KR101721960B1 - manufacturing method of decyl glucoside using zeolite catalyst - Google Patents

Abstract

The present invention relates to a method for producing decyl glucoside by using a zeolite catalyst. More specifically, the present invention relates to a method for producing decyl glucoside, wherein the method improves the yield of glucoside and simultaneously selectively adjusts the yield of a specific product by using a zeolite catalyst. The method of the present invention comprises: a feeding step of feeding 200 to 3000 parts by weight of decanol on the basis of 100 parts by weight of glucose; and a reacting step of generating decyl glucopyranoside and decyl glucofuranoside by reacting glucose and the decanol under a zeolite catalyst.

Description

[0001] The present invention relates to a method for preparing decyl glucoside using a zeolite catalyst,

The present invention relates to a method for producing decyl glucoside using a zeolite catalyst, and more particularly, to a method for producing decyl glucoside using a zeolite catalyst, which can improve the yield of decyl glucoside and selectively control the yield of a specific product And a manufacturing method thereof.

An interface is the interface between gas and liquid, liquid and liquid, liquid and solid. Surfactants play a role in alleviating the boundaries of these interfaces. Surfactants are substances adsorbed on the surface of a liquid to enhance the activity of the interface and significantly change the properties of the liquid. Particularly, it has excellent detergency, dispersing ability, emulsifying power, solubilizing power and sterilizing power while lowering the surface tension, and is widely used in industrial fields including household detergents.

Surfactants are widely used as foods, emulsifiers for cosmetics, and moisturizers in addition to detergent raw materials. Surfactants have a chemical structure that is hydrophilic and lipophilic in one molecule. Surfactants vary in their chemical properties even though they are slightly modified. In general, surfactants are classified as anionic, cationic, amphoteric, nonionic, and special surfactants depending on the charge of the hydrophilic moiety when dissociated from water.

Some of the surfactants pollute the environment due to low biodegradability and exhibit high irritation to the human body. Therefore, such a problem is increasing as the demand increases. Therefore, in the field of surfactants, much efforts have been made to develop a surfactant which is very less irritating to the environment and human body, and in particular, a surfactant using glucose, which exists in the natural world, among which glucose and higher fatty alcohols The high-alkylpolyglucoside prepared by the above process has attracted attention as a surfactant.

Natural high-grade alkylpolyglucosides are very good biodegradable, and have better bubble power and detergency than other non-ionic surfactants. Especially, since they are remarkably low in irritation to the skin and eyes, they can be used for body wounds, , Kitchen products, cosmetics, etc., can be used instead of the existing surfactants.

Decyl glucoside is an alkylpolyglucoside, a sugar-free vegetable non-ionic surfactant derived from sugarcane, corn, coconut, and palm kernel oil. Decyl glucoside is used as a raw material for surfactants and detergents necessary for the production of cosmetics and shampoos because it has no skin irritation.

The alkylpolyglucoside is known to be prepared by the Fisher method in which glucose is reacted with a lower alcohol such as methyl alcohol or ethyl alcohol in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid, But it can not be applied to the case of a higher alcohol having a higher alcohol content.

It is also possible to acetylate the hydroxyl group of glucose using bromination of Koenigs-Knorr and then brominate to the alpha carbon position and react with higher alcohols in the presence of a Lewis acid catalyst (Noller and Rockwell) published in the Journal of the American Chemical Society (J. Am. Chem. Soc., 96, 2076, 1938), a method for producing hexyl, octyl, decyl and dodecyl glucoside.

Although this method provides the first method for producing glucoside, it is difficult to industrially use it because of the disadvantage of using expensive reagents through a lot of manufacturing steps. Baak, W., et al., 1971, discloses a method for preparing a lower alkylpolyglucoside by first using butyl alcohol in the presence of a sulfuric acid catalyst, adding a higher alcohol thereto and then exchanging glucosylation to produce a higher alkylpolyglucoside And a similar method has been disclosed in US Pat. No. 3,707,535 in 1972 by the method of trans-glucosidation using methoxyethyl alcohol, ethoxyethyl alcohol, ethoxypropanol, butoxyethanol, etc., The production method requires a step of separating and purifying the low-alcohol forming the reaction solvent-reactive intermediate and the reaction product-producing ratio. On the other hand, since the residual wastewater containing the catalyst used in the reaction is acidic and requires a process for neutralizing the same, the process is complicated and the efficiency is low.

Korean Patent No. 10-0179519 discloses a process for producing a high purity high alkyl polyglycoside.

The patent discloses that glucose is reacted with a higher fatty alcohol in the presence of an organic acid catalyst such as phosphoric acid, oxalic acid, sulfosuccinic acid, paratoluenesulfonic acid and the like, neutralized and adsorbed with a neutralized adsorbent to remove the acid catalyst and decolorized using an oxygen- , The undegraded decolorizing agent is decomposed at a high temperature using a heat exchanger to produce a high alkylpolyglucoside.

Korean Patent No. 10-0179519: Method for producing high purity high alkyl polyglycoside

The present invention has been made in order to overcome the above problems, and it is an object of the present invention to provide a method of separating a catalyst after reaction by using zeolite instead of sulfuric acid, hydrochloric acid or organic acid conventionally used as a catalyst, The present invention provides a method for producing decyl glucoside.

It is another object of the present invention to provide a method for producing decyl glucoside which can improve the yield of decyl glucoside and selectively control the yield of a specific product by the kind of zeolite.

In order to accomplish the above object, there is provided a method for preparing decyl glucoside using the zeolite catalyst according to the present invention, comprising: feeding 200 to 3000 parts by weight of decanol to 100 parts by weight of glucose into a reactor; And a reaction step of reacting the glucose and the decanol under a zeolite catalyst to produce decyl glucopyranoside and decyl glucofuranoside.

Wherein the reaction step comprises the steps of: a) injecting nitrogen into the reactor to remove air from the reactor into which the glucose and the decanol have been charged, and b) charging the internal temperature of the reactor to 80 ° C C) stirring the mixture at 500 rpm for 30 minutes after acetic acid is injected into the reactor after the primary stirring, and d) stirring the mixture in the reactor after the secondary stirring, Zeolite catalyst is injected into the reactor, and then the internal temperature of the reactor is maintained at 80 ° C, followed by 3 rd stirring at 500 rpm for 1 hour. E) After the third stirring, the internal temperature of the reactor is raised to 130 ° C, And stirring the mixture at 500 rpm for 4 hours.

The zeolite catalyst is any one selected from H-MOR, H-MFI, H-FAU and H-BEA.

To increase the selectivity of the desilyl glucopyranoside, any one of H-MFI and H-FAU was used as the zeolite catalyst, and H-MOR and H-FAO were used as the zeolite catalyst in order to increase the selectivity of the desilyl glucopyranoside. BEA is used.

Wherein the H-MFI has a Si / Al molar ratio of 25, the H-FAU has a Si / Al molar ratio of 3, the H-MOR has a Si / Al molar ratio of 10, to be.

As described above, according to the present invention, since zeolite is used instead of sulfuric acid, hydrochloric acid or organic acid conventionally used as a catalyst, it is easy to separate the catalyst after the reaction and a neutralization treatment step is not necessary. Further, when the separated and recovered catalyst is calcined at 550 DEG C for about 5 hours, the catalyst performance can be recovered and reused, which is economically advantageous.

The present invention can greatly improve the yield of decyl glucoside by reacting zeolite with a catalyst. In addition, the yield of any one of decyl glucopyranoside and decyl glucopuronoside, which are reaction products, can be selectively controlled by controlling the kind of zeolite.

1 is a graph showing an X-ray diffraction pattern of MOR (10), MFI (25), FAU (3) and BEA (13)
FIG. 2 is a SEM image of the MOR 10, FIG. 3 is the MFI 25, FIG. 4 is the FAU 3, and FIG.
6 is a graph showing nitrogen adsorption isotherms of MOR (10), MFI (25), FAU (3) and BEA (13)
7 is a graph showing NH ₃ -TPD curves of H-MOR (10), H-MFI (25), H-FAU (3) and H-
8 is a graph showing NH ₃ -TPD curves of H-MFI 25, H-MFI 50, H-MFI 75 and H-MFI 350 catalysts,
9 is a graph showing conversion ratios with respect to the weight ratio of catalyst / glucose in order to investigate the change in the conversion rate of glucose according to the injection amount of the catalyst,
10 is a graph showing the conversion of glucose in H-MOR (10), H-MFI (25), H-FAU (3) and H-BEA (13)
11 is a graph showing the surface tension and contact angle of decyl glucopyranoside and nonylphenol,
12 is a graph comparing the proliferation of estrogen MCF-7 cells against 17? -Estradiol, nonylphenol, and decyl glucopyranoside.

Hereinafter, a method for preparing decyl glucoside using a zeolite catalyst according to a preferred embodiment of the present invention will be described in detail.

The present invention relates to a process for producing an alkyl glucoside of Chemical Formula 1 or Chemical Formula 2 by reacting glucose with an alcohol. In the formulas (1) and (2), 'R' means an alkyl group (C _n H _{2n + 1} , n = 6 to 12).

Glucose is a monosaccharide having six carbon atoms and having an aldehyde group, and glucose (D-glucose) can be used.

As the alcohol, a higher alcohol having 6 to 12 carbon atoms can be used. For example, hexanol, heptanol, octanol, nonano, decanol, undecanol, dodecanol, and the like. When the carbon number is less than 6 or the carbon number exceeds 12, the surfactant does not function as a surfactant since it is difficult to satisfy physical and chemical properties required of the surfactant such as viscosity and density of the produced alkyl glucoside.

The alcohol may be used at 2 to 30 times the weight of the glucose.

Alkyl glucoside is a kind of nonionic surfactant. It has excellent biodegradability, good bubble power and detergency, and low stimulus to human body. Therefore, alkyl glucoside can be used as a detergent for western line, a product for children, a shampoo, And is widely used.

The alkyl glucoside produced by the reaction of glucose and alcohol has different alkyl groups depending on the kind of alcohol. In particular, when decyl alcohol is used, decyl glucoside is produced. Decyl glucoside is used as a raw material for surfactants and detergents necessary for the production of cosmetics and shampoos because it has no skin irritation.

The decyl glucoside produced in the present invention is decyl glucopyranoside whose sugar component is pyranose type and decyl glucofuranoside whose sugar component is furanose type.

The reaction in which desilyl glucopuronoside and decyl glucopyranoside are produced by the reaction of D-glucose and decanol can be shown as an example.

The present invention uses zeolite as a solid catalyst as a reaction catalyst. The present invention can improve the yield of decyl glucoside and selectively control the yield of a specific product by using a zeolite catalyst.

Zeolite is a general term of crystalline porous aluminosilicate, and the basic unit of the structure has a tetrahedral structure.

The International Zeolite Association (IZA) summarizes the skeletal structure of zeolite and zeolite-like materials and marks each skeletal structure as an IZA code consisting of three alphabetic characters. Examples of the zeolite that can be used in the present invention include MOR, MFI, FAU, and BEA. MOR, MFI, FAU, and BEA zeolites may also include acid forms such as H-MOR, H-MFI, H-FAU and H-BEA. 'H-' means ion exchange of Na ⁺ ion in zeolite skeleton with H ⁺ ion.

The zeolite catalyst preferably has a Si / Al molar ratio of 2 to 500. When the molar ratio of Si / Al is less than 2, the synthesis of zeolite is difficult. When the molar ratio of Si / Al exceeds 500, the content of aluminum is very low, so that the acid sites participating in the reaction are insufficient and the synthesis reaction of decyl glucoside is difficult to occur.

The amount of the catalyst used in the reaction is suitably 5 to 50 parts by weight based on 100 parts by weight of glucose. If the amount of the catalyst is less than 5 parts by weight, dissolution of glucose to alcohol does not occur well and conversion is low. When the amount of the catalyst is more than 50 parts by weight, stirring of the reactant becomes difficult.

To prepare the decyl glucoside, first, an input step of feeding 200 to 3000 parts by weight of decanol to 100 parts by weight of glucose is carried out.

A batch reactor in which a condenser is installed as a reactor can be used. Also, a reactor capable of temperature maintenance and magnetic stirring is used as the reactor.

Next, a reaction step of adding glucose and decanol to the reactor and then reacting glucose and decanol under a zeolite catalyst to produce decyl glucoside is performed. During the reaction, the reactants vaporized in the reactor may be liquefied in the condenser and then introduced into the reactor.

In order to carry out the reaction step, it is possible to inject glucose and decanol into the reactor and directly inject the zeolite catalyst into the reactor, but in this case, the solubility of glucose to decanol is low and the reactivity is low. Therefore, as a technical means for increasing the solubility of glucose, acetic acid is injected into the reactor before the zeolite catalyst is injected into the reactor and stirred at a constant temperature.

Specifically, the reaction step may be performed by the following detailed process as an example.

The reaction step includes the steps of: a) injecting nitrogen into the reactor to remove air inside the reactor into which glucose and decanol are introduced; b) maintaining the internal temperature of the reactor at 80 ° C after nitrogen charging, C) adding acetic acid to the reactor after the primary agitation and then agitating the reactor at 500 rpm for 30 minutes, d) adding the zeolite catalyst to the reactor after the secondary agitation, Maintaining the internal temperature of the next reactor at 80 ° C and then performing third stirring at 500 rpm for 1 hour, e) after the third stirring, raising the internal temperature of the reactor to 130 ° C, .

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

(Example)

1. Reaction experiment

Decyl glucoside was prepared through a solid-liquid reaction. 2.5 g of D-glucose (Sigma, 99%) and 50 ml of 1-decanol (Sigma, 99%) were mixed with 1.0 g of the catalyst and reacted. The reactor was a batch reactor equipped with a condenser. Reactants and zeolite catalysts were placed in a reactor capable of temperature maintenance and magnetic stirring and reacted.

For the reaction, 2.5 g of D-glucose (Sigma, 99%) and 50 mL of 1-decanol (Sigma, 99%) were added to the reactor.

Nitrogen was injected into the reactor to remove the air inside the reactor into which the glucose and decanol were introduced, and the internal pressure of the reactor was filled with nitrogen to 1 atm. After the reactor was sealed with nitrogen, the internal temperature of the reactor was raised to 80 DEG C, and the reactor was stirred at 500 rpm for 20 minutes. After the primary agitation, 5 ml of acetic acid was injected into the reactor using a syringe, and then the secondary agitation was performed at 500 rpm for 30 minutes. After the secondary agitation, the inlet of the reactor was opened and 1.0 g of zeolite catalyst was injected, and the reactor was sealed. The internal temperature of the sealed reactor was maintained at 80 캜, and then stirred for 3 hours at 500 rpm for 1 hour. After the third stirring, the internal temperature of the reactor was raised to 130 ° C, followed by stirring for 5 hours at 500 rpm for 4 hours to produce decyl glucoside. The fourth agitation was carried out while the vaporized reactants in the reactor were liquefied in a condenser maintained at 5 캜 and then introduced into the reactor again.

The composition of the product produced by the reaction was analyzed with a capillary column (HP-1, 50 mm) and a gas chromatograph (GC) equipped with an FID detector (Younglin Co.). The analysis conditions were as follows: the temperature of the detector and the injector was raised to 250 ° C at a rate of 10 ° C / min at 250 ° C and the temperature of the column was maintained at 20 ° C for 20 minutes.

2. Zeolite catalyst

MOR, MFI, FAU and BEA zeolites with different pore sizes and different acidities were used as zeolite catalysts.

MFI zeolite was prepared by mixing synthetic mother liquor containing colloidal silica (Ludox, 40 wt% SiO ₂ , Aldrich), aluminum hydroxide (98%, Fluka), potassium hydroxide (98%, Daejung) And then heated at 190 캜 for two days in a high-pressure reactor. The Si / Al molar ratios of MFI zeolite synthesized with different concentrations of the synthetic mother liquor were 50 and 350, respectively. MFI zeolites with Si / Al molar ratios of 25 and 75 were purchased from Zeolyst.

And ion-exchanged water at 60 ℃ the Na ⁺ of MFI zeolite with 0.5N ammonium nitrate (> 99wt%, Duksan) solution to convert the Na ⁺ ions in the zeolite framework in a H-type ion exchange MOR zeolite in H ⁺ ions, and this And calcined at 550 DEG C for 6 hours to convert to H-type MFI zeolite (H-MFI).

MOR zeolite with Si / Al molar ratio of 10 was purchased from Tosoh. In order to obtain MOR zeolite having different Si / Al molar ratios, MOR zeolite having Si / Al molar ratio of 10 was put into a 6.0 N acetic acid solution and heated at 60 ° C. to remove aluminum in the zeolite skeleton to obtain MOR zeolite having Si / Al molar ratio of 100 . The prepared MOR zeolite having a Si / Al molar ratio of 100 was washed with distilled water, dried at 100 ° C, and then calcined at 550 ° C for 12 hours.

The ion exchange process for converting the MOR zeolite to the H-type zeolite (H-MOR) was the same as the one described in the above process for producing H-MFI zeolite.

Conversion of BEA zeolite (PQ Co., Si / Al molar ratio = 13) and FAU zeolite (Union Carbide, Si / Al molar ratio = 3) to H type BEA (H-BEA) and H type FAU (H- FAU) The same procedure was applied for the ion exchanging process described in the above process for producing H-MFI zeolite.

In this experiment, the nomenclature of zeolite was named MOR, MFI, FAU, and BEA according to the IZA code name, and the Si / Al mole ratio was written in the brackets. H-type zeolite ion exchanged Na ⁺ ion with H ⁺ ion indicated 'H-' before MOR, MFI, FAU and BEA code names.

3. Characterization of zeolite

The X-ray diffraction pattern of the zeolite was examined with an X-ray diffractometer (D / MAX Ultima III, Rigaku). The CuKα X-ray passed through the Ni-filter at 40 kV and 40 mA was injected at a rate of 2 ° / min in the range of 5 to 50 °.

The particle size and shape of the zeolite were observed with a SEM (Hitachi, S-4700) at Gwangju Center for Basic Science Research. The Si / Al molar ratio was calculated by measuring the content of silicon and aluminum with EDX (Horiba, EX-250) mounted on a SEM.

The nitrogen adsorption isotherm was obtained by measuring with a nano-porosity analyzer (Nano Porosity-XQ, Mirae SI Co.). After evacuation at 150 ° C for 2 hours, nitrogen was adsorbed at -196 ° C. The surface area was calculated using the BET equation.

In order to investigate the acidity of the zeolite catalyst, ammonia temperature desorption (NH ₃ -TPD) curves were drawn using a temperature elevation desorption apparatus (Bel Japan, BELCAT). The catalyst was exhausted from the helium air stream at 550 DEG C for 1 hour and then cooled to 150 DEG C. [ Ammonia (standard gas, 99.999%) was sent as a pulse to the catalyst and adsorbed until saturated. In order to remove physically adsorbed ammonia, ammonia was desorbed while raising the temperature to 600 ° C at a rate of 10 ° C / min after discharging while flowing a helium stream for 1 hour. The amount of the acid sites of the zeolite catalyst was calculated by deconvolution of the measured TPD curves, and the amounts of weak acid sites and strong acid sites were determined.

4. Experimental results

(1) Physicochemical properties of zeolite

The XRD patterns of the MOR (10), MFI (25), FAU (3) and BEA (13) catalysts used in the experiment are shown in FIG.

Referring to FIG. 1, the X-ray diffraction pattern of zeolite was in good agreement with the characteristic peaks of each zeolite shown in the literature. The characteristic peak size of the X-ray diffraction pattern of the zeolite was also close to that of the literature value, and it was confirmed that the crystallinity was excellent.

2 to 5 show SEM photographs of the zeolite catalyst. FIG. 2 shows MOR 10 zeolite, FIG. 3 shows MFI 25 zeolite, FIG. 4 shows FAU 3 zeolite, and FIG. 5 shows BEA 13 zeolite.

Referring to FIGS. 2 to 5, the crystal size of FAU and MFI zeolite was about 0.5 μm, and the MOR zeolite was 1.5 to 2.0 μm, slightly larger than that. On the other hand, the crystal size of BEA zeolite was found to be very small, about 0.2 μm or less.

FIG. 6 shows nitrogen adsorption isotherms of MOR (10), MFI (25), FAU (3) and BEA (13) catalysts.

Referring to FIG. 6, the zeolite used in the experiment was a microporous zeolite having many fine pores, showing a typical Langmuir adsorption isotherm pattern. On the other hand, BEA zeolite with relatively large pore size and large surface area increased the adsorption amount at a relative pressure of 0.2 to 0.7. BEA and FAU zeolite show a large adsorption amount because zeolite has a large pore size and many vacancies such as a super cage in a pore.

The BET surface area and pore structure parameters determined from the nitrogen adsorption isotherm of each zeolite are summarized in Table 1 below.

Zeolite Pore topology Pore size (A) BET Surface area (m ² / g) MFI (25) 10 -oxygen ring 5.1 x 5.5 [100]
5.3 × 5.6 [010] 413 MOR (10) 12-oxygen ring 6.5 × 7.0 [001] 419 FAU (3) 12-oxygen ring 7.4 × 7.4 [111] 574 BEA (13) 12-oxygen ring 6.6 x 6.7 [100]
5.6 x 5.6 [001] 577

Referring to Table 1, unlike other zeolites such as MOR, the MFI zeolite has 10 pore openings, and the pore size is smaller than that of other zeolites. The MOR zeolite has a linear pore structure, whereas the MFI zeolite has a zigzag shape. The BET surface areas were in the order of BEA> FAU> MOR> MFI.

FIG. 7 shows the NH ₃ -TPD curves of H-MOR (10), H-MFI (25), H-FAU (3), H-BEA (13) and silicalite catalysts.

The acidity of the zeolite depends on the type of zeolite. Even if the Si / Al molar ratios are similar, the acidity differs if the zeolite types are different. The method of measuring the acidity of the catalyst with ammonia TPD is well known. The acid amount of the catalyst can be compared with the area of the ammonia TPD curve, and the acid strength can be determined from the maximum temperature ( T _max ) of the desorption curve peak.

As shown in FIG. 7, the strong acid peak point of the zeolite catalyst appeared between 350 and 550 ° C, and the weak acid point peak appeared at 150 to 250 ° C. It is known that this is due to the physical adsorption of ammonia. H-MOR zeolites have the strongest acid sites compared to other zeolites. On the other hand, silicalite showed little strong acid sites. The strong acid point is indicated by the skeletal structure of the zeolite, which is determined by the number of Si-O-Al bonds. Therefore, the degree of strong acidity depends on the molar ratio of Si / Al in the case of the same zeolite. Even if the Si / Al molar ratio is similar, the difference in the type of zeolite differs because the skeleton formation structure differs depending on the zeolite, and thus the content of aluminum is different. Since silicalite is a material in which most of aluminum is removed from the MFI zeolite structure, the Si / Al molar ratio is very large and there is almost no aluminum in the skeleton. Therefore, silicalite shows almost no desorption peak showing strong acid point even in ammonia TPD.

FIG. 8 shows NH ₃ -TPD curves of H-MFI zeolites having different Si / Al molar ratios. As the Si / Al molar ratio of the H-MFI zeolite increased, that is, as the aluminum content decreased, the strong acidic peak decreased and the peak temperature decreased. From the NH ₃ -TPD curves of H-MFI zeolites with different Si / Al molar ratios, the peak acidity of the strong acid decreased with increasing Si / Al mole ratio.

(2) Decyl glucoside formation reaction

The major products produced by the reaction of glucose with decanol were decyl glucopyranoside and decyl glucofuranoside. And some by-products (degraded alcohol, oligosaccharide, etc.) were produced.

Glucose conversion was calculated as the percentage of glucose consumed in the reaction to the amount of glucose before the reaction, and the yield of the product was calculated as a percentage of the specific product relative to the amount of total product.

FIG. 9 is a graph showing conversion ratios with respect to the catalyst / glucose weight ratio in order to investigate the change in conversion of glucose according to the amount of H-MFI (50) catalyst. When the amount of catalyst was more than 1.0 g per 2.5 g of glucose, the conversion did not change significantly. Therefore, when the glucose is 2.5 g, the amount of suitable catalyst is 1.0 g.

FIG. 10 shows the conversion of glucose in the H-MOR (10), H-MFI (25), H-FAU (3) and H-BEA (13) catalysts. The conversion of glucose reached equilibrium after 4 hours of reaction time. The conversion of glucose in the zeolite catalyst was high in the order of H-FAU> H-BEA> H-MFI> H-MOR. The conversion of the H-MOR zeolite catalyst with the lowest conversion was 60% or less.

The conversion of glucose and the yield of decyl glucoside were summarized in Table 2 below when the reaction time was 4 hours in the absence of a zeolite catalyst, a 1 N hydrochloric acid solution catalyst and a catalyst.

catalyst
Conversion Rate (%)
yield(%) Decyl glucopyranoside Decyl glucopuranoside Sum H-FAU (3) 82.2 50.4 15.6 66 H-BEA (13) 80.3 31.1 35.9 67 H-MFI (25) 78.1 38.9 27.3 66.2 H-MOR (10) 65.4 15.4 43.5 58.9 silicalite 0 0 0 0 HCl 36.1 12.4 30.2 42.6 non-catalyst 0 0 0 0

Referring to Table 2 above, the conversion of glucose exceeded 65% in H-MOR, H-MFI, H-FAU and H-BEA zeolite catalysts with acid sites. However, the silicalite catalyst, which has few acid sites and only pores, shows little reaction activity. This shows that the acid sites of the H-MOR, H-MFI, H-FAU and H-BEA zeolite catalysts contribute to the reaction.

The yields of decyl glucopyranoside and decyl glucopuranoside in each zeolite catalyst were affected by the acid strength and pore structure of the catalyst and showed different results. In H-FAU and H-MFI, the yield of decyl glucopyranoside was higher than that of decyl glucopuranoside. The yield of decyl glucopuranoside was higher in the H-BEA and H-MOR catalysts. Therefore, the selectivity of decyl glucopyranoside for H-FAU and H-MFI was high, and the selectivity of decyl glucopuronoside for H-MOR and H-BEA was high.

It was confirmed that it is preferable to use either H-MFI or H-FAU as the zeolite catalyst in order to increase the selectivity of the decyl glucopyranoside among the decyl glucopyranoside and decyl glucopyranoside produced by the reaction. In particular, it was found that H-MFI had a Si / Al molar ratio of 25 and H-FAU had a Si / Al molar ratio of 3.

It has been confirmed that it is preferable to use either H-MOR or H-BEA as a zeolite catalyst in order to increase the selectivity of decyl glucopyranoside in decyl glucopyranoside and decyl glucopuronoside produced by the reaction. In particular, it was found that H-MOR had a Si / Al molar ratio of 10 and H-BEA had a Si / Al molar ratio of 13.

In the reaction using 1N hydrochloric acid solution as a catalyst, conversion rate was about 36%. In the product distribution, about 60% of byproducts such as oligomers except decyl glucoside were produced.

In addition, not only the reaction did not occur at all in the reaction without using the catalyst, but also the reaction products of glucose and decanol did not completely dissolve even at the reaction temperature.

(3) Properties of the reaction product

On the other hand, contact angle and estrogen MCF-7 cell proliferation experiments were carried out to characterize the decyl glucopyranoside produced using H-FAU (3) as a zeolite catalyst.

Nonylphenol, which has been widely used as a conventional surfactant, has been found to be an environmental hormone substance having a large estetone activity. Therefore, the desilyl glucopyranoside, which can be easily prepared by the production method of the present invention, does not have an environmental hormone action and the possibility of replacing the existing nonylphenol has been examined.

11 shows the surface tension and the contact angle of decyl glucopyranoside and nonyl phenol as a comparative substance.

The CMC (Critical Micelle concentration) value was determined at the inflection point where the surface tension value is no longer changed even when the concentration of decyl glucopyranoside and nonylphenol is increased. The measured CMC of decyl glucopyranoside was 2.2 x 10 ^-3 mol / L at surface tension of 31.2 mN / m and 1.2 x 10 ^{- 4} mol / L of CMC of nonylphenol at surface tension of 34.2 mN / / L. ≪ / RTI >

The contact angles of decyl glucopyranoside and nonylphenol were measured. The contact angle of decyl glucopyranoside was smaller than that of nonylphenol and water. This suggests that the desilyl glucopyranoside is more hydrophilic and has greater wettability than nonylphenol.

The surface tension of CMC, which is the basic property of surfactant, is similar to that of nonylphenol, indicating that it satisfies basic properties as a surfactant. The contact angle was lower than that of water or nonylphenol, so that the hydrophilicity was excellent and the wettability was better than nonylphenol. Therefore, it was confirmed that the decyl glucoside can be applied as a surfactant which can substitute nonylphenol because the physical properties are similar to nonylphenol and higher than that of nonylphenol.

12 shows the proliferation of estrogen MCF-7 cells compared to 17β-estradiol, nonylphenol, and decyl glucopyranoside (DGP). Cell proliferation of 17? -Estradiol and nonylphenol was promoted. 17β-estradiol significantly increased cell proliferation at 10 pM concentration. The cell proliferation rate of nonylphenol was also increased at a concentration of 100 nM than that of decyl glucopyranoside. On the other hand, the cell growth rate of the decyl glucopyranoside was not substantially increased.

In Table 3, the relative proliferation effect (RPE) of decyl glucopyranoside and nonylphenol was compared with that of 17β-estradiol.

compounds concentration (nM) RPE (%) RPP (%) 17β-estradiol 100 100 100 Nonylphenol 100 84.4 100 Decyl glucopyranoside 10 36.4 0.001

As can be seen from the above results, RPE and RPP of decyl glucopyranoside were lower than nonylphenol. And when the concentration of decyl glucopyranoside was 10 pM or more, it did not affect cell proliferation. This is a result that the decyl glucopyranoside shows very low estrogenic cell proliferation compared to nonylphenol.

Surfactants are substances that are widely used in general household products such as emulsifiers, detergents, and cosmetics as well as industrial applications, and are highly likely to be exposed to human bodies. However, nonylphenol, which has been used in the past, has been found to be an environmental hormone substance that has estrogen activating properties and impairs hormone function. In the above experiment, it was concluded that the estrogenic cell proliferation of decyl glucopyranoside to replace nonylphenol is much lower than that of nonylphenol, and that when the concentration is above 10 pM, it does not affect cell proliferation. It means that there is little fear of activating estrogenic proliferation and causing hormone degeneration.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation. Accordingly, the true scope of protection of the present invention should be determined only by the appended claims.

Claims (5)

A feeding step of feeding 200 to 3000 parts by weight of decanol to 100 parts by weight of glucose into the reactor;
And a reaction step of reacting the glucose and the decanol under a zeolite catalyst to produce decyl glucopyranoside and decyl glucofuranoside,
Wherein the reaction step comprises the steps of: a) injecting nitrogen into the reactor to remove air from the reactor into which the glucose and the decanol have been charged, and b) charging the internal temperature of the reactor to 80 ° C C) stirring the mixture at 500 rpm for 30 minutes after acetic acid is injected into the reactor after the primary stirring, and d) stirring the glucose 100 5 to 50 parts by weight of a zeolite catalyst is fed into the reactor, and then the internal temperature of the reactor is maintained at 80 DEG C and then the reactor is stirred for 3 hours at 500 rpm for 1 hour. E) And then stirring the mixture at 500 rpm for 5 hours,
Wherein the fourth stirring step includes liquefying the reactants vaporized in the reactor in a condenser maintained at 5 DEG C and introducing the reactants into the reactor,
The zeolite catalyst is any one selected from H-MOR, H-MFI, H-FAU and H-BEA,
To increase the selectivity of the desilyl glucopyranoside, any one of H-MFI and H-FAU was used as the zeolite catalyst, and H-MOR and H-FA were used as the zeolite catalyst in order to increase the selectivity of the desilyl glucopyranoside. BEA. ≪ / RTI > delete delete delete The method of claim 1, wherein the H-MFI has a Si / Al molar ratio of 25, the H-FAU has a Si / Al molar ratio of 3, the H-MOR has a Si / Al molar ratio of 10, And a Si / Al molar ratio of 13. ≪ RTI ID = 0.0 > 11. < / RTI >

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