Bulletin

of the Chemists and Technologists

of Macedonia,

Vo!. 12. No. 1 - 2, p. 45 - 50 (1993) ISSN 0350 - 0136

GHTMDD - 216
Manusript received: November 5th, 1991 UDC:

549.69 : 661.183 Professional Paper

DETERMINING THE ADSORPTION CHARACTERISTICS OF THE ZEOLITE 4A TYPE SYNTHESIZED FROM NATURAL RAW MATERIALS
Blagica Cekova and Vladan Zlatanovic
School of Chemistry "Maria Curie-Sklodowska'~ 91000 Skopje, Macedonia Faculty of Technology and Metallurgy, The "Sv. Kiril & Metodij" University, 91000 Skopje, Macedonia

From a practical point of view the reserves of natural zeolites are definitely limited. Therefore, in the work reported here we try to synthesize zeolite type 4A starting from various raw materials. The zeolite type 4A was obtained by low-temperature synthesis at 363 - 373 K from oxides whith molecular ratios as follows: . SiOz/A1203 = 1.3 NazO/SiOz = 3 HzO/NazO = 50 . The prepared mixture for synthesis was characterized with the following chemical composition: 3.9 NazO .1.3 SlOZ .AlP3 .195 HzO. By determining their adsorption characteristics and applying thestatical gravimetric method, the results obtained were compared to the commercial zeolite type 4A "Birac"- Zvornik produkt. Key words: adsorption; zeolite; BET; Langmuir's equation

INTRODUCTION The zeolite type 4A is characterized by a threedimensional net structure consisting of channels and cavities. This porous structure has an affinity to adsorb molecules having a definite size and shape. These cavities and channels are filled with water, known as zeolite water. In cases where the hydric water is drawn out, the intercrystal structure remains with empty spaces. The volume of the empty space amounts 45% . The volume of the empty space ofthe type 4A amounts 3 0.28 - 0.35 g/cm . The process of penetration of the molecules adsorbed through the frames of the cavities in the zeolite has a complex "physical-chemical" nature. In order to describe this process, the terms "effective diameter" of the frames and "critical diameter" of the adsorbed molecules are frequently used [1,2] The molecules can easily penetrate through the frames of the cavities, if their critical diameter is considerably smaller than the effective diameter of the cavities.

EXPERIMENTAL The adsorptional characteristics of the products obtained (Tests 11, Ill, IV) are determined by the statical gravimetric method. Test I - commercial zeolite type 4A "Birac" Zvornik Test 11- product obtained from a blue loose from Montenegro. lest III - product obtained from the SiOz precipitate, precipitated from hydrated Na-silicates. Test IV - product obtained from hydrated Nasilicates. All four products were held at 298 K for 3 hours. The results obtained were compared to the adsorptional characteristics of the commercial "Birac" Zvornik product, tested under the same conditions (lest I). The quantity values of the adsorbed water vapour at 297 K depending on the pressure are given in Thble 1 in Langmuir's equation, .and in Thble 2 in B.E.T. equation for multilayer adsorption. The course of the adsorptional isotherms (Fig.1) correspond to Langmuir's equation type isotherms, but for the microporous adsorbents, such as zeolites, the best applicable equation proved to be M. M. Dubinin and V.A. Astahov's equation [3,4,5]. The adsorption capacities for water vapour ofthe products 11,Ill, IV and the commercial product I were determined by the graphic dependency of the linear form of the isotherms in Langmuir's coordinates, given in Fig. 2. The values of the adsorptional cap~cities of the products obtained and the commercial product are

46

B. Cekova, V. Zlatanovic

given in Thble 1. The adsorption capacities are used to determine the specific surface using the formula: S

= A m . Na

. IQ-18

[m2/kgJ

= Na

. am . W

The RE.T. equation was also applied for the multilayer adsorption. P a(Po - P) The adsorption Fig. 4. 1 C-l
am C

= am C'

. Po
presented in

isotherms are

Na - Avogadro's number, am - adsorptional capacity (mol/kg), monolayer capacity determined by the linear form of the isotherm in RE.T. coordinates, W - surface covering by the molecule of the adsorbent in the complemented monolayer [6], Am - capacity of one molecule of water at 298 K which amounts 0,125 nm2.
The values for the determined adsorptional capacities and for the specific surfaces of the products Il, Ill, IV and the commercial product I are shown in Thble 2. 'I~. 10
~

The adsorption capacities were determined by the linear form of the adsorption isotherms in RE.T. coordinates, and their values were used to determine the specific surface by the RE.T. equation: ~ ~8 d

/II

~
ci- 8
1I

11 N

Plpo'

Q1
Fig. 3. Adsorptional commercial

Q2

Q3

Q4 P/Po
and

Fig. 1. Adsorptional isotherms of the products of synthesis and commercial zeolite for water vapour steam at 298 K IV , ~

isotherms of the products of synthesis zeolite for water vapour at 298 K

~ " d: <:

1,6

'} ~
Q06

"1" 1..

~ Cl;

1,2

Q05
1.0 '\ 0,04 0,

0.6

0,03

0.02

PI~G.

a1

Q2

03

I.

05 P/Po

Fig. 2. Linear dependency on pressure of the quantity of water vapour adsorbed for the products of synthesis and commercial zeolite in Langmuir's coordinates

Fig. 4. Linear dependency on pressure of the quantity of water vapour adsorbed for the products of synthesis and commercial zeolite in RE.T. coordinates

BuII.Chem.TechnoJ.Macedonia,

12, 1-2, p.45-50(1993)

Detennining

the adsorption characteristics of the zeolite

47

Ta b 1e 1 Adsorpti0J1alcharacteristics of the obtained products II, IIf, W

and the commercialproductI in dependingon thepresure- Langmuir'sequation

Test T [K] I 298 P [hPa] 1.371 3.005 5.220 7.910 1.371 3.005 5.220 7.910 1.371 3.005 5.220 7.910 1.371 3.005 5.220 7.910 0.1824 0.3601 0.5961 0.8777 0.3692 0.6759 1.0723 1.5077 0.2221 0.4126 0.6606 0.878 0.5165 0.9015 1.3213 1.8048 Pia a [mol/kg] 7.5131 8.3428 8.7558 9.0120 3.7127 4.4457 4.8679 5.2464 6.1715 7.2820 7.9011 9.0077 2.6543 3.3333 3.9506 4.3827 am [mol/kg] 9.375 S [m2/kg 103] 70.58

II

298

5.45

41.03

III

298

8.86

66.70

IV

298

5.00

37.64

Ta b 1e 2 Adsorptional characteristics of the obtained products If, IIf, W and the commercial product I - B.E. T. equation
Test T [K] I 298 P [hPa] 1.371 3.005 5.220 7.910 1.371 3.005 5.220 7.910 1.371 3.005 5.220 7.910 1.371 3.005 5.220 7.910 0.0433 0.0949 0.1650 0.250 0.0433 0.0949 0.165 0.250 0.0433 0.0949 0.165 0.250 0.0433 0.0949 0.165 0.250 PIPa a [mol/kg] 7.5131 8.3428 8.7558 9.012 3.7127 4.4457 4.8679 5.2464 6.1715 7.2820 7.9011 9.0077 2.6543 3.3333 3.9506 4.3827 0.006 0.012 0.0229 0.0369 0.0122 0.0235 0.0405 0.0634 0.00733 0.0144 0.0249 0.0369 0.0170 0.0315 0.0497 0.0759 Pia (Po-P) am [mol/kg] 8.58 S
[m2/kg

103]

64.59

II

298

4.22

31.77

III

298

8.87

66.78

IV

298

3.63

27.33

RESULTS AND DISCUSSION By comparing the results obtained in the B.E.T and Langmuir's equations, it can be noticed that the results of the product III are compatible with the results of the commercial product while for the other products there are some deviations probably due to the lower percentage of Si02 in the initial raw materials used for synthesis. The results show that Langmuir's equation, which is characteristic of the micro porous adsorbents such as zeolites, proved to be more applicable. Concerning the micro porous adsorbents, the assumption for the adsorptional surface has no physical meaning because the adsorption in such adsorbents is carried out by the filling of the total volume of the

fJIac.xeM.TeXHOJI.MaKe,L{OHHja,

12, 1-2,

c.45-50(1993)

48

B. Cekova, V. Zlatanovic

i :1 , ~

'T

:1 I

j 35

J 30

25 'lA

20

1$ 29

1(1

Fig. 5 - Diffractogram

of the commercial

zeolite

type 4A "Birac" - Zvornik

1.

35

30

25

lO

15

10 .<:-e

Fig. 6 - Diffractogram

of the blue lose from Montenegro

(Test II)

BuII.Chem.Technol.Macedonia,

12, 1-2, p.45-50(1993)

Detennining
1 ;,
.,

the adsorption characteristics of the zeolite

49

'I !I
~
I ~

"

ii
i

il

jl "
I

li !

I;

'\
,I

'I

i:

I:
11

I
"

I
~

'I

~)UV~~
3()

25

16

.
IS 10

'i

,
Fig. 7 - Diffractogram

of the precipitate

SiOz (Test III)

..

30
Fig. 8 - Diffractogram

25

20

15
from the hydrated

10
Na-silicates

S
(Test IV)

of the z~olite obtained

cavities. The adsorptional field in the zeolite is distributed through the total free internal volume. The dimensions of the micro pores correspond to the molecular diameters which leads to the overlapping of the potential fields from the opposite sides. Unlike the other adsorbents, the micro porus structure

of the zeolites is determined by their crystal structure which, on the other hand, determines one of the essential characteristics of the zeolites as adsorbentsthe stability of the pore dimensions. Diffractograms of the tests are shown in Fig. 5, 6, 7,8.

rnaC.xeM.TeXHoJl.MaKeLlOHHja,

12, 1-2, c.45-50(1993)

1I
50 B. Cekova, V. Zlatallovic

CONCLUSION From the results obtained on the adsorptional characteristics of the obtained products 11,Ill, IV at can be concluded that product III has a longer specific surface than the commercial zeolite which is due to Product 11and IV have similar specific surfaces which in product 11is due to the polymeric structure of the blue loose boxide, and for product IV to the fact that the water glass has a simillar silicate module, Le., the quantityofSi02 is low, and the percentage ofNa20 [8] is high.

the pure starting material - precipitated SiOz from

hydrated Na-silicates.

REFERENCES
[1] R. M. Barrer, Brit. Chem. ElIg. 4, 5 (1959).
[5] M. M. ):{y6I1HI1H,B. A. ACTaxoB, H3B. AH CCCp, 1,5-21(1971) Cep. XI1M.

[2] B. Cekova,Master's Thesis, Facultyof Technology- Skopje,

1983. [3] M. M. Dubinin, J. Colloid. IlIterface Sci. 23, 487 (1967). [4] M. M. Dubinin, V. A. Astakhov, Molecular Sieves Zeolites Il., Adv. Chem, Ser: 102, American Chemical Society, Washington, D. C. 1971, p. 69

[6] 11. E. Hel1MapK, A.llcoPllI.lUJI U nOp03HTOCTb, H3L1aTenbCTBO "HaYKa", MocKBa, 1976. [7] rper, K. CI1Hr, A,l.lcop6I.luJI ,Y,l.leJ1bHHaJI, nOBcpxHOCTb, nopucToCTb, Ml1p, MocKBa 1984. [8] B. Cekova, Ph. D. Thesis, Faculty of Technology, Skopje, 1988.

Pe311Me O)];PEj(YBAI-bE HA A)];COPI1IUIOHJlTE KAPAKTEPJlCTJlKJI )];OEJlEH 0)]; I1PJlPO)];HJI CYPOBJlHJI

EJIarHua I(eKOBa 11BJIIl)J;IlH 3JIaTIlHOBHK*

HA 3EOJIJlT TJII14A

XYI( "Mapuja KHPU-CKJIO,l.lOBCKa'; CKonje, MaKc,l.lOHuja * TCXHOJIOlllKD-MCT8JIYPlllKUt/JaKYJITcr, CKonje, MaKC,l.lOHuja KJlY'IHH 36opOBH: aLlcopm.\l1ja; 3eOJII1T;BET; JIaHrMYl1poBa paBeHKa

):{0611eHI1Te pe3YJITaTI1 OLll13BpWeHI1Te I1cnl1TYBal-ba noKa>Kaa LleKa e MO>KHaCI1HTe3a Ha 3eOJII1T Tl1n 4A OLlnpl1pOLlHI1 CYPOBI1HI1, aLl0611eHI1Te BpeLlHOCTI13acneUl1lpl1'1HaTa nOBpWI1Ha

nOTBPLlYBaaT LleKa co HajrOJIeM Kpl1CTaJII1HI1TeT e npOLlYKTOT Ll0611eH OLlnpeUl1nl1TaT SiOz (np06a Ill).

Bull.Chem.Technol.Macedonia,

12, 1-2, p.45-50(1993)