TR201819830A2 - DEVELOPMENT OF BORON-DERIVATED CHROMATOGRAPHIC FILLER - Google Patents

Abstract

The new boron-derived zeolite filler named DAZB and DSZB within the scope of the present invention, free silanol and aluminum hydroxide groups formed in the structure of dealumine and decilyl zeolites with different Si / Al ratios, and boric acid in different molar ratios, boric acid ethyl alcohol ester or boric acid methyl alcohol It has been obtained from the chemical reactions of its ester. Using solid phase extraction cartridges developed from DAZB and DSZB filler, sunset yellow, patent blue V colorants and sucrose-containing products were separated into said components. The present invention has demonstrated that processes similar to the separation of colorants and sugars can be performed relatively inexpensively, easily by DAZB and DSZB materials developed under the present invention. As a result of these studies, DAZB and DSZB fillers are suitable materials for the use of public research institutions dealing with food, medicine, chemistry, environment and similar fields, R&D departments of private sectors and even in large-scale production stages of sectors.

Description

DESCRIPTION DEVELOPMENT OF BORON DERIVATIVE CHROMATOGRAPHIC FILLER The invention is the synthesis of a new boron-derived zeolite filler for chromatographic studies, its characterization and applications. Related chromatographic fillers easy production, low cost and rich raw material resources in industrial food products, pharmaceutical and chemical production processes. They have a high potential for use in purification and recovery studies.

State of the Art Zeolite, dealuminated zeolite and boric acid are commonly known substances. much in the literature He has several works with different applications [Weitkamp, Jens. " Zeolites Energetics: a new field of applications for hydrophobic zeolites. "Journal of the Mesopore-modified zeolites: preparation, characterization, and applications.

Dealumination and desilylation of zeolites in acidic and basic conditions His work has been done by many groups. Today, this dealumination and zeolite modification by desilylation is accepted as classical studies [Silaghi, Marius-Christian, Celine Chizallet, and Pascal Raybaud. "Challenges on molecular aspects of dealumination and desilication of zeolites. " Microporous and Mesoporous of hierarchical zeolite catalysts by desilication. " Catalysis Science & Technology 1.6 properties-A case revised. "Advances in Materials Science and Engineering (2014)].

Zeolites are often used as direct catalysts or catalyst components in catalytic reactions. used as carrier adsorbents. For example, as direct catalysis The most successful substances used in cracking applications in the petrochemical industry zeolites [Masters, A. F.; Maschmeyer, T. "Zeolites - From Curiosity to Cornerstone." Some studies of its adsorbtion on zeolites and investigation of its effect as a catalyst have been carried out. by research groups [Zhang, Wengui, et al. "Efficient dehydration of bio-based 2, 3-butanediol to butanone over boric acid modified HZSM-5 solimannejad "lnteraction between NaY Zeolite and boric Acid: a preliminary Vasile et al. "Conversion of Industrial Feedstock Mainly with Butanes and Butenes Over B-HZSM-5 and Zn-HZSM-S Modified Catalysts." Revista de Chimie 66.3 (2015): 336-341] In related studies, zeolites were used as boric acid carrier catalysts. used. Boronization of zeolites has not been studied and boron-derived chromatographic Not used as fillers. Besides, in the state of the art, Obtaining boron esters of silicon-containing compounds and polymeric borosiloxane materials studies are also available [Yajima, S., Okamura, K., Hayashi, J., & Shishido, T.

Office; Polymeric organosilanol-boronic acid reaction products and method for making Timothy S. Chen. "Boron-containing organosilane polymers and ceramic materials The Technical Problem That The Invention Aims To Solve The chromatographic filler should have good separation properties, be inexpensive, and should be applicable. In this context, alternative ways to reduce production costs should be investigated. In addition, the availability of current analytical techniques and related fillers mixtures containing a large number of compounds, which are not well purified, problems such as long procedures, being unstable in different pH ranges. New materials need to be developed.

Alternative to commercially available and widely used chromatographic fillers new chromatographic filler, most of which are derivatives of polymeric resins or silica gels There are also many studies on the derivation of substances [Hosoya, Ken, et al. "Polymer packing material for liquid chromatography and a producing Frantisek Svec, and Ken Hosoya. "Process for producing uniform macroporous porous copolymers and ion-exchange resins prepared therefrom." U.S. Patent No. dihydroxypropane (diol) modified silica gels and silica gel 60 are commercially known and many They are the most important fillers commonly used in the study. These fillers as direct powder chromatographic fillers or as liquid chromatography columns, chromatographic extraction cartridges (SPE), in the form of thin alumina or glass sheets they are sold as modified and end-user oriented. However, high production costs of this type of adsorbents are preferred industrially. is lowering. Less costly and richer in raw materials, more practical There is a need for chromatographic fillers that can be produced by various techniques.

present invention. in prior art analytical or chromatographic techniques lower cost, industrial and suitable for laboratory scale applications, available in the state of the art development of new chromatographic fillers (synthesis, characterizations, applications and related topics). containing silicon as the output product by a method similar to the production of borosiloxane compounds from obtained from various inexpensive aluminosilicate compounds (zeolites) used Free metal hydroxyl (M-OH) groups in the structure of dealuminated and decyl zeolites, boron-derived zeolites (boron-derived aluminosilicates) by adding boric acid with different techniques (DAZB: Boron derived zeolite synthesized with Dealuminated zeolite; DSZB: Decilyl boron derived zeolite synthesized with zeolite). DAZB and DSZB fillers are known completely different from borosiloxane substances. Developed filler, production method and applications are not available in the state of the art. Developed separately The fact that the natural raw material source of the fillers is high, they are easy to obtain. and has a wide application area due to their low cost.

Description of Figures Figure 1. Block of boron-derived zeolite synthesis process using dealuminated zeolite (DAZ) current sky.

Figure 2. Block flow of boron derived zeolite synthesis process using decyl zeolite (DSZ) sky

Figure-3. Visualize the binding of boric acid to the silanol groups of DAZ and DSZ derivatives. to be expressed as Figure-4. Powder phase XRD patterns of DSZB, DAZB and ZSM-5 structures Figure-5. FT- of DAZ and DSZ zeolite derivatives in the wavenumber range of 400 - 1800 om1 Figure-9. FT-IR spectrum of DAZB and DSZB in the wavenumber range of 450 - 1800 om'1 and related chemical bonds Figure-12. FT-IR in different wavenumber range of DAZB and DSZB collectively spectra and chemical bonds Figure-13. SEM images of DAZB at 10 pm and 30 pm scale Figure-14. SEM images at scale of DSZBl Figure 15. Surface area (BET), particle size and boron adsorbents of DAZB and DSZB rates Figure 16. Results of HPLC analysis with DAZB or DSZB enhanced column Explanation of References in Figures A. The step of carrying out the reaction in the presence of acidic solution 2. HCl, H2SO4 or HNOs 3.1. Temperature (A) 4. Cooling .one. Solution B. Filtering step 6. Pure water 7.1. filtrate C. Wash step 6. Pure water 8. Removed acid solution 9.1. Washed dealuminated zeolite D. Drying step . Temperature (D) E. Cooling step 12. Vacuum 4. Cooling 13.1. Chilled dealuminated zeolite F. Nickname for boric acid or boric acid ester 14. Boric acid, boric acid methyl alcohol ester, boric acid ethyl alcohol ester . Xylene 12. Vacuum 16. warming 17.1. Mix (F) B. Filtering step 12. Vacuum 18.1. filtrate G. The step of washing the filtrate with organic solution 19. Dichloromethane .one. Filtrate washed with organic solution (G) H. Drying 21. Temperature 22.1. Dry mix (H) I. Cooling 12. Vacuum 4. Cooling J. The step of carrying out the reaction in the presence of a basic solution 24. NaOH or KOH 3.2. Temperature (A) 4. Cooling .2. Solution B. Filtering step 6.Pure water 7.2. Filtrate (B) C. Wash step 6. Pure water . Removed base solution 9.2. washed out solution D. Drying step . Temperature (D) 11.2. drying decyl zeolite E. Cooling step 12. Vacuum 4. Cooling 13.2. Chilled decilyl zeolite F. Nickname for boric acid or boric acid ester 14. Boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester . Xylene 12. Vacuum 16. warming 17.2. Mix (F) B. Filtering step 12. Vacuum 18.2. filtrate G. Filtrate washing step 19. Dichloromethane .2. Filtrate washed with organic solution (G) H. Drying 21. Temperature 22.2. Dry mix (l) I. Cooling 12. Vacuum 4. Cooling Description of the Invention It has a high ratio of Si/Al ratios available and cheap in the market. silica-containing (Si/AI X or A type zeolite products and boric acid, boron-derived zeolite filler are the starting raw materials. Boron derived from these raw material sources zeolite filler development method steps are shown in Figures 1 and 2; DAZ and DSZ The binding of boric acid to the silanol groups of its derivatives is explained in Figure 3.

In the presence of mineral acid solution, the dealumination reaction is performed (A). 40-. The amount of zeolite slow in volume carried out and cooled to room temperature (4). Thus, an acidic acid containing dealuminated zeolite solution is obtained (5.1). Then, 1-4 times (preferably 3 times) volume of pure zeolite Filtering is performed by adding water (6) (B) and acidifying in the previous step. The filtrate is obtained which is treated and washed with distilled water (7.1). The amount of filtrate 1- It is washed 1-3 times (preferably 2 times) by adding distilled water (6) in 4 times (preferably 3 times) volume (C), the acidic solution is removed (8) and the dealuminated zeolite (DAZ) washed back remains (9.1).

Thus, the acid (1) added in the dealumination (A) step is completely removed (pH dried (D). In vacuum (12) it is cooled to room temperature (4) (E) and refrigerated DAZ is obtained (13.1) and boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester alias (F). 0.05-1 mol on with boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester (14) Xylene (15) is added 1-3 times (preferably 2.5 times) by volume of DAZ (13.1). Vacuum A mixture containing DAZB1 is obtained (17.1). Filtering process in vacuum environment (12) performed (B). The organic matter of the filtrate (18.1) removed from the xylene obtained 1-3 times the volume of filtrate on filtrate (18.1) for solution washing (G) Add (preferably 2 times) dichloromethane (19) and wash (G), xylene completely (H) and the dried mixture (22.1) is cooled to room temperature in vacuum (12). (4) cooled (l). As a result, boron-derived zeolite (23.1) was obtained by using DAZ. Si/Al ratios of the products obtained as a result of the reactions under different conditions and their crystal structure arrangement, number of Si-OH and AI-OH groups, particle distribution and surface images, X-ray diffraction (XRD), Inductive Coupled Plasma (Inductively Coupled PIasma-lCP-OES), Inductively Coupled Plasma - Mass Spectrometry (Inductively Coupled Plasma Mass Spectroscopy-ICP-MS), Near Infrared Spectroscopy (NIR), Fourier Transformed Infrared Spectroscopy (Fourier Transform Infrared Spectroscopy-FT- has been detected. Analyzes of the obtained materials and crystallization of zeolites Considering the structure sequences; Optimum of the dealumination process conditions as a concentration of 2N HCl solution, a temperature of 150 0C and a reaction time of 6 hours has not been determined.

In the presence of a basic solution, the decylation reaction is carried out (J). 40-70 9 ZSM-S, X or type A zeolite (1) is added into the reaction vessel (J). Volume of zeolite is added slowly.

The reaction should be stirred for 3-12 hours. performed in the environment. and cooled to room temperature (4). Thus, basic zeolite-containing solution is obtained (5.2). Then, 1-4 times (preferably 3 times) volume of pure zeolite Filtering is performed by adding water (6) (B) and adding base in the previous step. The filtrate is obtained which is treated and washed with distilled water (7.2). The amount of filtrate 1- It is washed 1-3 times (preferably 2 times) by adding distilled water (6) in 4 times (preferably 3 times) volume (C), the basic solution is removed (25) leaving decyyl zeolite (DSZ) washed behind (9.2). Like this The base solution (24) added in the decylation (J) step is completely removed (pH dried(11.2). In vacuum (12) it is cooled to room temperature (4) (E) and refrigerated DSZ is obtained (13.2) and boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester alias (F). 0.05-1 mol on with boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester (14) Xylene (15) is added 1-3 times (preferably 2.5 times) by volume of DSZ (13.2). Vacuum A mixture containing DSZB is obtained (17.2). Filtering process in vacuum environment (12) performed (B). The organic matter of the filtrate (18.2) removed from the xylene obtained 1-3 times by volume (preferably 2 layers) on filtrate (18.2) for solution washing (G). solid) dichloromethane (19) is added and washing (G) is done, xylene is completely removed. dried (H) and the dried mixture (22.2) in vacuum (12) at room temperature (4) cooled (I). As a result, boron derived zeolite (23.2) is obtained by using DSZ.

Si/AI ratios of the products obtained as a result of the reactions under different conditions and their crystal structure arrangement, number of Si-OH and AI-OH groups, particle distribution and surface detecting images using IR, NlR, ICP-MS, ICP-EOS, XRD, SEM techniques has been made. Analyzes of the obtained materials and the crystal structure of the zeolites Considering the sequences; Optimum conditions for the decylylation process 2N KOH solution concentration, 110°C temperature and 6 hours reaction time. has not been determined.

DAZ and DSZ obtained under optimized conditions with ZSM-5 type zeolite are shown in Figure 4. DAZB and DSZB obtained from the reaction of the same mole ratio with boron XRD patterns of products are given. When the XRD results are examined, the general results of the zeolites It was observed that the crystalline structures were preserved and the effects of boron groups on the main structure were observed. released after modification. However, 27.94 and 28.48 of DAZB The peak intensities at 29 degrees are higher than the peaks of DSZB at the same place. has not been observed.

FT-IR of DAZ and DSZ substances obtained under the above-mentioned optimized conditions spectrum and the corresponding transmittance and wavenumbers of its important functional groups. It is stated in Figure-5. According to the results shown in Figure 5, DAZ and DSZ zeolite Although the derivatives have common permeability bands, the difference in peak intensity are available. This means different Si/Al ratios and different mole ratios in the same unit surface area. It is due to the fact that it contains Si-OH and Al-OH groups.

In addition, treatment of the initial zeolitic material with acid or base in the first step In the particle sizes of DAZ and DSZ, the corresponding initial reductions occurred compared to those of the items. On the contrary, as a result of boronization The particle size of the boron-derived zeolite fillers obtained increased. has been observed.

Different ratios of dealuminated and decylyl zeolite obtained under optimized conditions (0.1; 0.2 and DAZB and DSZBs obtained by the reaction of 0.5 boron/zeolite (by weight) with boric acid. NIR spectra are shown in Figure 6 and Figure 7. Boric acid used in the reaction As the amount increased, changes were observed in the intensity of the relevant peaks. Si-O-B and B-OH increase in the peaks representing the chemical bonds and increase in the free Al-OH and Si-OH peaks. reduction is due to the production of DAZB and DSZB from the respective DAZ or DSZ intermediates. subsequently observed.

In Figure 8, DAZB and DSZB, which give the strongest peaks in Figures 6 and 7, were selected. DAZB produced from DAZ and DSZ treated with mole ratio boric acid, and NIR spectra of DSZB are given. The peaks at wavelength 7082 om'1 are free. It belongs to silanol (Si-OH) groups and after treatment with boric acid, these peaks bands are B-O-Si, which consists of boron compound bound to free silanol groups. It has been observed that the boron increases depending on the mole ratio (Figure 6) and this is more structured. indicates that more boron groups are formed. Peaks at wavenumber 5199 om'1 while it belongs to the AI-O-H group, the intensity of the peaks belonging to the Al-O-H bonds depends on the mole ratio of boron. decrease was observed (Figure 7), which is Si-O-B together with Al-O-B shows that ties are also formed. Peaks of B-OH groups 4490 - 4089 om*1 is in the wavenumber range. In DSZB and DAZB, these peaks correspond to the corresponding DSZ and DAZ more severe than those of the starting material. DAZ and DSZ B-OH groups The reason why they give peaks in this region despite the fact that they do not carry silol groups and water (Si-O --- H-O-H) interactions (Figure 7).

In the figure, it is boron-derived absorbing in the wavenumber range of 450 cm'1 - 1600 om'1 The spectrum of functional groups belonging to the zeolite material is indicated.

In Figures 10 and 11, DAZB and DSZB derived from DAZ and DSZ derivatives FT-1R spectra of the same are given. Common in the obtained DAZB and DSZB substances Absorption peaks were observed. 3200 - 3250 om'1 wavenumber range The adsorption peak belongs to the B-OH group. In the range of 500 - 900 cm'1 wave number The absorption peaks belong to the B-O-Si group.

In Figure 12, boron derivative obtained by using different amounts of boric acid. FT-1R spectra of zeolite materials can be seen. Depending on the amount of boric acid the intensity of the relevant bands varies in direct proportion.

DAZB synthesized using DAZ obtained under optimized experimental conditions The adsorption peaks of B-O-X(H, Si) and 8-0 bonds of the substance, in the same mole ratio more band than DSZB material obtained from boric acid and DSZ-derived zeolites. the intensity is greater.

10 pm and 30 µm of DAZB and DSZB substances obtained under optimized conditions scaled SEM images are given in Figure 13 and Figure 14, respectively.

Surface area (BET), particle size and boron ratio studies of fillers has been made. The results are given in Figure 15. and sugar purification procedure The developed boron-derived zeolites were used for the first time in the literature in the colorant sugar products. It was used as a chromatographic filler in the separation of mixtures. Boron derived zeolite filler is placed in solid phase extraction cartridges (SPE). sugar compound sunset yellow and patent blue V colorant compounds with the appropriate eluent It was obtained purely from sucrose. Boron derived zeolite filler, ESi-O-B(0H)2, ESi-OH, EAI-OH chemical groups and pores in its structure purification of the compounds, sugar (sucrose) and colorants, thanks to the combination of It provides the process successfully. Sucrose compound boron-derived zeolite adsorbent It adheres as a result of chemical interaction with the ESi-O-B(OH)2 groups in its structure.

Colorants (sunset yellow, patent blue V) are used to help boron-derived zeolite structures. weak interactions with unboronated free ESi-OH, EAI-OH hydroxyl groups, i.e. Besides, the large surface area of ZEOBOR adsorbents they are purified by separating from each other with their conservatism.

SPE filled with boron-derived zeolite using mobile phase at appropriate pH (pHZB) The colorants in the mixture of the cartridge and the sugar end product can be easily After being removed, the sugars retained in the SPE were adjusted to 5 by adjusting the pH value of the eluent. (pHSS) boron derived zeolite are removed from the filler. Because The boron-derived zeolite type fillers developed are both affinity and chromatographic. has features. In this study, boron-derived zeolites, which are a new type of filler, were investigated. Related SPE cartridge and HPLC column products have been developed.

SPE-Fill: 0.1 times by weight of DAZB or DSZB adsorbent per 1 volume SPE cartridge SPE cartridges have been developed using (filler).

For this, the unit volume of 3, 6, 12 and 20 cc empty and frit SPE cartridges is 0.1 9 filled with boron-derived zeolite filler (0.39 for 3 volume SPE cartridge, 6 volume For the SPE cartridge, the desired amount of 0.69 boron-derived zeolite voluminous cartridge is filled). By pressing from above to avoid any gaps in the SPE and The filling material is placed in the cartridge well by applying vacuum. SPE process in four stages performed using the vacuum manifold as follows: Conditioning: 3-5 volumes (preferably 4 volumes) of methanol and purified water from each cartridge is passed. At this stage, 1d/s (drop/second), 2d/s for flow rate optimization studies and 3d/s conditions were tested by applying adjustable vacuum.

Loading: The amount of dye and sugar mixture to be loaded into the cartridge is 1% of the adsorbent amount, Blue V, Sunset Yellow colorants and sucrose sugar compound were used. Sample it was dissolved in water directly and slowly loaded into the cartridge and again 0.5d/s, 1d/s and 2d/s Flow rate optimization studies have been carried out.

Washing: Approximately 1/3 of the cartridge volume is passed through methanol and hexane, respectively.

Elution: Elution solvent is added while the taps are closed. A clean experiment on the manifold tube is inserted. 1 mL of 0.1M ammonium acetate buffer solution (pH=7.5) from the cartridge passed and collected into the tube. Elution amount optimization studies 2 and 4 mL is repeated with Flow rate optimization studies will be 0.5 d/s, 1 tooth and 2 d/s has been made in this way. For dye and sugar analysis with the eluant HPLC collected at this step given. Sunset Yellow, Patent Blue V food when eluent conditions are pH26 It was determined that the dyes passed, and the sucrose remained in the adsorbent. Later on Detection by HPLC analyzes where sucrose passes when the eluent is adjusted to the pHSS value. has been made.

Recovery studies: lg DAZB or DSZB in 12 cc volume and SPE cartridge with frit substance is added. Under vacuum, 20 mL of methanol is passed through the cartridge. followed by 0.2 gramina w/w impregnated with 25% (0.05 9) dye (containing Sunset Yellow and Patent Blue V) DAZB or DSZB prepared by dissolving a sample of white sugar (sucrose) in 0.2 mL of water It is applied to the SPE cartridge. Then the methanol/acetonitrile (proportion) solution adjusted to zö is passed at 0.5 rpm at a speed of slicing to dye fractions per 1mL*. collected until it passes. Then, the pH value of the same mobile phase is adjusted to pHS5. sucrose compound is obtained. HPLC-RlD for sugar and dye contents of each fraction (sugar) and HPLC-DAD (dye) techniques. from SPEs recoveries of dyes and sugars are given in Table-2.

As a result of HPLC analysis, SPE filled sugars using DAZB or DSZB that it is completely retained in the cartridge and that the dyes are recovered by an average of 98%. win has been determined. Then the pH value of the same mobile phase sodium acetate Absorbed sugars (sucrose) by adjusting pH=5.0 with SPE carous is recovered. As a result of the efficiency calculation, 88% of the sucrose compound was recovered. has been earned.

Based on these results, it is a good adsorbent for sugar and dye separation of DAZB and DSZB. has not been determined.

As mentioned before, HPLC using DAZB and DSZB adsorbents. columns are prepared. DAZB and DSZB filler, HPLC column filler filled into columns. Pre-wash prepared before column filling process" as a solution of 80/20% or methanol/water (v/v) 80/20 is used.

In order to avoid air bubbles in the pump, hexane is passed before the column is filled. More Then the columns are filled with the synthesized DAZB or DSZB. Column with DAZB and DSZB filling procedures were carried out by following the steps below.

Weigh 3 g of synthesized filler into a beaker and add 20 mL of hexane to it. is added and mixed. Later on, The mixture is kept in an ultrasonic bath for 5 minutes.

The mixture is quickly filled into the reservoir where the column is attached.

A pressure gradient program is written from the software (flow rate and pressure optimization hexane for 10 minutes at 500 psi and 1000 psi pressure, respectively. after passing through a hexane column at 2000 psi for 30 minutes. is passed.

2D and 3D pressure during flow to ensure proper filling. and graphs showing flow rates are obtained by pressing the Log data icon. Hexane was passed through the system for minutes. pump at the end of the period is stopped. The column is removed from the system and filling is applied to the ends of the column. Covers are placed so that the material does not dry out.

How the Invention is Applied to Industry The invention can be used in laboratory-scale R&D studies of related sectors or in industrial zeolite derived directly from boron in chromatographic purification studies to be carried out Boron developed as a chromatographic filler or using this filler Derived zeolite in the form of HPLC columns and SPE cartridges in different sectors can be used. These products are specially designed to meet different industrial scale requests. Products in the form of boron-derived zeolite columns of different sizes designed as It can be produced and used for sectors.

Claims (5)

REQUESTS 1. It is a chromatographic filler, characterized in that it contains decyl or dealuminated ZSM-5, X or A type zeolite with boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester attached. 2. DAZB, which is a chromatographic filler, is a production method and its feature is; Dealumination of ZSM-5 type with high Si/Al ratio (Si/AI250) or X or A type zeolite with low Si/Al ratio (Si/AISS), Dealuminated zeolite boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester The installation is that it includes the processing steps. 3. DSZB, which is a chromatographic filler, is a production method and its feature is; Decylylation of ZSM-5 type with high Si/Al ratio (Si/Al250) or X or A type zeolite with low Sii'Al ratio (Si/Alsö), Decilyl zeolite boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester The installation is that it includes the processing steps. 4. DAZB production method, which is a chromatographic filler according to claim 2, and its feature is; adding to the reaction cabinet, starting the dealumination (A) reaction with the addition of 0.1-8 N HCl, H2804 or HNOs (2) at 1-4 times the volume of the zeolite, performing it in a stirred environment and cooling the mixture to room temperature (4) to obtain an acidic solution (5.1), Performing the filtration process by adding distilled water (6) 1-4 times the volume of zeolite (B) and obtaining filtrate (7.1), Adding distilled water (6) 1-4 times the amount of filtrate (7.1) by volume -3 times washing (C), removal of acidic solution (8) and obtaining DAZ (9.1), obtaining cooled DAZ (13.1) by cooling in vacuum (12) to room temperature (4) (E), on 0.05-1 mol boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester (14) and DAZ (13.1) addition of xylene (15) 1-3 times by volume, Boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester Obtaining the mixture including DAZ (17.1) by performing the insertion, leaching (B) and obtaining the filtrate (18.1) removed from xylene, washing by adding 1-3 times the filtrate (18.1) dichloromethane (19) to the filtrate (18.1) (G) and obtaining the filtrate (20.1), the drying mixture (22.1) It is cooled to room temperature (4) in a vacuum environment (12), and DAZB (23.1) is obtained as a result of the above process steps. 5. DSZB production method, which is a chromatographic filler according to claim 3, and its feature is; Addition to the reaction cabinet, Initiation of the decilylating (J) reaction by adding the amount of zeolite by volume, performing it in a stirred environment and obtaining a basic solution by cooling the mixture to room temperature (4) (5.2), Filtration with the addition of distilled water (6), 1-4 times the amount of zeolite by volume Carrying out the process (B) and obtaining the filtrate (7.2), Washing the filtrate (7.2) 1-3 times by adding distilled water (6) up to 1-4 times the volume by volume (C), Removing the basic solution (25) and obtaining DSZ (9.2 ), Obtaining DSZ (13.2) cooled by cooling (E) to room temperature (4) in a vacuum environment (12), with 0.05-1 mole ratio of boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester (14) on it. Addition of DAZ (13.2) 1-3 times by volume xylene (15), Obtaining the mixture including DSZ by adding boric acid, boric acid ethyl alcohol ester or boric acid methyl alcohol ester (17.2), Vacuum environment (12) performing the filtration process (B) and xylene removed The filtrate (18.2) is obtained, the filtrate (18.2) is washed by adding 1-3 times the dichloromethane (19) to the filtrate (18.2) by volume (G) and the filtrate is obtained (20.2), the drying mixture (22.2) is heated to room temperature in vacuum (12). (4) cooling, DSZB (23.2) is obtained as a result of the above process steps. . It is a chromatographic extraction (SPE) cartridge, characterized in that it contains DAZB or DSZB as filler. . It is a high pressure liquid chromatography (HPLC) column and its feature is that it contains DAZB or DSZB as filler. . It is a purification method of a colorant-sugar mixture, and its feature is to fill the unit volume of a 3-20 cc SPE cartridge containing DAZB or DSZB with 0.1 9 DAZB or DSZB, 3-5 volumes of methanol and pure methanol at 1-3 d/s from each cartridge. conditioning by passing water, loading the sugar-colorant mixture of 1-5% of the DSZB or DAZB amount into the cartridge at a flow rate of 0.5-2 d/s, Washing approximately 1/31 of the cartridge volume by passing methanol and hexane, respectively, 0 It includes the process steps of elution by adding 1-4 mL of 0.1 M acetate buffer solution at a flow rate of ,5-2 d/s.