KR100966306B1 - Membrane and Media of metalIII orthophosphates for extraction of bioethanol of high purity and Preparation method of the same and bioethanol of high purity - Google Patents

Abstract

The present invention relates to a trivalent metal orthophosphate separation membrane and carrier for extracting high purity bioethanol, and a method for preparing the same, and a method for producing high purity bioethanol using the separation membrane and / or carrier, and more specifically, to a sugar system (corn, sugarcane, etc.). ), 93.0 ~ 93.2v / v% obtained by treating biomass such as starch-based (potato, sweet potato, etc.), cellulose (waste wood, etc.), and seaweeds (wooden, etc.) in a continuous process such as pretreatment, fermentation, and distillation. Octagonal oxygen ring trivalent metal orthophosphate that can selectively and continuously extract high-purity bioethanol of 99.6v / v% or more that can be used for alternative fuels such as fossil fuel and gasoline by adsorption and dehydration using It relates to a separation membrane and a carrier, a method for producing the same, and a method for producing high purity bioethanol using the separation membrane and / or carrier.

Biomass, trivalent orthophosphates, separators, carriers, high purity bioethanol, alternative fuels.

Description

Membrane and Media of metal (III) orthophosphates for extraction of bioethanol of high purity and Preparation method of the same and bioethanol of high purity}

The present invention relates to a trivalent metal orthophosphate separator (Membrane) and a carrier (Media) for high purity bioethanol extraction, and to a method for producing the same and a method for producing high purity bioethanol.

In recent years, countries around the world have been devoting themselves to developing eco-friendly bioenergy to prepare for the era of high oil prices and to reduce greenhouse gases.In particular, high-purity bioethanol of 99.5v / v% or more can be used for environmental pollutants such as carbon monoxide and Since there is no emission alone or mixed with gasoline at an appropriate ratio, it can be used as an alternative fuel for automobiles.

Currently, biomass of sugars, starch, cellulose and algae such as corn, sugar cane, potatoes, sweet potatoes, cassava, tapioca, waste wood, wood, etc. is pre-processed, fermented, distilled, etc. To obtain 93.0 ~ 93.2v / v% hydrous ethanol, followed by dehydration process using liquid or solid dehydrating agent to produce 99.3 ~ 99.5v / v% bioethanol.Brazil, USA, Canada, In countries such as China, India, and Europe, bioethanol is mixed with gasoline at an appropriate ratio and used as fuel for automobiles.

In the production of bioethanol for fuel, the adsorption dehydration method is the most important core technology, the prior art there is azeotropic distillation (Azeotropic distillation) method using a liquid dehydrating agent such as benzene, hexane. This method has the advantage that it is easy to construct a large-scale production facility capable of mass production, but benzene and hexane used to form a three-component azeotropic mixture of a non-polar solvent such as water-ethanol-benzene or hexane. The back is deadly toxic and requires skilled driving skills, and also requires a large amount of energy such as water and labor.

Due to this problem, the NaA type zeolite carrier, which is a method of adsorbing a strong adsorbate at high pressure by using a difference in adsorption amount between adsorbates and desorbing the adsorbate at low pressure, continuously separating gas mixtures or removing specific components, Adsorption dehydration method using the same solid dehydrating agent (eg, Molecular sieve distillation process, MSDP method) was developed. Adsorption dewatering method using solid dehydrating agent such as NaA type zeolite carrier is suitable for large scale production equipment, and also installation and maintenance cost Has the advantage of being inexpensive, on the other hand, there is a disadvantage in that the operation operation is complicated and energy consumption is high.

Therefore, an adsorption dewatering method using a separator obtained by crystallizing NaA-type zeolite in a thin film state on a ceramic support surface has been developed, and related technology is disclosed in Korean Patent No. 10-0534666, Japanese Laid-Open Patent No. 8-318141, US Patent No. 6273937, US Patent No. 5512179, M. Kondo, M. Komori, H. Kita, K. Okamoto, J. Membrane Sci., 133 (1997), X, Xu, Y. Bao, C. Song, W. Yang, J. Liu, L. Lin, J. Membrane Sci., 249 (2005) and M. Peratitus, J. Llorens, F. Cunill, R. Mallada, J Santa Maria, Catalysis Today 104 (2005) and the like. This method is suitable for small-scale installations, and has advantages such as easy operation and high operating efficiency. On the other hand, there is a disadvantage in that the production of the separator is cumbersome and the facility construction cost is excessive and cannot be used commercially.

Specifically, M.D.Davis, Ind. Eng. Chem. Res., 30 (1991), et al., Reported that the NaA zeolite has an octagonal ring in the form of an oxygen ring and a channel diameter of 0.42 nm. Therefore, since the size of the water molecule is 0.30 nm and the size of the ethanol molecule is 0.43 nm, the zeolite separator adsorbs small water molecules into the micro-pores by using the size difference between the water and ethanol molecules, and the ethanol The molecules can be adsorbed and dehydrated by passing.

Figure 1 shows a scanning electron micrograph of the surface of the ceramic support of the NaA zeolite separator, it can be seen that there is a portion of the separator is not formed partially, in order to solve this problem, two to three separator formation process It is necessary to go through a cumbersome process.

In addition, the thickness of the separator is reported to be 5 ~ 6㎛ by the repetitive formation process as described above (M. Kondo, M. Komori, H.Kita, K. Okamoto, J. Membrane Sci., 133 ( 1997). Generally, when the thickness of the separator is thick, it is advantageous in terms of durability. However, since the arrangement of the channels becomes irregular, there is a problem that the adsorption and dehydration ability of the mixed solution of water-ethanol or the mixed gas may decrease.

On the other hand, in the case of zeolite separation membranes, they are weakly alkaline (pH 8-9). However, since water and ethanol are hydrogen bonds, cleavage of hydrogen bonds is necessary to separate them. Generally, since cleavage of hydrogen bonds is highly dependent on acidity, the weak alkalinity of the zeolite separator is water- Undesirable for adsorption dehydration on ethanol. In addition, the zeolite separator has a short service life because of its low durability against acid, alkali and water.

Recently, research has been actively conducted on octagonal oxygen ring aluminum orthophosphate (α-AlPO ₄ ) which can replace the zeolite separator as described above. Referring to the related art, CAFyfe, HMAltenschildesche, KCWong, Solid State Nuclear Mag. Res., 9 (1997), KOKongshaug, H. Fjellvag, KPLillerud, Microporous and Meso. Mater., 32 (1999), RW Broach, ST Wilson, RM Kirchner, Microporous and Meso. Mater., 57 (2003), G. Guam, T. Tanaka, K. Kusakabe, K. Sotowa, S. Morooka, J. Membrane Sci., 214 (2003), etc. Octagonal oxygen ring aluminum orthophosphate (α-AlPO) ₄ ) powder synthesis, crystal structure analysis, etc. are reported.

However, there are no reports on octagonal oxygen ring gallium orthophosphate (α-GaPO ₄ ), iron orthophosphate (α-FePO ₄ ), or manganese orthophosphate (α-MnPO ₄ ). In addition, there has been no report on a method for preparing an octagonal oxygen ring trivalent metal orthophosphate separation membrane and a carrier capable of selectively continuously extracting high purity bioethanol from the hydrous ethanol obtained from biomass by adsorption dehydration.

An object of the present invention is to provide a trivalent metal orthophosphate separation membrane and a method for preparing a carrier which can selectively and continuously extract high purity bioethanol of 99.6v / v% or more that can be used for alternative fuels such as fossil fuel and gasoline. In particular, the present invention provides a method for preparing a trivalent metal orthophosphate separation membrane and a carrier having a long service life due to its high adsorption dehydration ability and high durability against acids, alkalis and water, and a method for producing high purity bioethanol using the membrane or carrier obtained thereby. It is.

Method for producing an octagonal oxygen ring trivalent metal orthophosphate separator according to the present invention,

(1) Mixing 90-95 vol% of one or more trivalent metal orthophosphate solutions selected from gallium orthophosphate solution, aluminum orthophosphate solution, iron orthophosphate solution and manganese orthophosphate solution with ammonia or an amine compound 5-10 vol% Hydrothermally reacting the solution to prepare an octagonal oxygen ring trivalent metal orthophosphate powder;

(2) hydrothermally reacting the powder obtained in the step (1) with the ceramic support in a reverse arrangement method of placing the powder obtained in the above step (1) on the upper part of the reaction vessel and the ceramic support on the lower part, thereby Forming a separator;

(3) heat-treating the ceramic support formed with the separator obtained in step (2);

Characterized in that it comprises a.

In the method for preparing a separator according to the present invention, the trivalent metal in step (1) of preparing the octagonal oxygen ring trivalent metal orthophosphate powder is preferably selected from gallium, aluminum, iron and manganese.

The gallium orthophosphate solution used to prepare the octagonal tricyclic metal orthophosphate powder is an aqueous solution of gallium sulfate (III) and a phosphoric acid solution, preferably 85% of a phosphoric acid solution in a 1: 2 molar ratio, orthophosphoric acid. The aluminum solution is an aqueous solution of aluminum sulfate (or aluminum hydroxide) and a phosphate solution, preferably 85% of a phosphate solution in a 1: 2 molar ratio, and the iron orthophosphate solution is an iron (III) sulfate and a phosphate solution, preferably 85 As for the aqueous solution which mixed the% phosphoric acid solution in 1: 2 molar ratio, and the manganese orthophosphate solution, the aqueous solution which mixed manganese sulfate (III) and phosphoric acid solution, Preferably 85% phosphoric acid solution in 1: 2 molar ratio is preferable. . The gallium orthophosphate solution, aluminum orthophosphate solution, iron orthophosphate solution and manganese orthophosphate solution (hereinafter also referred to as "starting solution") may be used alone or in combination.

In order to prepare an octagonal oxygen ring trivalent metal orthophosphate powder, ammonia or an amine compound should be added to the starting solution, and if the hydrothermal reaction is performed only with the starting solution without adding the ammonia or amine compound, the hexagonal oxygen ring trivalent Metal orthophosphate powder is obtained.

The ammonia or amine compound added to the starting solution is not particularly limited in its kind, but ethylenediamine, isopropylamine or tetraethylammonia is preferable, and the content thereof is It is preferable to add 5-10 vol% based on the total amount of the starting solution and the ammonia or amine compound. When the addition amount is less than 5 vol% or more than 10 vol%, octahedral oxygen ring trivalent metal orthophosphate powder cannot be obtained in a single phase.

Powder synthesis or crystallization of the mixed solution of the trivalent metal orthophosphate starting solution and ammonia or an amine compound includes hydrothermal method, wet method, sol-gel method or evaporation method, but does not require grinding and heat treatment. In addition, a high purity powder and a hydrothermal method capable of crystallization are preferred.

Hydrothermal method is a method using a reaction occurring under high temperature and high pressure of 100 ° C or higher in the presence of water (or aqueous solution) in a tightly sealed autoclave, that is, a hydrothermal reaction. It is suitable for the preparation method of trivalent metal orthophosphate powder because it can utilize at the same time.

The reaction vessel used for the hydrothermal reaction in step (1) may be either vertical or horizontal, but in order to obtain a single phase powder and to increase the yield at the same time, the horizontal type is preferable to the vertical type. .

The temperature for hydrothermally reacting the trivalent metal orthophosphate starting solution and the mixed solution of ammonia or an amine compound in a sealed state in the reaction vessel is preferably 200 to 210 ° C., and the reaction time is preferably 24 to 30 hours. If the hydrothermal reaction conditions are out of 200 ~ 210 ℃ or 24 ~ 30 hours, the yield of the powder produced is low, and the crystallinity is also inferior.

The octagonal oxygen ring trivalent metal orthophosphate powder prepared as described above has a reverse solubility curve. Figure 2 shows the results of measuring the temperature dependence of the solubility of the octagonal oxygen ring ortho gallium phosphate powder by the weight loss method.

Unlike conventional zeolite powder having a regular solubility curve, the octagonal oxygen ring trivalent metal orthophosphate powder has a reverse solubility curve as described above, and thus, the step (2) for forming a separator In the reaction vessel, it is preferable to use a hydrothermal method that induces a hydrothermal reaction by a reversed arrangement method in which a starting material is placed at an upper portion (low temperature region) and a ceramic support at a lower portion (high temperature region).

The ceramic support used in step (2) is preferably a porous rectangular or tubular ceramic support mainly composed of alumina or mullite.

The reaction vessel used in the step (2) can be used both horizontal or vertical type, it is easy to form the temperature difference between the high temperature region and the low temperature region, and the vertical type is used to efficiently induce convection and ion diffusion. desirable.

In the step (2), the temperature of the hydrothermal reaction is preferably 240 ° C. or higher, 250 ° C. or higher for gallium orthophosphate, 240 ° C. or higher for aluminum orthophosphate, or 270 ° C. or higher for iron orthophosphate, orthophosphoric acid In the case of manganese, 270 degreeC or more is more preferable. When the hydrothermal reaction condition is less than 240 ℃, the separator is not formed on the ceramic support.

In addition, gallium orthophosphate (α-GaPO4), aluminum orthophosphate (α-AlPO4), ortho iron phosphate (α-FePO4) and manganese orthophosphate (α-MnPO4) powders have a crystal structure of α type (low temperature). Phase transition from the low temperature form) to the β type (high temperature form), the production of the separator is preferably made at 570 ℃ or less.

In the hydrothermal reaction in step (2), the hydrothermal solvent used is preferably water, the reaction time is preferably 3 days or more, particularly 3-7 days. If the reaction time is less than 3 days, since the octagonal oxygen ring trivalent metal orthophosphate aqueous solution does not reach an equilibrium state, a uniform separator is not formed, and if it is 3 days or more, a uniform separator is formed. Figure 3 shows the results of measuring the time dependence of the solubility of the octagonal oxygen ring gallium orthophosphate powder under hydrothermal conditions using a reaction temperature of 250 ℃ and water as a hydrothermal solvent.

In the step (3), the ceramic support formed with the separator obtained in the step (2) is washed with water and dried, and then heat treated at a temperature of 400 to 500 ° C. for 5 to 12 hours to form the inside of the separator formed on the ceramic support. The remaining ammonia or amine compound is completely removed.

If the heat treatment time is less than 5 hours, the material of the ammonia or the amine compound is not sufficiently removed, and if more than 12 hours, the material is completely removed, and thus it is not necessary to further heat treatment. When the temperature of the heat treatment is less than 400 ° C, the material of the ammonia or amine compound is not sufficiently removed, and when the temperature exceeds 500 ° C, the phase transition of the separator occurs.

Method for producing an octagonal oxygen ring trivalent metal orthophosphate carrier according to the present invention,

(i) Mixing 90 to 95 vol% of one or more trivalent metal orthophosphate solutions selected from gallium orthophosphate solution, aluminum orthophosphate solution, iron orthophosphate solution and manganese orthophosphate solution with 5 to 10 vol% ammonia or amine compounds Hydrothermally reacting the solution to prepare an octagonal oxygen ring trivalent metal orthophosphate powder;

(ii) mixing 65 to 75 wt% of the powder obtained in step (i), 5 to 10 wt% of kaolin or bentonite as a plasticizer, 5 to 10 wt% of silica or diatomaceous earth as a sintering agent, and 15 to 20 wt% of water as a binder, forming and Drying and then solidifying to prepare a carrier;

Characterized in that it comprises a.

In the method for preparing the octagonal oxygen ring trivalent metal orthophosphate carrier, the description of step (i) is the same as that of step (1) of the membrane production method described above.

In the step (ii), a plasticizer, a sintering agent and a binder are mixed with the octagonal oxygen ring trivalent metal orthophosphate powder to prepare a carrier.

The plasticizer is preferably plate-shaped kaolin or bentonite, silica or diatomite is preferred as the sintering agent, and water is preferred as the binder.

In the step (ii), the content of each component is preferably octagonal oxygen ring trivalent metal orthophosphate powder 65 ~ 75wt%, plasticizer 5 ~ 10wt%, sintering agent 5 ~ 10wt%, binder 15 ~ 20wt% Do. If it is out of the content ratio, the functionality of the prepared carrier is inferior.

After the mixing, molding is carried out in the form of a sphere having a large specific surface area. In the present invention, it is preferable to use a commercially available pilling machine for shaping the mixed powder.

After the molding of the mixed powder is subjected to a drying process, the drying is preferably carried out for 18 to 30 hours in the temperature range of 90 ~ 100 ℃ after first drying naturally. If the solid phase reaction is carried out without drying the molded body, it is not preferable because a phenomenon such as cracking or breakage occurs.

After the drying process, the solid phase reaction for 10 to 12 hours in the temperature range of 500 ~ 550 ℃. If the temperature of the solid phase reaction is less than 500 ℃, the reaction is not sufficient, if the temperature exceeds 550 ℃, the phase transition of the carrier occurs, if the time of the solid phase reaction is less than 10 hours, the sintered state is not complete, if more than 12 hours Since it is sintered, there is no need to react any more.

The present invention relates to a module comprising a separator provided by the present invention alone or to a module comprising the separator and a module comprising a carrier provided by the present invention to the hydrous ethanol obtained from biomass, the module containing the separator alone or It provides a high-purity bioethanol production method characterized in that the high-purity bioethanol is obtained by passing through a module connecting the separator containing module and the carrier containing module.

In the manufacture of the module using the above-mentioned separator, the shape of the ceramic support is rectangular, tubular, or the like, and preferably tubular. The length of the ceramic support is preferably 1 meter or more. If the length is less than 1 meter, the specific surface area becomes small, which makes mass extraction of high purity bioethanol difficult.

In the production of the module using the carrier, a cylinder can be used, and the carrier can be filled in the cylinder vertically or horizontally. Preferably, the carrier is filled in a cylindrical shape vertically.

In order to manufacture high purity bioethanol, the membrane module may be used alone or may be used by connecting the membrane module and the carrier module, and the membrane module and the carrier module are preferably used together.

The biomass used in the method for producing high-purity bioethanol of the present invention is used in the seaweeds such as sugars such as corn and sugar cane, starch based potatoes, sweet potato, cassava and tapioca, cellulose based waste wood, and wood starfish. One or more types selected can be mentioned.

The high purity bioethanol prepared through the module of the present invention as described above has a high purity of 99.6 v / v% or more, and the high purity bioethanol prepared from 99.6v / v% or more of 10-20 wt% and gasoline 80-90 wt%. A mixed solution or a mixed solution of 10 to 20wt% of high purity bioethanol of 99.6v / v% or more, 3 to 5wt% of isopropyl alcohol and 75 to 85wt% of gasoline can be used as an alternative fuel such as fossil fuel or gasoline. .

Since the octagonal oxygen ring trivalent metal orthophosphate separator and carrier prepared by the present invention show weak acidity or neutral pH (pH 6 ~ 7), adsorption and dehydration ability is higher than that of conventional zeolite separator and carrier, and also acid, alkali and water Due to its high durability, the service life can be long.

In addition, by manufacturing a trivalent metal orthophosphate separation membrane and a carrier for high purity bioethanol extraction, which could not be achieved in the prior art, it is possible to solve the problems of the zeolite separation membrane and the like.

And high-purity bioethanol prepared by the present invention can be used as an environmentally friendly fuel that can replace fossil fuel, gasoline, etc., because there is no emission of environmental pollutants such as carbon monoxide, nitrogen oxide, etc. during combustion.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are for illustrative purposes only, and the present invention is not limited by the following examples.

Example  One

<Membrane Manufacturing>

Mixed solution prepared by adding 295.8 ml of 8vol% isopropylamine (99% purity) to 1204.2 ml of gallium orthophosphate starting solution prepared by mixing gallium sulfate (III) and 85% phosphoric acid solution in a 1: 2 molar ratio. After filling 1,500ml in a horizontal reaction vessel and sealing it tightly, and performing a hydrothermal reaction for 24 hours at a reaction temperature of 210 ℃ and filtered through a slurry (Slurry) while washing with distilled water and filter paper. After drying for 24 hours at 95 ℃ 635.2g of a powder having a particle size of 1 ~ 10㎛. Here, 120 g of powder was taken and placed in a separate container in the upper portion of the vertical reaction vessel (low temperature region), and a ceramic support (outer diameter 41 mm, inner diameter 30 mm, length 300 mm) was placed in the lower portion of the reaction vessel (high temperature region), and a hydrothermal solvent was placed. After adding 2,140 ml of water (distilled water) as a semi-applicator, the semi-applicator was tightly sealed, followed by hydrothermal reaction for 5 days at a reaction temperature of 250 ° C. After the hydrothermal reaction was completed, the ceramic support was washed with distilled water, dried at 95 ° C. for 24 hours, and then heat-treated at 480 ° C. for 10 hours. The photograph of the ceramic support body in which the separator of the octagonal oxygen ring gallium orthophosphate which was produced in this way was formed is shown in FIG. 5 shows a photograph of a scanning electron microscope for the cross section of the separator, its thickness was 2 to 3 μm, and the pH value of the separator was 6 to 7. FIG. On the other hand, the used system (durability) of the ceramic support on which the gallium ortho phosphate separator was formed was 30 to 34 months, and when this period was exceeded, the purity of bioethanol dropped to 99.6 v / v% or less.

< carrier  Manufacture

 The carrier is a spherical shaped body having a size of 2 to 5 mm using a pill maker with a mixed powder consisting of a mixture ratio of 70 wt% of octagonal oxygen ring gallium orthophosphate powder, 5 wt% of bentonite powder, 5 wt% of diatomaceous earth powder and 20 wt% of water. After the preparation, it was naturally dried, and after drying at 95 ° C. for 24 hours, was prepared through a solid phase reaction at 500 ° C. for 12 hours. Figure 6 shows a photograph of the octagonal oxygen ring gallium phosphate carrier. The pH value of such a carrier was 6-7, and the service life (durability) was 34-36 months. When this period was exceeded, the purity of bioethanol tended to fall below 99.6v / v%.

<Production of High Purity Bioethanol>

7 is a vertical support module (outer diameter 110mm, height 160mm, internal volume; 1,520cm ³ ) containing a carrier in a cylindrical cylinder connected continuously after mounting the module with a ceramic support (60mm in diameter, 50mm in inner diameter, 310mm in length) with a separator formed alone The high purity bioethanol production equipment including the adsorption dehydration device, which was manufactured by mounting alone, was shown. The pilot plant's production equipment consists of ① steam generation (heating) system, ② hydrous ethanol storage tank, ③ membrane module, ④ carrier module, ⑤ water recovery tank, ⑥ cooling system, ⑦ high purity bioethanol recovery tank The production scale is 540 ~ 600ℓ per month. Gas chromatographic analysis (total area; 35268263, ethanol area; 35137771) of bioethanol extracted by pervaporation of 93.0v / v% hydrous ethanol obtained from biomass using this equipment was performed. As shown in FIG. High purity bioethanol of 99.6 v / v% was prepared.

As a result of using a mixed solution of 99.6v / v% or more of high purity bioethanol prepared in the present example in gasoline at a ratio of 15 ± 5wt% as a gasoline alternative fuel, the use of gasoline alone in the starting, running, acceleration, etc. There was no big difference.

Example  2

In Example 1, in the method for preparing octagonal oxygen ring trivalent metal orthophosphate powder, 1204.2 ml of the starting solution of ortho aluminum phosphate prepared by mixing aluminum sulfate and 85% phosphoric acid solution in a 1: 2 molar ratio. 1,500 ml of a mixed solution prepared by adding 295.8 ml of 9 vol% tetraethylammonia was used; In the production of the separator, the hydrothermal reaction temperature is 245 ℃; And in the preparation of the carrier, the same method as in Example 1 except for the use of a mixed powder of octagonal oxygen ring orthophosphate powder 70wt%, plate-shaped kaolin powder 10wt%, diatomaceous earth powder 5wt% and water 15wt% as a mixed powder A membrane and a carrier were prepared, and high purity bioethanol of 99.6 v / v% was obtained using a production facility including a membrane module and a carrier module, respectively.

Example  3

In Example 1, the starting solution of iron orthophosphate prepared by mixing the octagonal oxygen ring trivalent metal orthophosphate powder in a 1: 2 molar ratio with iron (III) sulfate and 85% phosphoric acid solution. 1,500 ml of a mixed solution prepared by adding 295.8 ml of 9 vol% tetraethylammonia to 1204.2 ml; In the production of the separator, the hydrothermal reaction temperature is 275 ℃; And in the preparation of the carrier, the same method as in Example 1 except for the use of a mixed powder of octagonal iron ring orthophosphate powder 70 wt%, plate-shaped kaolin powder 10wt%, silica powder 5wt% and water 15wt% as a mixed powder. A membrane and a carrier were prepared, and high purity bioethanol of 99.6 v / v% was obtained using a production facility including a membrane module and a carrier module, respectively.

Example  4

In Example 1, the starting solution of manganese orthophosphate prepared by mixing manganese sulfate (III) and 85% phosphoric acid solution in a 1: 2 molar ratio in the method of preparing an octagonal oxygen ring trivalent metal orthophosphate powder 1,500 ml of a mixed solution prepared by adding 295.8 ml of 8 vol% isopropylamine to 1204.2 ml; In the production of the separator, the hydrothermal reaction temperature is 280 ℃; And in the preparation of the carrier, the same method as in Example 1 except for the use of a mixed powder of octagonal manganese ring orthophosphoric acid powder 70wt%, plate-shaped kaolin powder 10wt%, silica powder 5wt% and water 15wt% as a mixed powder. A membrane and a carrier were prepared, and high purity bioethanol of 99.6 v / v% was obtained using a production facility including a membrane module and a carrier module, respectively.

1 is a scanning electron micrograph of the surface of a ceramic support of a conventional NaA zeolite separator.

FIG. 2 is a graph showing the temperature dependence of solubility for octagonal oxygen ring gallium orthophosphate powder.

3 is a graph showing the time dependence of the solubility of the octagonal oxygen ring gallium orthophosphate powder.

4 is a photograph of a ceramic support on which an octagonal oxygen ring gallium orthophosphate separator prepared in accordance with Example 1 of the present invention is formed.

FIG. 5 is a photograph of a scanning electron microscope of a cross section of a ceramic support on which a octagonal oxygen ring gallium orthophosphate separator prepared according to Example 1 of the present invention is formed. FIG.

6 is a photograph of a octagonal oxygen ring gallium orthophosphate carrier prepared according to Example 1 of the present invention.

Figure 7 is a photograph of the high purity bioethanol production equipment used in Example 1 of the present invention.

FIG. 8 is a result of gas chromatography analysis of bioethanol extracted by pervaporation of 93.0v / v% hydrous ethanol obtained from biomass using the high purity bioethanol production equipment of FIG. 7.

Claims (15)

(1) Mixing 90-95 vol% of one or more trivalent metal orthophosphate solutions selected from gallium orthophosphate solution, aluminum orthophosphate solution, iron orthophosphate solution and manganese orthophosphate solution with ammonia or an amine compound 5-10 vol% Hydrothermally reacting the solution to prepare an octagonal oxygen ring trivalent metal orthophosphate powder; (2) hydrothermally reacting the powder obtained in the step (1) with the ceramic support in a reverse arrangement method of placing the powder obtained in the above step (1) on the upper part of the reaction vessel and the ceramic support on the lower part, thereby Forming a separator; (3) heat-treating the ceramic support formed with the separator obtained in step (2); Method for producing a octagonal oxygen ring trivalent metal orthophosphate separator for high purity bioethanol extraction comprising a. The gallium orthophosphate solution, the aluminum orthophosphate solution, the iron orthophosphate solution and the manganese orthophosphate solution are gallium sulfate (III), aluminum sulfate or aluminum hydroxide, iron (III) sulfate and manganese sulfate (III), respectively. ) Is prepared by mixing a phosphoric acid solution with a 1: 2 molar ratio. The method of claim 1, wherein the ammonia or amine compound in step (1) is a tetraethylammonia, ethylenediamine or isopropylamine, characterized in that the preparation of octagonal oxygen ring trivalent metal orthophosphate separation membrane for high purity bioethanol extraction Way. According to claim 1, wherein the hydrothermal reaction in the step (1) the production of octagonal oxygen ring trivalent metal orthophosphate separation membrane for high purity bioethanol extraction, characterized in that carried out for 24 to 30 hours at a temperature of 200 ~ 210 ℃ Way. According to claim 1, wherein the hydrothermal reaction in the step (2) of the octagonal oxygen ring trivalent metal orthophosphate separation membrane for high purity bioethanol extraction, characterized in that performed for 3 to 7 days at a temperature of 240 ~ 270 ℃ Way. The method according to claim 1, wherein the heat treatment in step (3) is performed for 8 to 12 hours at a temperature of 400 to 500 ° C. for extracting an octagonal oxygen ring trivalent metal orthophosphate membrane for extracting high purity bioethanol. . (i) Mixing 90 to 95 vol% of one or more trivalent metal orthophosphate solutions selected from gallium orthophosphate solution, aluminum orthophosphate solution, iron orthophosphate solution and manganese orthophosphate solution with 5 to 10 vol% ammonia or amine compounds Hydrothermally reacting the solution to prepare an octagonal oxygen ring trivalent metal orthophosphate powder; (ii) mixing 65 to 75 wt% of the powder obtained in step (i), 5 to 10 wt% of kaolin or bentonite as a plasticizer, 5 to 10 wt% of silica or diatomaceous earth as a sintering agent, and 15 to 20 wt% of water as a binder, forming and Drying and then solidifying to prepare a carrier; Method for producing a octagonal oxygen ring trivalent metal orthophosphate carrier for high purity bioethanol extraction comprising a. The method of claim 7, wherein the ammonia or the amine compound in step (i) is tetraethylammonia, ethylenediamine or isopropylamine for the preparation of octagonal oxygen ring trivalent metal orthophosphate carrier for high purity bioethanol extraction, characterized in that Way. According to claim 7, wherein the hydrothermal reaction in the step (i) the production of octagonal oxygen ring trivalent metal orthophosphate carrier for high purity bioethanol extraction, characterized in that carried out for 24 to 30 hours at a temperature of 200 ~ 210 ℃ Way. The method of claim 7, wherein the solid phase reaction in the step (ii) of the octagonal oxygen ring trivalent metal orthophosphate carrier for high purity bioethanol extraction, characterized in that carried out for 10 to 12 hours at a temperature of 500 ~ 550 ℃ Way. A octagonal oxygen ring trivalent metal orthophosphate separator for extracting high purity bioethanol prepared by the method of claim 1. An octagonal oxygen ring trivalent metal orthophosphate carrier for extracting high purity bioethanol prepared by the method of claim 7. A module comprising the separator of claim 11 or a module comprising the separator and a module comprising the carrier of claim 12 is connected to the hydrous ethanol obtained from biomass, the membrane containing module alone or the module containing the membrane and the carrier containing module A method of producing high purity bioethanol, characterized by obtaining high purity bioethanol by passing through a connected module. The method of claim 13, wherein the biomass is at least one selected from the group consisting of corn, sugar cane, potatoes, sweet potatoes, cassava, tapioca, waste wood, and loach. The method for producing high purity bioethanol according to claim 13, wherein the obtained high purity bioethanol has a purity of 99.6 v / v% or more.

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