochloric acid to stop the alkali catalytic reaction and continuing to react for 10-60 min, wherein the molar ratio of the hydrochloric acid to the ammonia water is 1-2: 1, the whole reaction temperature is 40-60 ℃, and finally the PSQ sol is prepared.
Wherein the concentration of the hydrochloric acid is 1-10 wt% and the concentration of the ammonia water is 1-10 wt%.
The PSQ precursor is one or two of 1, 2-di (triethoxysilyl) methane, 1, 4-di (triethoxysilyl) benzene and 1, 2-di (triethoxysilyl) ethylene; the alcohol solvent is one or two of ethanol and isopropanol.
The method adopts an acid-alkali-acid alternative catalysis process, firstly adds acid for catalysis, the grain diameter ratio obtained after catalysis is smaller and is about 1-2nm, then adds alkali (pH is greater than 7) for alkali catalysis reaction, the whole sol is spread after alkali catalysis, the grain diameter is increased to more than ten nanometers, the whole silicon network is spread, then adds acid, the grain diameter is reduced from large to small and is about 1-5 nm, and acid catalysis enables the silicon network to be further condensed. The invention adopts acid-base-acid alternative catalysis to lead the particle size to change from small to large and from large to small, the change of the silicon network structure in the whole process is polymerization-stretching-polymerization, the particle size of the sol is regulated again, the pore diameter of the membrane is regulated again, the whole silicon network structure is more compact, and thus the acid resistance is realized.
(2) A silica-zirconia sol was applied to a ceramic support to form a transition layer, which was a silica-zirconia sol having a mass fraction of 0.5 wt% (molar ratio Si/Zr: 1/1). The transition layer is prepared by soaking a ceramic support body in silica-zirconia sol for 10-60s, drying at room temperature for 5-10min, calcining for 15-30 min at 500-600 ℃ in air atmosphere, and repeating the process for 2-3 times.
Wherein the ceramic support comprises tubular or sheet alpha-Al2O3The support body has a porosity of 40-50% and a pore diameter of 50-200 nm. The silica-zirconia sol raw material is one or more of ethyl orthosilicate, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium tert-butoxide, and the transition layer can reduce the surface pore diameter of the membrane layer, increase the thermal stability of the membrane and prevent poresThe phenomenon of bleeding occurs.
(3) And (3) coating the PSQ hydrosol prepared in the step (1) on the surface of the transition layer in the step (2) by a dipping-pulling method to prepare the PSQ composite film.
Wherein the separation layer was coated on a ceramic support containing a silica-zirconia sol transition layer by dip-coating and flash-fired in air at 250 ℃ for 20 min.
The prepared acid-resistant PSQ composite membrane is used for dehydration in an acidic organic solution, and has good hydrothermal stability and excellent acid resistance.
The acidic organic solution is an organic solvent/water/acid ternary system, wherein the organic solvent is one or more of ethanol, ethylene glycol and n-butanol, and the acid is one or more of acetic acid, nitric acid and methanesulfonic acid.
The invention has the beneficial effects that:
(1) the prepared acid-resistant PSQ composite membrane can not swell in the pervaporation dehydration of an organic solvent (including an aprotic solvent NMP); compared with a polymer organic membrane, the ceramic membrane (the support and the transition layer material) has superior solvent resistance; the ceramic membrane has stronger mechanical stability and chemical stability, low requirement on use environment conditions, wide range and long service life.
(2) In the process of pervaporation dehydration of the prepared acid-resistant PSQ composite membrane as an organic solvent, the composite membrane has high temperature resistance (the pervaporation dehydration temperature is at least 190 ℃) and acid resistance (the range is 2< PH <8), higher temperature leads to higher flux, the area of the membrane required is reduced, and the overall cost is reduced.
(3) According to the invention, an acid-base-acid alternative catalysis process is adopted, so that the pore size distribution of the membrane can be effectively regulated and controlled to be 0.5-1 nm, the PSQ composite membrane can be widely applied to the membrane separation fields of reverse osmosis, nanofiltration and the like, and the applicability of the PSQ composite membrane in the membrane separation field is increased.
(4) The PSQ material combines the excellent performances of an organic component and an inorganic component, and has the characteristics of good hydrothermal stability, excellent chemical resistance and the like. Compared with the traditional inorganic silicon dioxide film material based on tetraethyl orthosilicate (TEOS), the material has the unique advantages of regular structure, adjustable surface property and the like.
Drawings
FIG. 1 dehydration was performed on BTESM composite membranes using a mixture of ethanol/water/acetic acid (95/5/1.5 wt%) at 70 ℃.
Fig. 2 is an SEM image of the BTESM composite membrane.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Dissolving 1, 2- (triethoxysilyl) ethylene (BTESEthyl) in an alcohol solvent according to the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 50 ℃, wherein the molar ratio of BTESM to water to hydrochloric acid is 1:80: 0.1.
(2) Adding ammonia water to perform alkali catalytic reaction after the acid catalytic reaction in the step (1), wherein the molar ratio of ammonia water: adding ammonia water with the mass fraction of 5 wt% into hydrochloric acid (the hydrochloric acid in the step (1)) at the ratio of 9:1, and continuously stirring for 60min at the temperature of 50 ℃ in a water bath to perform alkali catalytic reaction so as to increase the particle size of the sol.
(3) Adding hydrochloric acid for acid catalytic reaction after alkali catalysis, and adding hydrochloric acid according to the molar ratio: and (3) adding 2 wt% hydrochloric acid into ammonia water in a ratio of 1.2:1 to stop the base catalytic reaction in the step (2), wherein the reaction time is 45min, the reaction temperature is 45 ℃, and stable BTESEthyl sol is generated in an acidic environment.
(4) Coating silica-zirconia sol on a ceramic support to generate a transition layer, wherein the transition layer is silica-zirconia composite sol with the mass fraction of 0.5 wt%. The transition layer is prepared by soaking a ceramic support body in silica-zirconia sol for 10-60s, drying at room temperature for 5-10min, calcining for 15-30 min at 500-600 deg.C in air atmosphere, and repeating the process for 2-3 times, wherein the ceramic support body comprises tubular or sheet alpha-Al2O3And a support body. The transition layer can reduce the pore diameter of the surface of the membrane layer, increase the thermal stability of the membrane and prevent the occurrence of the pore permeation phenomenon. Then coating the BTESEthyl sol prepared in the step (3) on the surface of the transition layer, and carrying out dipping-liftingCoated on a ceramic support containing a silica-zirconia sol transition layer and flash-fired in air at 250 ℃ for 20 min. Obtaining the BTESEthyl composite membrane.
Example 2
(1) Dissolving 1, 2-bis (triethoxysilyl) methane (BTESM) in an alcohol solvent according to the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 50 ℃, wherein the molar ratio of BTESM to water to hydrochloric acid is 1:60: 0.1.
(2) Ammonia water according to molar ratio: adding ammonia water with the mass fraction of 5 wt% into hydrochloric acid with the proportion of 10:1, and continuously stirring for 60min at 50 ℃ in a water bath to perform alkali catalytic reaction so as to increase the particle size of the sol.
(3) According to molar ratio, hydrochloric acid: and (3) adding 2 wt% hydrochloric acid into ammonia water in a ratio of 1.5:1 to stop the base catalytic reaction in the step (2), wherein the reaction time is 45min, the reaction temperature is 45 ℃, and stable BTESM sol is generated in an acidic environment.
(4) Coating silica-zirconia sol on a ceramic support to generate a transition layer, wherein the transition layer is the silica-zirconia sol with the mass fraction of 0.5 wt%. The transition layer is prepared by soaking a ceramic support body in silica-zirconia sol for 10-60s, drying at room temperature for 5-10min, calcining for 15-30 min at 500-600 deg.C in air atmosphere, and repeating the process for 2-3 times, wherein the ceramic support body comprises tubular or sheet alpha-Al2O3And a support body. The transition layer can reduce the pore diameter of the surface of the membrane layer, increase the thermal stability of the membrane and prevent the occurrence of the pore permeation phenomenon. Then coating the BTESM sol prepared in the step (3) on the surface of the transition layer, coating the BTESM sol on a ceramic support containing the silica-zirconia sol transition layer through dip-coating, and carrying out flash firing in air at 250 ℃ for 20 min. Obtaining the BTESM composite membrane.
The performance and stability of the composite membranes were investigated (no membrane replacement in long-term tests) in different solvent/water mixtures at different temperatures and acid concentrations at 10mbar osmotic pressure for the resulting BTESM composite membranes or BTESEthy composite membranes.
Dehydration tests were performed on a BTESM composite membrane using a ternary ethanol/water/acetic acid mixture. A mixed feed of 5 wt% water and 0.15, 1.5 or 15 wt% acetic acid was added to ethanol and dehydrated at 70 ℃.
FIG. 1 Long term stability dehydration experiments were performed on BTESM composite membranes using a mixture of ethanol/water/acetic acid (95/5/1.5 wt%) at 70 ℃. In a 360-hour test, the dehydration content is high, and the penetrating fluid almost contains more than 85 percent of water, so that the excellent acid resistance stability is achieved.
The BTESM composite membrane was used for dehydration tests with a mixture of ethylene glycol/water/acetic acid. A mixed feed of 5 wt% water and 1.5 wt% acetic acid was added to ethylene glycol and dehydrated at 130 ℃.
The BTESM composite membrane was used for a dehydration test of a mixture of n-butanol/water/nitric acid. A mixed feed of 5 wt% water and 0.005, 0.05 or 0.5 wt% nitric acid was added to n-butanol and dehydrated at 95 ℃. The data indicate that although the BTESM composite membrane is not suitable for use in permeation systems where 0.5 wt.% nitric acid is present, the maximum concentration of strong acid is at least 0.05 wt.%. Long-term tests with acid concentrations between 0.05 wt.% and 0.5 wt.% are required to confirm this preliminary result.
A more demanding acid stability test was also performed. After the n-butanol was stabilized by dehydration, 0.1 wt.% methanesulfonic acid (MSA) was added, and after several days the MSA concentration increased to 1 wt.%, and the solution was dehydrated at 95 ℃. The results of all the above experiments are shown in Table 1.
Comparative example 1
Comparative example 1 is different from example 2 in that: the BTESM sol was prepared by an acid-base catalysis method, and the other operations were the same as in example 2.
(1) Dissolving 1, 2-bis (triethoxysilyl) methane (BTESM) in an alcohol solvent according to the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 50 ℃, wherein the molar ratio of BTESM to water to hydrochloric acid is 1:60: 0.1.
(2) Ammonia water according to molar ratio: adding ammonia water with the mass fraction of 5 wt% into hydrochloric acid with the proportion of 10:1, and continuously stirring for 60min at 50 ℃ in a water bath to react to generate BTESM sol.
(4) Coating silica-zirconia sol on a ceramic support to form a transition layer0.5 wt% silica-zirconia sol. The transition layer is prepared by soaking a ceramic support body in silica-zirconia sol for 10-60s, drying at room temperature for 5-10min, calcining for 15-30 min at 500-600 deg.C in air atmosphere, and repeating the process for 2-3 times, wherein the ceramic support body comprises tubular or sheet alpha-Al2O3And a support body. The transition layer can reduce the pore diameter of the surface of the membrane layer, increase the thermal stability of the membrane and prevent the occurrence of the pore permeation phenomenon. Then coating the BTESM sol prepared in the step (3) on the surface of the transition layer, coating the BTESM sol on a ceramic support containing the silica-zirconia sol transition layer through dip-coating, and carrying out flash firing in air at 250 ℃ for 20 min. Obtaining the BTESM composite membrane.
Comparative example 2
Comparative example 2 differs from example 2 in that: BTESM sol was prepared by acid catalysis, and the other operations were the same as in example 2.
(1) Dissolving 1, 2-bis (triethoxysilyl) methane (BTESM) in an alcohol solvent according to the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 50 ℃ to obtain BTESM sol, wherein the molar ratio of BTESM to water to hydrochloric acid is 1:60: 0.1.
(2) The BTESM composite membrane is prepared by adopting the BTESM sol in the step (1) under the same preparation conditions as in the step (4) of the example 2.
The performance and stability of the composite membranes were investigated under the same experimental conditions as in comparative examples 1 and 2 and example 2, and it was found that the acid resistance of the composite membranes prepared in comparative examples 1 and 2 was limited to weak acids (such as acetic acid), and the membrane structure was easily destroyed in strong acids, and thus the composite membranes could not be used for dehydration in nitric acid and MSA strong acid systems.
And when the composite membranes of the comparative examples 1 and 2 are used for dehydration in an ethanol/water/acetic acid (95/5/1.5 wt%) system, the performance is unstable, the dehydration stability is obviously reduced along with the increase of time, and the dehydration performance is kept for not more than 50h at 70 ℃.
TABLE 1
The specific conditions not specified in the examples were carried out under the usual conditions. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Obvious improvements, changes and modifications to some technical features in the foregoing embodiments can be made by those skilled in the art without departing from the technical idea of the present invention, and the technical scope of the present invention is not limited to the contents of the specification, but must be determined from the scope of the claims.
Claims (6)
1. A preparation method of an acid-resistant PSQ composite film is characterized by comprising the following steps:
(1) dissolving a PSQ precursor in an alcohol solvent, and sequentially adding hydrochloric acid, ammonia water and hydrochloric acid to perform acid-base-acid alternative catalytic reaction to obtain PSQ hydrosol; the PSQ precursor is one or two of 1, 2-di (triethoxysilyl) methane, 1, 4-di (triethoxysilyl) benzene and 1, 2-di (triethoxysilyl) ethylene; the alcohol solvent is one or two of ethanol and isopropanol;
the first step of acid catalytic reaction is to dissolve a PSQ precursor in an alcohol solvent, add hydrochloric acid and water to carry out hydrolysis reaction, wherein the molar ratio of the PSQ precursor to the water to the hydrochloric acid is 1: 30-240: 0.1, the reaction time is 10-60 min, and the reaction temperature is 40-60 ℃;
adding ammonia water after the first-step acid catalytic reaction for carrying out alkali catalytic reaction, wherein the molar ratio of the ammonia water to the hydrochloric acid in the alkali catalytic reaction is 2-10: 1, the reaction time is 5-90 min, and the reaction temperature is 40-60 ℃;
and adding hydrochloric acid after base catalysis for acid catalysis reaction, wherein the molar ratio of the hydrochloric acid to ammonia water in acid catalysis is 1-2: 1, the reaction time is 10-60 min, and the reaction temperature is 40-60 ℃;
(2) coating silica-zirconia sol on a ceramic support to generate a transition layer;
(3) and coating the PSQ hydrosol on the surface of the transition layer by dipping-pulling method to generate a separation layer, thus obtaining the PSQ composite membrane with the structure of the support layer, the transition layer and the separation layer.
2. The method for preparing the acid-resistant PSQ composite film according to claim 1, wherein: in the acid-alkali-acid alternative catalytic reaction process, the concentration of the hydrochloric acid is 1-10 wt%, and the concentration of the ammonia water is 1-10 wt%.
3. The method for preparing the acid-resistant PSQ composite film according to claim 1, wherein: the ceramic support comprises tubular or sheet alpha-Al2O3The support body has a porosity of 40-50% and a pore diameter of 50-200 nm.
4. The method for preparing the acid-resistant PSQ composite film according to claim 1, wherein: the mass concentration of the silica-zirconia sol is 0.5 wt%; the raw material of the silica-zirconia sol is one or more of tetraethoxysilane and zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium tert-butoxide through hydrolysis and copolymerization.
5. The method for preparing the acid-resistant PSQ composite film according to claim 1, wherein: and the transition layer is prepared by soaking the ceramic support body in silica-zirconia sol, drying at room temperature and calcining, wherein the calcining temperature is 500-600 ℃, the calcining atmosphere is air, and the soaking and calcining are repeated for 2-3 times.
6. The use of the acid-resistant PSQ composite film prepared by the method of any one of claims 1-5 for solvent dehydration in an acidic system.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626933A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | Polysilsesquioxane-polyacrylate-nano SiO2 composite emulsion and preparation method and application thereof |
| CN105597561A (en) * | 2015-12-25 | 2016-05-25 | 常州大学 | Preparation method and application of organosilicone sol based on pH swing |
| CN106110909A (en) * | 2016-08-03 | 2016-11-16 | 常州大学 | The preparation method of a kind of organosilicon membrane and infiltration evaporation thereof process the application of high slat-containing wastewater |
| CN106669430A (en) * | 2016-11-21 | 2017-05-17 | 重庆云天化瀚恩新材料开发有限公司 | Nano-structured organic-inorganic hybrid molecule modified reverse osmosis membrane and preparation method thereof |
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| US7771609B2 (en) * | 2002-08-16 | 2010-08-10 | Aerogel Technologies, Llc | Methods and compositions for preparing silica aerogels |
| EP1976621B1 (en) * | 2006-01-16 | 2016-10-05 | Stichting Energieonderzoek Centrum Nederland | Microporous molecular separation membrane with high hydrothermal stability |
| NL2007705C2 (en) * | 2011-11-02 | 2013-05-21 | Stichting Energie | Low cost polymer supported hybrid silica membrane and production thereof. |
| CN108423685A (en) * | 2018-04-29 | 2018-08-21 | 浙江工业大学 | The atmospheric preparation method of aerosil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626933A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | Polysilsesquioxane-polyacrylate-nano SiO2 composite emulsion and preparation method and application thereof |
| CN105597561A (en) * | 2015-12-25 | 2016-05-25 | 常州大学 | Preparation method and application of organosilicone sol based on pH swing |
| CN106110909A (en) * | 2016-08-03 | 2016-11-16 | 常州大学 | The preparation method of a kind of organosilicon membrane and infiltration evaporation thereof process the application of high slat-containing wastewater |
| CN106669430A (en) * | 2016-11-21 | 2017-05-17 | 重庆云天化瀚恩新材料开发有限公司 | Nano-structured organic-inorganic hybrid molecule modified reverse osmosis membrane and preparation method thereof |
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