MITSUBISHI CHEMICAL DIAION. Ion Exchange and Water Treatment. Mitsubishi Chemical Corporation Separation Material Department 2009/04

Transcription

1 DIAION Ion Exchange and Water Treatment Mitsubishi Chemical Corporation Separation Material Department 2009/04

2 Application of I.E.R. for industry water treatment for boiler water teatment for power plants purification of medicine Ion exchange resins ultra pure water for LSI purification of sugar purification of amino acid

3 Uses of I.E.R. in Japan Share of DIAION 40 % 7% 8% 47% 20% 9% 0% 0% 53% 3% 4% 3%5% 4% 37% Water treatment Special uses Boiler Steam power plant Atomic power plant Ultra Pure water Others Catalyst Sugar Pharmacuitlcals Separation Process Amino acid & Nucleic acid

4 Manufacturing Process of I.E.R Polymerization + (DVB) (+ porousing agent) CH 2 Cl Amination CH 2 N + Cl - Anion exchange resin CH 2 N CH 2 COONa CH 2 COONa Chelate resin cross-linked polystyrene Sulfonation SO 3 - Na + Cation exchange resin gel porous High-porous Synthetic Absorbent

5 Physical Structure of I.E.R Porous Type Gel Type High Porous Type (Macroreticuler) Macro pore (10-10,000Å) Micro pore (0-300 Å) Macro pore (10-1,000Å) Cross Linkage (DVB %) Porous, Gel: 2-16% High por.: >15% Reaction Rate Porous > Gel > High Porous

6 Product List of DIAION & its Applications Gel Porous Highy Basic Structure Porus Applications Types & Classes Cation Exchange Resins Strongly acidic cation e.r. SK PK HPK Water treatment R-SO3 Na UBK RCP Refining sugar solutions Separation of Fluctose,Amino acid, Catalyst Weakly acidic cation e.r. WK Recovery of metals R-COO H, etc. Water treatment Anion Exchange Resins Strongly basic anion e.r. SA PA HPA Water treatment R-N(CH3)3 Cl Refining sugar solutions R-N(CH3)2(C2H4OH) Cl Purification of drugs Separation of Amino acid, Weakly basic anion e.r. WA Water treatment R-N(CH3)2 Decolorization of sugar solution Special Resins Chelating resins CR Recovery of metals ex.r-n-(ch2cooh)2 Brine purification Synthetic absorbents HP HPMG Purificasion of drugs SP Protein separating agents FP Protein separation other;resins for ultra pure water,mixed resins,powdered resins,etc..

7 DIAION line up & Crosslinkage S.A.Cation S.Anion; Type I S.Anion; Type II DVB (%) Gel Porous Gel Porous Gel Porous 3 PA SK104 SK1B SK110 PK208 PK216 PK220 SA11A SA12A SA10A PA308 PA312 PA316 SA21A SA20A PA408 PA412 PA SK PK228

8 Influence with Crosslinkage (DVB%) < Efficiency of IER is decided by Crosslinkage > Capacity : high cross > low cross Reaction Rate : low cross > high cross 8~12% is used for water treatment DVB vs Moisture & Capacity (gel cation) Reaction Rate (Na adsorption of gel cation) Moisture Content (%)) Cap Mois Capacity(meq/mL) Reaction time (sec) DVB(%) DVB(%)

9 Strongly Acidic Cation E. R. Insoluble in any solvents and strongly acidic like HCl or H 2 SO 4 Ion Exchange Reaction <Neutralization> R-SO 3 H + NaOH R-SO 3 Na + H 2 O <Salt Splitting> R-SO 3 H + NaCl R-SO 3 Na + HCl <Softening> 2R-SO 3 Na + CaCl 2 (R-SO 3 ) 2 Ca + 2NaCl Selectivity (in dilute solution) (Ba 2+ > Ca 2+ > Mg 2+ ) > (NH 4+ > K + > Na + > H + ) Regeneration (R-SO 3 ) 2 Ca + 2HCl 2R-SO 3 H + CaCl 2 More regenerates is required than the ex. Capacity.

10 Weakly Acidic Cation E.R. Insoluble in any solvents and show weakly acidic like carboxylic acids. Dissociation occurs in H 2 O above ph 4. Ion Exchange Reaction WK react only with base, not with neutral salt. R-COOH + NaOH R-COONa + H 2 O 2R-COOH + Ca(HCO 3 ) 2 (R-COO) 2 Ca + 2H 2 CO 3 Selectivity H + > ( Ba 2+ > Ca 2+ > Mg 2+ ) > > > Na + Regeneration Salt form is easily regenerated with theoretical amount of regenerant. Hydrolysis R-COONa + H 2 O R-COOH + NaOH

11 Difference between Strongly and Weakly acidic Cation E.R. Total Capacity ph range Regeneration Volume change Application Strongly acidic C.E.R. (SK1B) 2 meq/ml-r From 1 to 14 Difficult Small Widely used Weakly acidic C.E.R. (WK40) 4.6 meq/ml-r Above 4 Easy Big (e.g. Ca/H=1.1 Na/H=1.6) Suitable for containing large amount of HCO 3-, With hardness.

12 Strongly Basic Anion E. R Insoluble in any solvents and strongly basic like NaOH, KOH Ion Exchange Reaction <Neutralization> R 4 -NOH + HCl R 4 -NCl + H 2 O <Salt Splitting> R 4 -NOH + NaCl R 4 -NCl + NaOH R 4 -NOH + SiO 2 R 4 -NHSiO 3 Selectivity (in dilute solution) SO 2-4 > NO 3- > HSO - 4 > Cl - > HCO 3- > SiO2 > OH - Regeneration R 4 -NCl + NaOH R 4 -NOH + NaCl More regenerates is required than the ex. Capacity.

13 Comparison of Type I and Type II resins Exchange group Diaion Type I Trimethylammonium CH 3 R-N-CH 3 CH 3 SA10A,SA12A,SA11A PA300 series HPA25 Type II Dimethlyethanolamine CH 3 R-N-C 2 H 4 OH CH 3 SA20A,SA21A PA400 series HPA75 Basicity Strongly basic Strongly basic, but slightly weaker than Type I Ease of regeneration Regeneration is difficult Regeneration is facile and and a large quantity of economical. regenerant is required. Leakage in exchange Only slight Slightly weaker of weak acids. (SiO2) (SiO2 spec. 0.1ppm at Co-CR) (SiO2 spec. 0.2ppm at CoCR ) Chemical stability Cl form : up to 80 o C OH form : up to 60 o C Cl form : up to 60 o C OH form : up to 40 o C Regeneration Counter current regen. Co-current regen.

14 Difference between typeⅠand typeⅡ SBAnion Reg. Efficiency : TypeⅡ > TypeⅠ SiO2 leakage : Ⅱ > Ⅰ BTC : Ⅱ > Ⅰ Regeneration efficiency 強塩基樹脂の再生レベルと再生率 SiO2 leakage and BTC 強塩基樹脂 Ⅰ Ⅱ 型の脱シリカ比較 Regenerated 再生率 Percentage (%) (%) SA20A(Ⅱ) SA10A(Ⅰ) シリカ濃度 (ppb as SiO2) SiO2 leakage (ppb) 樹脂 300mL 原水 TA 520ppmCaCO3(Cl/SO4=1) SiO2 比 =9.2% (44ppmCaCO3) 再生 N-NaOH 100g/L-R(30min) 流速 SV=25 SA20A(Ⅱ) Regeneration 再生レベル level (g-naoh/lr) (g-naoh/l-r) 0 SA10A(Ⅰ) 処理量 (L/L-R) Treated volume (L/L-R)

15 Degradation when using for water treatment (SB-Anion typeⅠ,Ⅱ) As for type 2, Degradation of SSC is big. Influence of oxygen is big. Decline of Capacity(%) SSCⅡaerated SSCⅡdeaerated TotalⅡ SSCⅠ TotalⅠ Use period (yer)

16 Weakly Basic Anion E.R. Insoluble in any solvents and show weakly basic like NH 4 OH. Dissociation occurs in H 2 O under ph 9. Ion Exchange Reaction WA react only with strong acids or NH4Cl, not with neutral salts or carboxylic acid R 3 -NOH + HCl R 3 -NCl + H 2 O R 3 -NOH + NH 4 Cl R 4 -NCl + NH 4 OH Selectivity SO 2-4 > NO 3- > Cl - Regeneration R 3 -NCl + NaOH R 4 -NOH + NaCl Salt form is easily regenerated with theoretical amount of regenerant.

17 Selectivity coefficients for SK Type of ion 4% D.V.B.% 8% 16% Type of ion 4% D.V.B.% 8% 16% Li + H + + Na + NH 4 + K Rb Cs Ag Te 2+ UO 2+ 2 Mg 2+ Zn Co 2+ Cu 2+ Cd Mn Be Ni Ca Sr Pb 2+ Ba 2+ Cr 2+ Ce La

18 Selectivity of ion Ca++, Mg++, Na+ Ca Mg Na H Selectyvity:Ⅱvalence>Ⅰvalence MW rage > small 2R-Mg + Ca 2R-Ca + Mg 2(R-Na) + Mg 2R-Mg + 2Na R-H + Na R-Na + H By Selectivity, ion is separated

19 Degradation of I.E.R(1) S.A.Cation E.R Phenomenon A. Increasing of moisture content and leakage B. Decreasing of I.E. capacity per volume Reason Irreversible swelling by oxidation Counter measure 1. Removal of oxidizing agents by pretreatment (ex. Na 2 SO 3, AC). (The degree of oxidation depends temperature, ph, Fe,Cu..) 2. To use high cross linkage resin. (ex. to change from SK1B to SK110,SK112)

20 Decomposition of S.A.Cation Structure of SAC ー CH ー CH2ー CH ー CH2ー CH ー CH2 ー ー CH ー CH2 ー ー + SO3 H ー + SO3 H Hydration: thermal decomposition (>120 ) R-SO3 H + H2O 1R-OH + H2SO3 2R-H + H2SO4 Oxidation Oxidation:decomposition of copolymer matrix Main decomposition in case of water treatment Oxidizing agents, Metals(Cu,Fe,Al etc) Hydration products 1H2SO3 2H2SO4 3 Polystyrene Sulfonic Acid ー CH ー CH2ー CH ー CH2 ー + SO3 H ー + SO3 H

21 Relation between Crosslinnkage and Oxidative Degradation of SAC Tolerance to Oxidation : 12 > 10 > 8 (DVB%) Residual exchange capacity (%) DVB 12 % 10 % 8 % Period of use (years) Irreversible swelling by oxidation Decline of Cap.( meq/ml) meq/g doesn t change

22 Cl2 Tolerance of SK1B Cause of Oxidation of IER Oxidizing agents : O2, Cl2, H2O2, NaClO3 Oxidation accelerates with Catalyst effect by metals (Cu, Fe, Al) Influence of metals 酸化に対する金属の影響 2.5 金属形 SK1B 5 ml 10%H2O2-100mL Temperature ( ) Maximum Cl2 (ppm) 中性塩分解能力 (meq/ml-r) SSC (meq/ml) Ca Na Al FeⅢ Cu Time (hrs) 浸漬時間 (hrs)

23 Degradation of I.E.R(2) S.B.Anion E.R Phenomenon A. Decreasing of total capacity or salt splitting capacity. B. Decreasing of moisture content. C. Increasing of silica leakage. D. Decreasing of reaction rate. Reason 1. Thermal decomposition of resin. 2. Oxidative decomposition. 3. Organic contamination. Counter measure 1. Refilling the resin. 2. Removal of oxidizing agents by pretreatment Removing of organic compound by pretreatment such as A.C To use porous resin. (e.g. PA312, PA418) 3-3. Treatment by HCl or NaOH + NaCl for recovery.

24 Decomposition of S.B.Anion (TypeⅠ) Structure of SBA ー CH ー CH2 ー ー CH ー CH2 ー products + CH3 CH2 ー N ー CH3 CH3 ー OH (Quaternary ammonium) SA10A,SA12A,PA312 etc Weak basicity Detach CH3 CH2 ー N CH3 (Dimethylamin=WBA-Resin ) ー CH ー CH2 ー CH2OH + CH3OH + (Methanol) CH3 N ー CH3 CH3 (Trimethylamin) SBA are decomposed by heat and oxidation

25 Organic contamination and reaction rate A - A - Diffusion in solution Film diffusion Organic substance Particle diffusion (Resin)

26 Comparison between Gel and Porous (Adsorption of organic substance) Test condition IER : R-Cl 15 ml Organic sub. : Fast Green FCF 30ppm (dye MW=808) Used Resin : after 80cycle (water treatment) PA418/SA20A F.G. Reakage (ppm) Treated volume (L/L-R) New Gel Anion New Porous Anion Used Gel Anion Used Porous Anion

27 Comparison between Gel and Porous (Efficiency of 2B3T-water treatment) 2 Comparison between PA418/SA20A <COD, CL reakage> Resin:after 80cycle use in many COD areas (in japan) 40 COD reakage (ppm) Cl reakage (ppm) SA20A-COD PA418-COD SA20A-CL PA418-CL Treated volume (L/L-R)

28 Selection of DIAION for water treatment (1) CATION There are a larger amount of oxidizing agents in influent water. yes SK110,SK112 The influent water contains a large quantity of HCO 3-, and Ca 2+, Mg 2 + & total ions. (Standard) SK1B yes WK40-SK1B (4B5T) WK40-SK112L (D.L)

29 Selection of DIAION for water treatment (2) ANION You want to make much of regeneration cost or quality of effluent water. Co-current regen. yes SA20A There are a large amount of natural organic substance in influent water. The influent water contains a large quantity of mineral acids. SA12A yes yes PA312,PA418 WA30-SA12A (4B5T) WA30-SA10DL (D.L)

30 System when there are many organic substance 4B5T WK40 SK1B DG WA30 PA312 4B5T SK1B PA418 SK1B PA312 DG 2B3T SK1B DG WA30 SA10DL Dual layers Bed

31 4B5T system Influent water Regenerants Regenerants WC SC DG WA SA Weakly Acidic Cation Strongly Acidic Cation Degasifier Weakly Basic Anion Treated water Strongly Basic Anion HCO - Mg 2+ 3 Ca 2+ Cl - Na + SO 2-4 SiO 2 HCO - Cl - 3 Mg 2+ Ca 2+ Cl - Na + SiO 2 SO 2- SO HCO - Cl - 3 Cl - SO 2- SO Cl - SO 4 2- SiO 2 SiO 2 SiO 2 This system suitable for treating water with a very large quantity of HCO3-, hardness and total ions.

32 Other Applications Effluent treatment & recovery of valuable materials. Foodstuffs and food additives. Refining of sugar solution. Separation of amino acids. Purification of chemicals. Purification of brine Separation and purification of antibiotics Catalyst of chemical material manufacture DIAION manual (II)

33 Home Page of DIAION Introduction of product Specification and application Mail for question and data request There is English version