목차
표제지=0,1,1
제출문=1,2,2
보고서 초록/이제근=3,4,2
요약문=5,6,6
SUMMARY=11,12,6
Contents=17,18,2
목차=19,20,2
List of Table=21,22,4
List of Figure=25,26,8
제1장 연구개발과제의 개요=33,34,1
1. 연구의 배경 및 목적=33,34,2
2. 연구개발의 최종목표 및 연구범위=34,35,2
3. 연구개발 추진체계=36,37,1
제2장 국내외 기술개발 현황=37,38,1
1. 제올라이트 합성=37,38,1
2. 적조구제기술 개발=38,39,5
3. 생물학적 질소.인 제거공정=43,44,6
4. 본 과제를 통한 연구결과의 차별성(독창성)=49,50,1
제3장 연구개발수행 내용 및 결과=50,51,1
1. 소각재 용융 최적화 및 용융슬래그 제조=50,51,27
2. 0.2톤/일급 제올라이트 합성장치 설계.제작 및 용융슬래그 제조=77,78,50
3. 5톤/일급 제올라이트 합성장치 설계=127,128,24
4. 제올라이트 특성제어법=151,152,20
5. 적조제거용 제오플럭(Zeofloc)제조 및 장치 설계.제작=171,172,11
6. 제올플럭을 이용한 적조구제 현장적용 및 최적조업 조건=182,183,22
7. EnZeo-BM 제조장치 및 공정 개발=204,205,7
8. EnZeo-BM을 이용한 질소ㆍ인 제거공정 개발=211,212,37
9. 합성제올라이트를 이용한 기타 고부가 제품 개발=248,249,53
10. 경제성 평가 및 사업성 검토=301,302,12
제4장 연구개발목표 달성도 및 대외기여도=313,314,1
1. 연구개발목표 달성도=313,314,1
2. 연구결과의 대외 기여도=314,315,1
제5장 연구개발결과의 활용계획=315,316,1
1. 추가연구 및 연구개발 결과 활용=315,316,1
2. 타 연구에의 응용=315,316,1
제6장 연구개발과정에서 수집한 해외과학기술정보=316,317,1
참고문헌=317,318,18
부록=335,336,1
1. 제올라이트 합성 장치 설계도면 및 specification=335,336,35
2. 기능성 제품 제조 공정의 경제성 평가=370,371,21
3. 특정연구개발사업 연구결과 활용계획서/이제근=391,392,13
영문목차
[title page etc.]=0,1,17
Contents=17,18,16
Chapter 1. Preface=33,34,1
1. Background and objectives=33,34,2
2. Scope of study=34,35,2
3. Propulsion organization of this study=36,37,1
Chapter 2. Present Condition of the Technology Development=37,38,1
1. Zeolite synthesisis=37,38,1
2. Development of removal agents of red tide organisms=38,39,5
3. Biochemical Treatment process for nitrogen and phosporus removal=43,44,6
4. Originality of this study=49,50,1
Chapter 3. Contents and Results=50,51,1
1. Optimization of ash melting process=50,51,27
2. Design and Construction of 0.2ton/day capacity of zeolite synthesis equipment and zeolite synthesis=77,78,50
3. Basic and Detail design of 5ton/day capacity of zeolite synthesis equipment=127,128,24
4. Specilized control method of zeolite=151,152,20
5. Manufacture of Zeofloc and Constracture of the equipment=171,172,11
6. Field-test of Zeofloc for application=182,183,22
7. Development and Manufacture of EnZeo-BM=204,205,7
8. Development of the removal process of nitrogen and phosphorus with EnZeo-BM in sewage and wastewater=211,212,37
9. Development of other high value-added products with zeolite=248,249,53
10. Evaluation of economic efficiency and feasibility study=301,302,12
Chapter 4. Research Achievements and Contributions=313,314,1
1. Research achievements=313,314,1
2. Contributions=314,315,1
Chapter 5. Application Plan=315,316,1
1. Additional study and application=315,316,1
2. Application to other study=315,316,1
Chapter 6. Abrod Science Technology Information obtained from this research=316,317,1
Chapter 7. Reference=317,318,18
Appendix=335,336,69
Table 2-2-1 Characteristics comparison for removal agents of red tide organism=42,43,1
Table 2-3-1 Comparison of activated sludge process and biofilter process=48,49,1
Table 3-1-1 Chemical composition of flyash from Municipal waste incineration=57,58,1
Table 3-1-2 Composition of ash and waste cast-iron sand=59,60,1
Table 3-1-3 Ash composition characteristics with mixing ratio of ash to waste cast-iron sand=59,60,1
Table 3-1-4 Melting temperature and pouling index change characteristics with mixing ratio of ash to waste cast-iron sand=60,61,1
Table 3-1-5 Inorganic matters and heavy metal with each part on melted slag separated by gravity=61,62,1
Table 3-1-6 Leaching test result of ash according to quenching methods=73,74,1
Table 3-2-1 Chemical compositions of melting slag from Lord-Tech industry=78,79,1
Table 3-2-2 Result of semi-quantitative XRD analysis on the bulk sample of selectively synthesized zeolite=81,82,1
Table 3-2-3 Quantitative XRD analysis of Na-P type of zeolite depending on the particle size=86,87,1
Table 3-2-4 Quantitative XRD analysis of Na-A type of zeolite depending on the particle size=87,88,1
Table 3-2-5 Diffractometer conditions for mineral identification=90,91,1
Table 3-2-6 Diffractometer conditions for quantitative analysis the chemistry of the solution=90,91,1
Table 3-2-7 Experimental results of zeolitization depending on the chemistry of the solution=95,96,1
Table 3-2-8 Experimental results of zeolitization depending on the chemistry of the solution=96,97,1
Table 3-2-9 Experimental results of zeolitization depending on the chemistry of the solution=100,101,2
Table 3-2-10 Experimental results of zeolitization depending on the chemistry of the solution=102,103,1
Table 3-2-11 Comparison of the experimental condition and its results of zeolitization=114,115,1
Table 3-2-12 Experimental results of zeolitization with the melting slag=120,121,1
Table 3-2-13 Chemical composition of the mother liquid(ppm)=120,121,1
Table 3-2-14 Heavy metal content of the waste water after washing process in press filter(ppm)=122,123,1
Table 3-2-15 Variation of chemical composition of the waste water,showing the effect of application of ultrasonic cleaner(ppm)=122,123,1
Table 3-2-16 Variation of heavy metals in the waste water,according to the applied time of ultrasonic cleaner(ppm)=123,124,1
Table 3-2-17 Analytical results of leaching in time(ppm)=123,124,1
Table 3-2-18 Analytical results of heavy metals of synthesized Na-A type zeolite(ppm)=124,125,1
Table 3-2-19 Analytical result of chemical composition of the ion-exchanged Ca-A type zeolite(%)=125,126,1
Table 3-2-20 Analytical result of clorine content in waste water after washing of the ion-exchanged Ca-A type zeolite(%)=125,126,1
Table 3-3-21 Mass and heat balance of Zeolite synthesis=129,130,6
Table 3-3-22 Equipment specifications and conditions of Zeolite synthesis process=135,136,9
Table 3-3-23 Sources and products chemical data of Zeolite=144,145,1
Table 3-4-1 Typical formulae and selected physical properties of important zeolites=152,153,1
Table 3-4-2 Physical and chemical properties of Zeolite A=155,156,1
Table 3-4-3 Chemical composition and pore size of Zeolite A=156,157,1
Table 3-4-4 Selected molecules absorbed to the Zeolite=156,157,1
Table 3-5-1 Chemical composition of Zeofloc and Loess=171,172,1
Table 3-5-2 Particle distribution of Zeofloc=171,172,1
Table 3-5-3 Variation of pH in sea water with adding loess/zeolite/Zeofloc at 3hr of settling time=173,174,1
Table 3-5-4 Variation of turbidity in sea water with adding loess/zeolite/Zeofloc at 3hr of settling time=173,174,1
Table 3-5-5 Particle size distribution of Zeofloc and loess=175,176,1
Table 3-5-6 Leaching test results of heavy metal in Zeofloc=177,178,1
Table 3-5-7 Stability test of Zeofloc to cultured fishes=177,178,1
Table 3-5-8 Specification of Mixer/Spray system=181,182,1
Table 3-6-1 Removal efficiency of C. polykrikoides with adding to Zeofloc/loess opowder in Column test=198,199,1
Table 3-6-2 Removal efficiency of C. polykrikoides with adding to Zeofloc/loess powder in field test=198,199,1
Table 3-7-1 Physical and chemical characteristics of EnZeo-BM=205,206,1
Table 3-8-1 Characteristics of samples used and analysis methods=213,214,1
Table 3-9-1 Biodegradability of various contaminants in a biofilter=250,251,1
Table 3-9-2 Summary of important properties of common media materials=258,259,1
Table 3-9-3 Physical and chemical characteristics of toluene=267,268,1
Table 3-9-4 Composition of nutrient solution=270,271,1
Table 3-9-5 Analytical condition of gas chromatography=270,271,1
Table 3-10-1 Evaluation of economic efficiency for 5(7.5)ton/D zeolite synthesis process=302,303,4
Table 3-10-2 Evaluation of economic efficiency for 10(15)ton/D=306,307,4
Table 3-10-3 Evaluation of econnomic efficiency of 5ton/day EnZeo-BM manufacturing process=310,311,4
Fig. 2-2-1 Occurrence number of red tide in Setto inland sea(1968~1994)=39,40,1
Fig. 2-2-2 "ECOHAB" research project portion with each topic in USA=40,41,1
Fig. 2-3-1 A2/O process=44,45,1
Fig. 2-3-2 Five-stage bardenpho process=45,46,1
Fig. 2-3-3 UCT process=46,47,1
Fig. 2-3-4 MUCT process=47,48,1
Fig. 2-3-5 VIP process=47,48,1
Fig. 3-1-1 Classification of melting technology of incineration residues=52,53,1
Fig. 3-1-2 Types of melting furnace(1)=55,56,1
Fig. 3-1-3 Types of melting furnace(2)=56,57,1
Fig. 3-1-4 XRD analysis results of ash from municipal waste incinerations=58,59,1
Fig. 3-1-5 Pouling Index test results of mixed ash and waste silicate sand as ratio of 9:1 at 1300℃=60,61,1
Fig. 3-1-6 Diagram for gravitational separated parts of melting slag=62,63,1
Fig. 3-1-7 Separation eficiency of heavy metals from slag with melting atmosphere:S-O,slowly cooled slag in oxidizing condition; S-R,slowly cooled slag in reducing condition=64,65,1
Fig. 3-1-8 Separation efficiency of heavy metals from slag with melting time=65,66,1
Fig. 3-1-9 X-ray diffraction pattern with colling methods=67,68,1
Fig. 3-1-10 Representative X-ray diffraction patterns of slag in oxidizing condition=68,69,1
Fig. 3-1-11 Representative X-ray diffraction patterns of slag in reducing condition=69,70,1
Fig. 3-1-12 Leaching rate of heavy metals in the ash and slag used in this experiment=72,73,1
Fig. 3-1-13 DC electric resistance melting furnace=73,74,1
Fig. 3-1-14 Photo. of melting furnace used this work=74,75,1
Fig. 3-1-15 Photo. of draining slag=75,76,1
Fig. 3-1-16 Lay-out diagram of ash melting process=76,77,1
Fig. 3-2-1 X-ray diffraction pattern of melting slag as starting materials=78,79,1
Fig. 3-2-2 Results of size analysis of Na-A type of zeolite from slag=82,83,1
Fig. 3-2-3 XRD pattern of P-type of zeolite depending on the particle size=83,84,1
Fig. 3-2-4 XRD patterns of A-type of zeolite depending on the particle size=84,85,1
Fig. 3-2-5 X-ray diffraction pattern of A-type zeolite=103,104,1
Fig. 3-2-6 SEM microphotograph of synthesized zeolite in this study=106,107,1
Fig. 3-2-7 SEM microphotograph of Na-A type of zeolite with cubo-dodecahedron shape and twinned crystals=107,108,1
Fig. 3-2-8 Scanning electron micrographs of aggregated Na-P Zeolite synthesized from slag=108,109,1
Fig. 3-2-9 Scanning electron micrographs of Na-P zeolite formed inside of void=108,109,1
Fig. 3-2-10 SEM microphotograph of euhedral calcite crystals=109,110,1
Fig. 3-2-11 Unreacted,massive type slag. Zeolitization on the slurface of the slag can be partly observed=109,110,1
Fig. 3-2-12 Zeolitization on the surface of the void-type slag=110,111,1
Fig. 3-2-13 Zeolitization and etch figure on the surface of the slag=111,112,1
Fig. 3-2-14 CaO phase existing inside of the viod-type slag=112,113,1
Fig. 3-2-15 Synthetic process for the production of zeolite=113,114,1
Fig. 3-2-16 Bench-scale hydrothermal apparatus for the synthesis of zeolite A=118,119,1
Fig. 3-2-17 Filter press used by this study=119,120,1
Fig. 3-3-1 Basic schematic flow diagram of fabrication process of zeolite,zeofloc and EnZeo-BM. (Zeolite:5 t/day,Zeofloc:10 t/day,EnZeo-BM:5 t/day)=127,128,1
Fig. 3-3-2 Basic schematic flow diagram of fabrication process of zeolite(5 t/day)=128,129,1
Fig. 3-3-3 Analysis results summary from design data of 5ton/day zeolite synthesis process=145,146,2
Fig. 3-3-4 Gantt chart 5ton/day zeolite synthesis process (1 batch)=148,149,1
Fig. 3-3-5 Equipment utilization chart per day of 5ton zeolite synthesis process=149,150,1
Fig. 3-3-6 Productivity comparison with unit process and equipment=150,151,1
Fig. 3-4-1 Secondary Building Units identifiable in zeolite framework. T atoms are at cross-section and termination of lines. O atoms (not shown) are located about midway between T atoms (Meier and Olson,1987)=153,154,1
Fig. 3-4-2 Typical zeolite pore sizes illustrated with exygen packing model=154,155,1
Fig. 3-4-3 Illustration of molecular sieve effect. Straight chain molecule of normal octane(top) passes through eight ring aperture of 5A(CaA) zeolites; branched molecule of iso-octane(bottom) cannot=154,155,1
Fig. 3-4-4 Flow chart for the industrial manufacturing of 4-A zeolite by the chemical process=168,169,1
Fig. 3-4-5 Flow chart for the industrial manufacturing of 4-A zeolite by the clay conversion process=170,171,1
Fig. 3-5-1 Zeta potential of zeolite vs pH=172,173,1
Fig. 3-5-2 DO change with amount of input of Zeofloc and loess and settling time=174,175,1
Fig. 3-5-3 SEM microphotograph of fabricated Zeolite=176,177,1
Fig. 3-5-4 Reactor for stability test of Zeofloc for cultured fishes=178,179,1
Fig. 3-5-5 Cultured fishes used this work=178,179,1
Fig. 3-5-6 Lab-scale Zeofloc testing reactor=179,180,1
Fig. 3-5-7 Schematic diagram of Zeofloc manufacturing equipment=180,181,1
Fig. 3-5-8 Pilot plant Mixer/Spray system for producing Zeofloc=181,182,1
Fig. 3-6-1 Removal mechanism of red tide organism by Zeofloc=185,186,1
Fig. 3-6-2 Photo. of Chattonella antiqua=186,187,1
Fig. 3-6-3 Photo. of Cochlodinium polykrikoides=186,187,1
Fig. 3-6-4 Chattonella antiqua settled by loess=187,188,1
Fig. 3-6-5 Chattonella antiqua destroyed by Zeofloc=187,188,1
Fig. 3-6-6 Cochlodinium polykrikoide setled by loess=188,189,1
Fig. 3-6-7 Cochlodinium polykrikoide destroyed by Zeofloc=188,189,1
Fig. 3-6-8 Removal efficiency of Cochlodinium polykrikoides according to mitigation agent concentration:2,500cells/ml=190,191,1
Fig. 3-6-9 Removal efficiency of Cochlodinium polykrikoides according to mitigation agent concentration:8,800cells/ml=191,192,1
Fig. 3-6-10 Removal efficiency with amount of input Zeofloc and loeaa powder at constant particle size(Cochlodinium polykrikoides:4500-5000cells/ml)=193,194,1
Fig. 3-6-11 Column test (2001. 8. Kwang-An beach,Busan)=194,195,1
Fig. 3-6-12 Column test (2001. 9. Pohang fhishes high school,Pohang)=195,196,1
Fig. 3-6-13 Removal efficiency of red tide organism with settling time and Zeofloc concentration in column test(Cochlodinium polykrikoides:10000 cells/ml)=196,197,1
Fig. 3-6-14 Photo. of Zeofloc field testing for red tide=199,200,1
Fig. 3-6-15 Zeofloc mizer/spray equipment for field test=200,201,1
Fig. 3-6-16 Photo. of Zeofloc spraying for red tide removal=201,202,1
Fig. 3-7-1 EnZeo-BM produced by injection methods=206,207,1
Fig. 3-7-2 EnZeo-BM manufacturing process=207,208,1
Fig. 3-7-3 Photo. of EnZeo-Bm=208,209,1
Fig. 3-7-4 Injection molder of EnZeo-BM=209,210,1
Fig. 3-7-5 Injection molding mechine of EnZeo-BM.=210,211,1
Fig. 3-8-1 Schematic diagram of SBR=214,215,1
Fig. 3-8-2 Operating condition for SBR=215,216,1
Fig. 3-8-3 Scanning electron micrographs of EnZeo-BM surface=217,218,1
Fig. 3-8-4 Scanning electron micrographs of growth microbe after 15 days operating in SBR=218,219,1
Fig. 3-8-5 Scanning electron micrographs of growth microbe after 30 days operating in SBR=219,220,1
Fig. 3-8-6 Photo. of EnZeo-BM after 30 days operating in SBR=220,221,1
Fig. 3-8-7 Variation of DO and pH with the Run 1=222,223,1
Fig. 3-8-8 Variation of DO and pH with the Run 2=223,224,1
Fig. 3-8-9 Variation of DO and pH with the Run 3=224,225,1
Fig. 3-8-10 Variation of DO and pH with the Run 4=225,226,1
Fig. 3-8-11 Influence of operating type on COD removal efficiency=226,227,1
Fig. 3-8-12 Variation of DO,pH and COD with the Run 2=227,228,1
Fig. 3-8-13 Variation of DO,pH and COD with the Run 3=228,229,1
Fig. 3-8-14 Variation of DO,pH and COD with the Run 4=229,230,1
Fig. 3-8-15 Influence of operating type on NH₄+(이미지참조)-N removal efficiency=231,232,1
Fig. 3-8-16 Variation of DO,pH and NH₄+(이미지참조)-N with the Run 2=232,233,1
Fig. 3-8-17 Variation of DO,pH and NH₄+(이미지참조)-N with the Run 3=233,234,1
Fig. 3-8-18 Variation of DO,pH and NH₄+(이미지참조)-N with the Run 4=234,235,1
Fig. 3-8-19 Influence of operating type on T-N removal efficency=236,237,1
Fig. 3-8-20 Influence of operating type on NO³-(이미지참조)-N concentration=237,238,1
Fig. 3-8-21 Variation of DO,pH and T-N with the Run 2=238,239,1
Fig. 3-8-22 Variation of DO,pH and T-N with the Run 3=239,240,1
Fig. 3-8-23 Variation of DO,pH and T-N with the Run 4=240,241,1
Fig. 3-8-24 Influence of operating type on T-P removal efficency=242,243,1
Fig. 3-8-25 Variation of DO,pH and T-P with the Run 2=243,244,1
Fig. 3-8-26 Variation of DO,pH and T-P with the Run 3=244,245,1
Fig. 3-8-27 Variation of DO,pH and T-P with the Run 4=245,246,1
Fig. 3-9-1 Schematic diagram for waste gas treatment in biofiltration=249,250,1
Fig. 3-9-2 Schematic diagrams of above-ground closed biofilter=252,253,1
Fig. 3-9-3 Schematic diagrams of below-ground open biofilter=253,254,1
Fig. 3-9-4 Schematic diagram of biological trickling filter=254,255,1
Fig. 3-9-5 Schematic diagram of bioscrubber=255,256,1
Fig. 3-9-6 Schematic diagram of biotrickling filter=264,265,1
Fig. 3-9-7 Biotrickling filter used in this study=265,266,1
Fig. 3-9-8 Pathway of toluene biodegardation(type A)=268,269,1
Fig. 3-9-9 Pathway of toluene biodegardation(type B)=269,270,1
Fig. 3-9-10 Scanning eletron microscope of biomass attached EnZeo-BM media which taken from biotrickling filter=271,272,1
Fig. 3-9-11 Change removal efficiency until steady-state in biotrickling filter with EnZeo-BM=273,274,1
Fig. 3-9-12 Toluene removal patterns at constant inlet concentration and varying EBRT=274,275,1
Fig. 3-9-13 Toluene removal patterns at constant inlet concentration and varying EBRT=275,276,1
Fig. 3-9-14 Toluene removal patterns at constant inlet concentration and varying EBRT=276,277,1
Fig. 3-9-15 Change of toluene concentration with bed depth under various inlet concentration=278,279,1
Fig. 3-9-16 Relationship between inlet concentration and elimination capacity=279,280,1
Fig. 3-9-17 Pressure drop as a function of gas velocities under various bed depth=280,281,1
Fig. 3-9-18 Photo. of Microcystis=284,285,1
Fig. 3-9-19 Removal efficiency of Microcystis with zeolite dose and NaOCI concentration=286,287,1
Fig. 3-9-20 Characteristics of concentration of NH₄+(이미지참조)-N and PO₄3-(이미지참조)-P with operation time=290,291,1
Fig. 3-9-21 Freundlich isotherm for ion exchange on zeolite at various temperature=293,294,1
Fig. 3-9-22 Freundlich isotherm for NH₄+(이미지참조) ion exchange on zeolite at various concentration.(seawater,intial temperature:(a) 10℃ (b) 20℃ (c) 30℃)=294,295,1
Fig. 3-9-23 Freundlich isotherm for PO₄3-(이미지참조)-P ion adsorption on zeolite at various adsorption temperature. (a) 8,(b) 5,(c) 3 ㎎ PO₄3-(이미지참조)-P/L=296,297,1
Fig. 3-9-24 Freundlich isotherm for PO₄3-(이미지참조)-P ion adsorption on zeolite at various adsorption temperature. (a) 10℃ (b) 20℃ (c) 30℃,y=㎎/g,x=Ce (1:25℃,2:35℃,3:45℃,)(102),(temp.:a:10℃,b:20℃,c:30℃)=298,299,1
Fig. 3-9-25 Removal efficiency of PO₄3-(이미지참조)-P according to reaction time(initial concentration of PO₄3-(이미지참조)-P:8㎎/L)=299,300,1
Fig. 3-10-1 Manufacturing process of 5ton/day EnZeo-BM=310,311,1