한외여과막시스템을이용한금속가공폐수의실험실적처리및현장적용연구

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1 Korean Chem. Eng. Res., Vol. 43, No. 4, August, 2005, pp 한외여과막시스템을이용한금속가공폐수의실험실적처리및현장적용연구 m Ç m Çn * o e p nn 2-2 * p qp (t) ne k e 56-1, n re l 312 (2005 3o 21p r, o 13p }ˆ) A Study on Laboratory Treatment of Metalworking Wastewater Using Ultrafiltration Membrane System and Its Field Application Jae Heum Bae, In-Gook HwangGand Sung Duk Jeon * Department of Chemical Engineering, The University of Suwon, San 2-2, Wau-ri, Bongdam-eup, Hwaseong-si, Gyeonggi-doG , Korea *Separation Design Tech Co., Ltd.,G#312, Institute of Chemical Process, Seoul National University, San 56-1, Shilim-dong, Gwanak-gu, Seoul , Korea (Received 21 March 2005; accepted 13 May 2005) k h q,, rq l ll tp r rl om s r~ p o p eˆ. l l n n o mm t r n l edšp pn l } q m. p e l p p polyacrylonitrile(pan)p n p mm p l nl Œ o (CODr p)p r l nl } p rr l s m. t rrm n o mm p n nl p 10 kdal 100 kda v l COD r pp 90 wtí-95 wtí p pr v Œ d 4 p v m. p mm 3wtÍl 10 wtí v nl p COD r pp v v Œ d m. t rrm n mp mm p n mm p v COD r pp p pr v Œ d p l tl. p p nl qvp p PANp l n mpp p v p p p p., n mpp o rkp qvp PANp 100 kdap nl } rr p Ž l. p e n l PAN qvp (MWCO=100 kda)p n nl pilot edšp nr l n p o mm k r kp } k rrm p o q n q m. q e nl rp rrm n mpp rp l q n pl s rl l rr n p 12 p v eˆ pl. Abstract Nowadays a large amount of wastewater containing metal working fluids and cleaning agents is generated during the cleaning process of parts working in various industries of automobile, machine and metal, and electronics etc. In this study, aqueous or semi-aqueous cleaning wastewater contaminated with soluble or nonsoluble oils was treated using ultrafiltration system. And the membrane permeability flux and performance of oil-water separation (or COD removal efficiency) of the ultrafiltration system employing PAN as its membrane material were measured at various operating conditions with change of membrane pore sizes and soil concentrations of wastewater and examined their suitability for wastewater treatment contaminated with soluble or insoluble oil. As a result, in case of wastewater contaminated with soluble oil and aqueous or semi-aqueous cleaning agent, the membrane permeability increased rapidly even though COD removal efficiency was almost constant as 90 or 95 as the membrane pore size increased from 10 kda to 100 kda. However, in case of the wastewater contaminated with nonsoluble oil and aqueous or semi-aqueous cleaning agent, as the membrane pore size increased from 10 kda to 100 kda and the soil concentration of wastewater increased, the membrane permeability was reduced rapidly while COD removal efficiency was almost constant. These phenomena explain that since To whom correspondence should be addressed. jhbae@suwon.ac.kr 487

2 488 q Ër the membrane material is hydrophilic PAN material, it blocks nonsoluble oil and reduces membrane permeability. Thus, it can be concluded that the aqueous or semi-aqueous cleaning solution contaminated with soluble oil can be treated by ultrafiltration system with the membrane of PAN material and its pore size of 100 kda.g Based on these basic experimental results, a pilot plant facility of ultrafiltration system with PAN material and 100 kda pore size was designed, installed and operated in order to treat and recycle alkaline cleaning solution contaminated with deep drawing oil. As a result of its field application, the ultrafiltration system was able to separate aqueous cleaning solution and soluble oil effectively, and recycle them. Further more, it can increase life span of aqueous cleaning solution 12 times compared with the previous process. Key words: Aqueous Cleaning Solution, Semi-aqueous, Soluble Oil, Insoluble Oil, Ultrafiltration, Oil Separation, Membrane Permeability, COD Removal 1., ~, q p ll qlp q p p v k qlp o o l o n. o o qnp rp n om qnp t rp n o. n op o(base oil)l d(straight chain)p Ž ˆ (ring structure) p Š ˆ p pp l ~ rp n p n Š mpp n op o t n p. n o o v om p om rp o l l ro(emulsion oil), o(semi-synthetic oil), o(synthetic oil) [1]. qlp o l kpp n, q p qll p p. r p vp eˆ o l rl n o r r rp p rneˆ p. ms Ž p r prl p r rp rr 1,1,1-TCE(1,1,1-trichloroethane) t n l l k 1987 m pr l 1,1,1-TCE ms Ž v vr v l 1996 n p v l n m p p q rp n p s pp 2010 np r v m rl p [2]. 1,1,1-TCEp ~ rr, t, ~ m, ˆ, k m, p rr p l lv p. p~l o, ql kr, r p k p rr tl t rr q o ~ rr p [3, 4]. t r rp r,, s p lv. r l rr pn l r p mmp vr } rp pr re p v mm rr, l, r p pn l mm p r l rr q n pr p p mm n rr eˆ rr Œp l n. l r l q rkp mm p } rp r p ~r l p v(,, )p r. s l p r p l s, k s, air knife s p p s. p, rp r r t rl p rl mm r (gravity separation), ˆ r(activated-carbon processing), pm (ion exchange process), nl (ultrafiltration), l Œk (reverse osmosis) p pn o q l p ln q n p. p o q p pp p o l opq r l, o o mm p r r dˆ (skimming) p o m mm p t p n k p r} q pn p [1]. l l t redšp r, rl n / n om rr mm } q n o l nl l m. l, nl p q, nrk e p mm l } p Œ d, o p(cod r p) p r mp mm nl p q n o l p rl Œ pl e m. p nl p e erp l n l H qp rrm o o mm } q n o l rne k m e l t rr((t) mž; N-58) n o((t) nš; Cutmax 226)m n o Table 1. Physical properties of cleaning agents used in this work Classification Neopharm NEOZOL-150S Neopharm NEOZOL-750H Aqueous cleaning agent Semi-aqueous cleaning agent Major components Anionic surfactant, alcohol, builders, water etc. Oils, primary alcohol ethoxylate, BDG water etc. Viscosity (25 o C) 2.35 cp 7.50 cp Water content 77 8 Specific gravity (25 o C) Surface tension (25 o C) Flash point ( o C) None None ph (20) o43 o k

3 nl edšp pn p e er } q rn l 489 Table 2. Specifications of metalworking cutting oils Classification Houghton Hocut SSK-H Houghton Cutmax 226 Emulsion-type cutting oil Non-aqueous cutting oil Major components Base oil, chloroparaffin, fatty acid, etc. Base oil, chloroparaffin, fatty acid, alkanolamine, esters of fatty acid, sodium alkylsulfonate Viscosity (25 o C) 20 cp 25 cp Specific gravity (15 o C) ph (20 o C) 9.0 (10 dilution) 4.7 Appearance Light yellow (milky white in dilution; opaque) Dark brown Table 3. The Specifications of UF membrane module used in this study Item Unit PN01 PN03 PN10 Molcular weight cut off MWCO 10,000 30, ,000 (Dalton) Length of membrane mm Diameter of membranegid/od mm 0.8/ / /1.5 Number of membrane EA Area of membrane m Fig. 2. Schematic flow diagram of basic ultrafiltration membrane system. 1. Feed tank 5. Flowmeter 2. Feed pump 6. Membrane module 3. Valve 7. Pump bypass 4. Pressure gage 8. Mixer Fig. 1. Schematic diagram for preparation of oily contaminated rinse water. (Hocut SSK-H; (t) nš) p l n m. p l kp Table 1 Table 2l ˆ l. nl ((t) k)p qvp PAN(polyacrylonitrile)p rp m 2, q (molecularweight cut-off, MWCO)p 10 kda, 30 kda, 100 kdap s p p n m. e l n p qop Table 3. mp o mm Fig. 1 p rrl o 3wtÍ ~ l p rr o kp 3wtÍ, 5 wtí, 10 wtí l rs m { mnk nl e nl l p mm } e p q (10, 30, 100 kda) mm (3 wtí, 5 wtí, 10 wtí) l o Œ d e p 8e k nr l m. p nrk p m e p l rp Œ d p s l nr m e l 1.5 kg f /cm kg f /cm 2 p nr m. mm p o r nl Œ r p e tp COD r l m. l l pn nl p pn } q n e q Fig. 2m. l m p mm l p rqs l. mm p opo Œ p o p o l p r l k p p yp k l p r l. r rm o mm p pr ov o k Œ e. rqsl l k Œ m q rn e q p r l~ }s n p p n pp ~ l~ n p t p t n p s l. Fig. 3p k q deep drawing(p ) l p rs p H qp nl edšp mp o } q n r p. p rl n p mpp n o(houghton Houghto Draw 7002)p n pp p rp l l p t o coating } p. Coatingp r} rp k rr l l p o } r rp p. l l srl l edšp l k r pr n r r tl p o mm rkp } p Fig. 3 p nl p } edšp p l r kp l r mp k r l l r mpp e q n k r rs q e n q m. p n nl p q PVDF ( p 3 m, KOCH Model HFP-276-FNO, MWCO=100 kda, Material=PAN)p n m nrk p 1.8 kg f /cm 2 p mp o rr k 2wÍp n p o o l p. Korean Chem. Eng. Res., Vol. 43, No. 4, August, 2005

4 490 q Ër Fig. 3. Schematic flow diagram of recycling of alkaline solution and reuse of cutting oil in H motor company. Table 4. Specification of chemical membrane cleaner(koch KLEEN KLD II) Classification Specification MODEL KOCH KLEEN KLD II Original ph 12 Constituents Alkali type surfactant solution Operating temperature below 50 o C Operating ph nl } }k qpn edš, l r mp } l n t nl p ˆo l mm lp Œ o p d v p mmol p lp n Œ o p p o rr n l p } n p. rr e el ph 11 r p p (NaOH) nk v } p Œ d r l n l p Œ o r r m. ql KOCH l nl (UF p) rn }r(koch KLEEN KLD II) n m. n p p rsl n k 2/3 r }n rsl l p n p m k 40 o C r meˆ n p ph k 10 r m o (NaOH) l p KLD II rs n p k 0.5-1Í r. p KLDm nkp p edšl q e pp mm p }. p }e p p rp n k 1-2e }. Table 4 ql n p rkp KOCH KLEEN KLD II }k vp ˆ l [5-8] COD standard methodp Colorimeter l t l r o43 o k m. Colorimeter p COD meter(aqualytic PC compact, Germany) n l e l eˆ l l r Žq (600 nm)p p t l p kp r l p COD p. o v(suspended Solid; SS)p r k p l v(pore size; 1 µm) l l l pr p e l eˆ p p s l k l r l vp r l o vp kp p n m. ˆo(skimming oil) n tp o rnk tl m pmm l l p l r mpp kp oe n l ˆo(skimming) kp kp r p f p lr. p ˆo o oe (MF 80/Hanil, Korea)p e s p 1,000 rpmp m. N- hexane kp e tp o vp kp vmm r e p r m. Bacteriam fungi p rp BIOSAN l SANI- CHECK BF pn m. r Ž p ky p l v l 2-3 k, Ž p o C m l 24-36e k SANI-CHECK BFl vp o k m. k bacteria fungi p BIOSAN l r SAI-CHECKp Conversion m s l rp bacteriam fungi r m. 3. y 3-1. ji { t rrm n o mm p } t rrm n o mm p q n e Fig. 4m Fig. 5 v ˆ l. p e p nr k p 1.5 kg f /cm kg f /cm 2 p nr 2.0 kg f /cm 2 nr

Fig. 4. COD removal and permeate flux of 3 wtl-contaminated rinsing water as a function of time at pressure of 2.0 kg f /cm 2 (contaminants: NEOZOL-750H cleaner and soluble cutting oil).

p Œ d po p v t rr n op p o p v p p mmr v p p Ž. nr e p l Œ d mmop n mp mml l r pr tp ov m. l p l rp mm l o mppqm l p n l p mmp l rp Œ dp m n l p p rrp.

5 Fig. 4. COD removal and permeate flux of 3 wtl-contaminated rinsing water as a function of time at pressure of 2.0 kg f /cm 2 (contaminants: NEOZOL-750H cleaner and soluble cutting oil). nl edšp pn p e er } q rn l 491 o mm q n o nl edšl q p 100 kdap p j rp p k pl. Fig. 5 mm p l Œ dm COD r pp ˆ p. l m p p mm 3wtÍl 10 wtí v eˆ n COD r pp 90Í pr v Œ d p mm v p ˆ. p Œ d po p v t rr n op p o p v p p mmr v p p Ž. nr e p l Œ d mmop n mp mml l r pr tp ov m. l p l rp mm l o mppqm l p n l p mmp l rp Œ dp m n l p p rrp. p mmp r l p Œ d oeˆ q t rrm n o mm p r e e Œ d pp 60Í r l tl t rrm n o mm p } t rrm n o mm p q n e Fig. 6 Fig. 7l ˆ l. p e p nr k p 1.5 kg f /cm kg f /cm 2 p nr Œ d p ll e s l 1.5 kg f /cm 2 p nr m. Fig. 6p nl p q l COD r pp ˆ p. q p 10 kdap p n COD r pp 90Í m Œ d k 15 L/m 2 hrp ˆ. q p 30 kda p p n Œ d 50 L/m 2 hrp v p ˆ q p 100 kdap n Œ d 75 L/m 2 hrp v p m. l COD r pp q p 10 kdap nm p 90Í mv Œ d r rp nre p l p lt p. Fig. 7p mm vp Œ dm COD r pl m p ˆ p p m FigU 5. COD removal and permeate flux of contaminated rinsing water with various concentration as a function of time at pressure of 2.0 kg f /cm 2 (contaminants: NEOZOL-750H cleaner and soluble cutting oil; membrane pore size = 30 kda). n 1.5 kg f /cm 2 Œ d 30Íp ƒ e s l 2.0 kg f /cm 2 p nr m. Fig. 4 nl p q l Œ dm COD r pp ˆ p. p q p 10 kdap n COD r pp 90Í m Œ d k 30 L/m 2 hrp ˆ. q p 30 kdap n Œ d 2 p v 70 L/m 2 hrp ˆ p q p 100 kdap n Œ d 4 p v 130 L/m 2 hr p p ˆ. COD r pp l l n p l 90Í m. rrm n Fig. 6. COD removal and permeate flux of 3 wtl-contaminated rinsing water as a function of time at pressure of 1.5 kg f /cm 2 (contaminants: NEOZOL-750H cleaner and insoluble cutting oil). Korean Chem. Eng. Res., Vol. 43, No. 4, August, 2005

492 q Ër r v k l q p p Ž. qp l qvp PANp n nl edšp n o mm p } l p lt p. 3-1-3. rrm n o mm p } Fig. 9m Fig 10l rrm n o mm p nrk p 2.0 kg f /cm 2 p n nl } e ˆ l. Fig. 9 nl p q l Œ dm COD r pp ˆ p.

5 kg f /cm 2 (contaminants: NEOZOL-750H cleaner and insoluble cutting oil; membrane pore size = 30 kda). Fig. 9.

6 492 q Ër r v k l q p p Ž. qp l qvp PANp n nl edšp n o mm p } l p lt p rrm n o mm p } Fig. 9m Fig 10l rrm n o mm p nrk p 2.0 kg f /cm 2 p n nl } e ˆ l. Fig. 9 nl p q l Œ dm COD r pp ˆ p. q p 10 kdap Fig. 7. COD removal and permeate flux of contaminated rinsing water with various concentrations as a function of time at pressure of 1.5 kg f /cm 2 (contaminants: NEOZOL-750H cleaner and insoluble cutting oil; membrane pore size = 30 kda). Fig. 9. COD removal and permeate flux of 3 wt -contaminated rinsing water as a function of time at pressure of 2.0 kg f /cm 2 (contaminants: NEOZOL-150S cleaner and soluble cutting oil). Fig. 8. Microscopic view of membrane surface by a polarimetric microscope (Nikon Model # ECLIPSE ME600). m 3wtÍl 10 wtí v eˆ n COD r pp lv Œ d r m. nr e p l d p ˆ p. Œ d po p v t rr n op p o p v p p mmr e r p p p p Ž. Fig. 8p p mm r mm p p m p lt p. l } p mm rl p l p vp r llp Œ d 0l p l mm p l p vp }ov p p pl. t rrm n o mm nl p r p p Œ d pp 30Í p n rs m. p po n op n qvp polyacylonitrile p p n mp p n v p q v k p l l rp q o43 o k Fig. 10. COD removal and permeate flux of contaminated rinsing water with various concentrations as a function of time at pressure of 2.0 kg f /cm 2 (contaminants: NEOZOL-150S cleaner and soluble cutting oil; membrane pore size = 30 kda).

7 p n COD r pp 95Íp p ˆ l Œ d k 75 L/m 2 hrp ˆ. q p 30 kdap p n Œ d 2 p v 130 L/m 2 hrp ˆ p q p 100 kdap n Œ d 4 p v 250 L/m 2 hr p p ˆ. pl l COD r pp q p 10 kdap nm 30 kdap 95Í 100 kdap n CODr pp k lv 90Í r l t p. p p p q p ƒvl mmpqp ƒ v pq p ppp ˆ., rrm n o mm nl edšp } o q p 100 kdap p 30 kdap p 10 kdap l l COD r pp s lvv Œ d 10 kdap 4 p v p k mm } l rp p k pl. Fig. 10p p mm v eˆ COD r pp l Œ d p ltv mm p pr nr e p l Œ d r pr tp ov p. p mm v Œ d po rr n op p o p v p p mm r r rp v p p Ž. mm nl p r Œ d Œ pp 80Í p p n k. p p rrm n o o PAN qvp nl p d mmeˆv kp mm l k rp d Œ oeˆ ppp p pl rrm n o mm p } Fig. 11p rrm n o mm p nrk p 2.0 kg f /cm 2 p n nl } e ˆ l. l m p rrm n o mm nl p m lp p mm nl edšp pn p e er } q rn l 493 l Œ d r p lt p. r rm n o mm qvp PANp n nl p l lp } lpp lt mnk Fig. 3 p k rr/ o q n pilot edšp v 2.2.2p nr s p nr Fig. 11 Table 5, Table 6p e ll. Fig. 12 nre l Œ o lt p. l Œ o p nre l r lv e v p Œ o p 10(L/min) l v KOCH KLEEN KLD II r l e nr m p. Œ pp n o mm r p e } m p 80Í p pp ltl. Table 5 }sm sp N-hexane extract, o v(ss) lt p. Table 5l } nre p l }sp N-hexane m o v p llv s p v p ˆ. p p sl nl p v N-hexane extract m SS p tn p n mpp v p p Ž. v rsp o }r pr ov pl. p p PAN qvp nl p mp p v k k sl l N-hexane v }rp o p d nl p l }sp o pr ov ppp lt p. Table 6p sl m pp om t o(original oil)p p lt p. Table 5. Change of solution properties in cleaning and concentration tanks Time(hr) Classification Cleaning tank N-hexane SS Cleaner Conc Conc. tank N-hexane 3,825 5,505 6,210 7,202 SS 2,100 4,210 6,320 8,170 Cleaner Conc Fig. 11. COD removal and permeate flux of contaminated rinsing water with various membrane pore sizes as a function of time at pressure of 2.0 kg f /cm 2 G (contaminants: NEOZOL-150S cleaner and nonsoluble cutting oil; soil concentration = 3 wtl). Table 6. Analysis for standard cutting oil and recycled cutting oil Classification Original oil Recycling oil Appearance White milky Milky ph Above Concentration ( ) 4 5 Tramp oil contents ( ) below Emulsion Stability Oil below Cream below Anti-corrosiveness 1 No rust within 6hrs No rust hrs Viable cell numbers Bacteria below (ea/ml) Fungi below Korean Chem. Eng. Res., Vol. 43, No. 4, August, 2005

8 494 q Ër Fig. 12. Permeate flux in pilot plant UF system as a function of time (day). Table 6l m p ky mpp p o l n l l o q n ppp p pl. l l o }k } e dšp }sp ov l n rpp lt p. 4. nl p pn l n, n o mm t redšp r nkp } o l m. nl e l } p mm p ( n, n ), nl p p nr l Œ d o o r s m. n mp mm rr t PAN qvp nl } pre n p mm nl p } q n ppp p m. n mp mm t redšp r nkp PAN qvp nl p p mm l Œ d } lpp p l. p p PAN p vp l n mpp eˆv p p Ž. p e n l H ql n p o mm k rkp } rnkp q n o l nl pilot plant nr l k. k rn kp 6 o p ov pl rrm o prp l q n pl. nl p mm l r 80Í p p Œ pp l s rl l rr n p 12 lq n p., l l nl edšp rr o mm rkp rp } q n rpp pv pl. l lqo p ~r lp l m q p vl l l ( ~r l, o ) vol p lp pl p p. y 1. Analysis of Physicochemical and Biological Properties of Metal Working Fluids and Evaluation of their Clarification System (final report), Separation Tech Co. Ltd-University of Suwon(2004). 2. Standard Methods for the Examination of Water Contamination, Waste and Soil Contamination, Dongwha Kisul(1998). 3. Shin, M. C., Lee, H. Y. and Bae, J. H., A Study on Cleanliness Evaluation of Aqueous/Semi-Aqueous Cleaning Agents, Journal of the Korean Industrial and Engineering Chemistry, 11(8), (2000). 4. Han, S. W., Lee, H. Y., Bae, J. H., Ryu, J. H., Park, B. D. and Jeon, S. D., Analysis of Monitoring and Recycling Technology Technologies of Cleaning Solution and Rinse Water in the Aqueous Cleaning System, Clean Technology, 7(4), (2001). 5. Greene, S., Dixon, B., Kuo, Y. S., Hagner, L. R., Pickering, Makovitch, T., Riza, F., Szymanowski, R., Tashjian, G. and Wenger, G., Aqueous and Semi-aqueous Alternatives for CFC- 113 and Methyl Chloroform for Cleaning of Printed Circuit Board Assemblies, ICOLP(1994). 6. David, A. W., Aqueous Cleaning of Vacuum Tube Components, Replacing 1,1,1, Trichloroethane, International Symposium on Electronics & The Environment, 7(1993). 7. Clesceri, L. S., Greenberg, A. E. and Eaton, A. D., Standard Methods for the Examination of Water and Wastewater, 19th. Ed., Washington, DC(1995). o43 o k

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