구리, 코발트 및 니켈 프탈로시아닌 염료 수용액의 평형흡착등온

배 영 한·유 명 호·김 형 준·이 성 식

동아대학교 화학공학과

Adsorption Equilibrium Isotherms of Copper, Cobalt and Nickel

phthalocyanine Dye Aqueous Solution

Young-Han Bae·Myung-Ho Yu·Hyung-Jun Kim·Sung-Sik Lee

Department of Chemical Engineering. Dong-A University.

1. INTRODUCTION

Metallophthalocyanine has been widely exploited in industry and academia, in a variety of applications ranging from conventional dye stuffs to catalysis, coating for read/write compact discs that appear gold or greenish gold, high-grade printing ink, paint, rubber, plastics and calico-printing paste for textile, chemical sensors including thin film resistive devices and as an anti-cancer agent, etc.

Because those structure is stable as hemoglobin, the metallophthalocyanine molecular exhibit properties such as superior light and wash-fastness than metal free phthalocyanine and any other dyes. However, metallophthalocyanines are highly toxic. That many solid-state properties of metallophthalocyanine critically depend on the solid-state structures is known, but until today, liquid-state properties in order to remove and recover of metallophthalocyanine from wastewater have not been reviewed in detail. Thus, the removal and recovery of metallophthalocyanine are important problems, due to the difficulty in treating them by the usual method.

In this paper, the effective removal of copper, cobalt or nickel and organics from metallophthalocyanine dye solution was investigated by adsorption method of using various adsorbents. And the adsorption isotherms of metallophthalocyanine in aqueous solution onto various adsorbents were studied.

2. EXPERIMENTAL

The used adsorbents are the anion exchange resin of styrene system (AES) and the strong basic anion exchange resin of styrene system (SBA) by Mitsubishi Chemie were used without further purification. and High silica zeolite (HSZ) by Toyo Chemie and granular activated carbon (GAC) by Calgon Ltd crushed by  14∼20 mash were used after getting rid of the suspended matter by means of decantation using the distilled water. The using adsorbates are Cobalt (Ⅱ), Nickel (Ⅱ) or Copper (Ⅱ) phthalocyanine tetrasulfonic acid tetrasodium salt which were produced by Fluka Chemie AG. The adsorbents and metallophthalcyanine used in experiment have the structure as Table.1.

The equilibrium amounts adsorbed were determined by the so-called batch bottle technique and the experiments carried out 298K. The organic and metal ions concentration were determined by total organic carbon analyzer (TOC, Model SHIMADZU TOC-5000) and atomic absorption spectrophotometer (AA, Model SHIMADZU AA-6501F), respectively.

Table 1.  The Structures of Used Adsorbents and Adsorbates.

Materials	Adsorbents													Adsorbate
		GAC			SSB			SSA			HSZ					Metallophthalocyanine dye (M : Co, Cu, Ni)
Functional groups

3. RESULT AND DISCUSSION

Figure 1 is adsorption capacity for metal ions in artificial dye waste-water onto various adsorbates. Preliminary experimental results showed that AES has superior adsorptibility. but, GAC has little.

Fig.1.Adsorption capacity for metal ions and

TOC in metallophthalocyanine dye

aqueous solution onto various adsorbents.

Adsorption isotherms of the metal ions and TOC on AES were studied with varying pH values to determine the optimum pH range for their removal.

Figure 2 shows the experimental results of adsorption isotherm of the cobalt, copper and nickel ions and TOC in metallo- phthalocyanine dye solution on AES. The optimum pH values for adsorption of Ni, Cu, Co and TOC on AES are 4.2, 8.6, 4.1 and 10.0, respectively.

The adsorption capacity of AES with cobalt ion is highly dependent on equilibrium concentrations. However, copper ion has a flat or shallow slope. and adsorbed amounts of copper ion onto AES is independent of equilibrium concentration.

Fig.2. Adsorption isotherms of metal ions on

AES in metallophthalocyanine dye solution

Figure 3 and 4 show typical experimental results of theoretical adsorption isotherms for nickel and copper ion in metallophthalocyanine dye solution onto AES, using the Henry, the Freundlich, the Langmuir, and Toth equation. The theoretical adsorption isotherms of nickel ion on the AES is linear. but, that of copper ion is favourable.

Equilibrium parameters were determined by so-call curve fitting method from equilibrium  data as shown Table 2.

Fig.3. Relation of between experimental and

theoretical adsorption isotherm of nickel

phthalocyanine

Fig.4. Relation of between experimental and

theoretical adsorption isotherm of copper

phthalocyanine

Table 2. Parameters in the Henry, Freundlich, Langmuir and Toth equation

Material and pH Equation		Co				Cu				Ni
		4.1	6.2	8.0	10.1	4.1	6.2	8.6	10.0	4.2	6.2	8.4	10.0
[eqn: q_e =K_p C_e]	[eqn: K_p]	1.17	1.02	0.88	0.78	0.12	0.07	0.05	0.06	0.62	0.51	0.47	0.36
[eqn: q_e =KC_e ^1/n]	[eqn: K]	1.74	1.79	1.02	0.78	0.14	0.09	0.09	0.11	1.39	1.10	0.34	0.32
	[eqn: n]	0.69	0.59	0.81	0.99	6.02	5.93	5.93	6.15	0.73	0.74	1.11	1.04
[eqn: q_e ={q_m CDOT K_L CDOT C_e} over {(1+K_L CDOT C_e )}]	[eqn: q_m]	63.4	47.0	61.1	30.7	0.14	0.10	0.09	0.13	4.09	10.4	5.03	2.80
	[eqn: K_L]	0.02	0.02	0.01	0.03	28.8	15.0	539	8.56	0.05	0.02	0.04	0.10
[eqn: q_e ={q^INF CDOT C_e} over {(b_T +C_e ^M )^1/M}]	[eqn: q^INF]	1.11	1.10	0.87	0.83	401	3.49	309	2025	1.76	4.55	3.86	1.41
	[eqn: b_T]	0.46	2.88	0.95	8.20	1.18	1.17	0.87	0.09	43.7	79.7	27.0	26.5
	[eqn: M]	14.8	13.6	66.7	31.5	0.11	0.36	0.10	0.10	1.76	1.41	1.14	1.91

CONCLUSIONS

The effective removal of metallophthalocyanine dye solution by adsorption process was studied.

1.Anion exchange styrene system resin(AES) has superior adsorbability of             metallophthalocyanine dye solution.

2.The optimum pH values for adsorption of Ni, Cu, Co and TOC on AES are        4.2, 8.6, 4.1 and 10.0, respectively.

3.The adsorption isotherms of metallophthalocyanine dye solution are favorably        adapted to the Freundlich and Toth isotherm equation.

LITERATURE CITED

1.Sung-Sik Lee, Myung-Ho Yu, Kum-Chan Choi, Dai-Ung Choi, □Removal of         Copper in Copper Phthalocyanine Dye Solution by the Chelate Resin Particles□,      Journal of Korean Society of Environmental Engineers, Vol.19, No.12 (1997).

2.Adsorption Technology : A Step-by-Step Aproach to Process Evaluation and         Application. Frank L.Slejko, Tall Oaks Publishing, Inc. (1985)

3. Kaneko, K.,“Adsorptive Separation”, Proceeding of Seiken Symposium, Japan,

Tokyo, 7, PP.143∼157(1991)

4.CHEMICAL JOURNAL , p 31∼36, Vol. 6  No. 202  (1996)