보고서 정보
주관연구기관 |
(사)고등기술연구원 |
연구책임자 |
이성규
|
참여연구자 |
추수태
,
조성수
,
강경훈
,
김종민
,
박근만
,
서민혜
,
전희승
|
보고서유형 | 최종보고서 |
발행국가 | 대한민국 |
언어 |
한국어
|
발행년월 | 2007-03 |
과제시작연도 |
2006 |
주관부처 |
환경부 |
연구관리전문기관 |
한국환경기술진흥원 |
등록번호 |
TRKO200800000952 |
과제고유번호 |
1480002846 |
사업명 |
차세대핵심환경기술개발 |
DB 구축일자 |
2013-04-18
|
키워드 |
기후변화가스.아산화질소.질소산화물.제올라이트.허니컴 촉매.질산제조공정.Greenhouse gases.Nitrous oxide.Nitric oxide.Zeolite.Honeycomb catalyst.Nitric acid manufacturing process.
|
초록
▼
$\blacktriangle$ 100 $cells/in^2$ 형태의 하니컴 담지체 제조 및 압출성형 조건 최적화 도출
: 하니컴 담지체 성형을 위해 원료 및 첨가제 비율을 조절하여 100 $cells/in^2$의 제조하였고, 제조한 담지체 후처리 공정에서 건조 소성에 맞는 최적의 운전조건 확립
$\blacktriangle$ Lab. Pilot plant를 이용한 촉매 성능평가
: Lab. test 결과 Pd-Fe-Mor 분말형태의 촉매를
$\blacktriangle$ 100 $cells/in^2$ 형태의 하니컴 담지체 제조 및 압출성형 조건 최적화 도출
: 하니컴 담지체 성형을 위해 원료 및 첨가제 비율을 조절하여 100 $cells/in^2$의 제조하였고, 제조한 담지체 후처리 공정에서 건조 소성에 맞는 최적의 운전조건 확립
$\blacktriangle$ Lab. Pilot plant를 이용한 촉매 성능평가
: Lab. test 결과 Pd-Fe-Mor 분말형태의 촉매를 사용할 경우 공간속도 10,000 $h^{-1}$, 반응온도 370 $^{\circ}C$, 환원제 $CH_4$를 주입하여 $N_2O$ 100% 저감하였고, pilot plant에서는 하니컴 촉매를 사용하여 공간속도 13,00 $h^{-1}$, 반응온도 400 $^{\circ}C$, 환원제 $CH_4$를 주입하여 $N_2O$ 100% 저감하였고, NOx의 경우 동일한 조건에서 환원제 $NH_3$을 주입하여 100% 저감하는 촉매 성능평가 완료
$\blacktriangle$ 온실가스 배출원에서의 현장검증
: 카프의락탐 제조사업장(울산, C사) SCR 반응탑 전단 공정에서 현장검증을 수행한 결과, SCR 반응탑 전단에서 Fe-HNZ 촉매를 사용하여 공간속도 5,000 $h^{-1}$에서 환원제 $NH_3$을 주입하여 $N_2O$는 480 $^{\circ}C$에서 100%, NOx는 300 $^{\circ}C$에서 100% 저감되는 것을 현장검증 확인
: 유동층 연소로(대전, 27 톤/일)에서의 $N_2O$ 현장검증을 수행하기 위해 Pd-Fe-Mor 촉매를 사용하여 공간속도 10,000 $h^{-1}$, 반응온도 380 $^{\circ}C$, 환원제 $CH_4$를 주입하여 $N_2O$를 98% 저감을 해당 사업장에서 검증
Abstract
▼
The main aspect of the present research is development of catalyst for removal of $NO_x$ and $N_2O$ gas emitted from nitric acid production. Essential aspects of the research are development of SCR catalysts with more than 80 - 90% $NO_x$ and $N_2O$ remova
The main aspect of the present research is development of catalyst for removal of $NO_x$ and $N_2O$ gas emitted from nitric acid production. Essential aspects of the research are development of SCR catalysts with more than 80 - 90% $NO_x$ and $N_2O$ removal efficiency in the presence of deactivating agents such as alkali metals, oxygen, moisture (water vapor), and $SO_2$. More specifically, the developed catalyst was expected to achieve more than 90% removal efficiency of $NO_x$ and $N_2O$ from lab scale effluent gases simulating actual nitric acid production plants. Most importantly, the catalysts developed in the present research were expected to accomplish 90% removal efficiency of $NO_x$ and $N_2O$ from real caprolactam manufacturing plant which is essentially similar to nitric acid manufacturing facilities as far as emission condition of $NO_x$ and $N_2O$ is concerned.
Suitable SCR catalysts for $NO_x$ and $N_2O$ removal had to be selected by trial and error among 7 catalyst supports and 10 active catalysts. The most suitable combination of catalyst support and active catalyst for efficient removal of $NO_x$ and $N_2O$ was thus selected and relevant research and development were carried out. The catalyst preparation procedure was also optimized by trial and error for efficient extrusion and pelletization.
The catalyst system thus prepared was put under model effluent gas containing deactivating agents for actual testing of its $NO_x$ and $N_2O$ removal efficiency. Also, the catalyst system was placed under actual caprolactam manufacturing environment for actual testing of its $N_2O$ and $NO_x$ removal efficiency.
The research objectives include: (1) Development of metal oxide catalyst powders and catalyst fabrication technology for simultaneous removal of nitric oxide ($NO_x$) and greenhouse gas ($N_2O$) emitted from nitric acid production; (2)
o Impregnation of catalyst material or optimization of wash coating process
o $NO_x\;(NO,\;NO_2,\;N_2O)$ removal test on catalyst preform
o X-ray examination on surface characterization of zeolite-base $deNO_x$ catalysts
(2) Second year
1) R & D objectives
o Continuous fabrication technology for honeycomb shape preform (natural zeolite, $TiO_2$) of 1 $cm^3$ size (100 CPSI): Completion of continuous fabrication from $3"{\times}3"$ size by extrusion method (fabrication of optimized honeycomb mold)
o $DeNO_x$ powder catalysts coating technology over honeycomb preform or impregnation technology for catalysts support : Powder catalysts coating weight more than 10 wt% of entire preform, coating performance comparable to commercially available catalysts
o $DeNO_x$ ($NO,\;NO_2,\;N_2O$) capability of developed catalysts more than 80% from low pressure difference reaction chamber: Catalysts performance evaluated under SCR condition using proper reducing agents, simulating actual nitric acid production environments
o Design of a pilot plant to completion of blue print stage for simulated effluent gas environment of actual nitric acid production (20 $Nm^3/h$)
o Build-up of pilot plant for catalytic removal of greenhouse gases
2) Scope and contents of present R & D
o Optimization of extrusion process for fabrication of metal oxides catalyst supports and study on forming process of final aft section of preform
o Optimization on extrusion process of honeycomb catalyst of 1 $cm^3$ size (100CPSI) catalyst support and catalyst coating process
o $NO_x\;(NO,\;NO_2,\;N_2O)$ removal test on developed catalyst preform under simulated nitric acid production effluent gas environments, both activating and deactivating conditions
o Pilot plant process design and optimization to realize simulated effluent gas environments of nitric acid production: automation of process, PLC system, other miscellaneous equipment for electrical system, system design for catalyst performance evaluation
o Actual installation of catalyst process pilot plant for efficient control and removal of greenhouse gases emitted from actual nitric acid powder plant: system PFD, P&ID, ASSAY, Instrument Index, etc
o x-ray examination for physico-chemical investigation on surface characterization of zeolite-base $DeNO_x$ catalysts in terms of actual catalysts performance
(3) Third year
1) R & D objectives
o Fabrication of catalyst reaction chamber from honeycomb shape preform of 1 $cm^3$ size (100 CPSI) for use in pilot plant tests and design and fabrication of catalyst reaction chamber module for actual test
o Operation of pilot plant under similar environment to that encountered in actual nitric acid production
o $DeNO_x\;(NO,\;NO_2,\;N_2O)$ capability of developed catalysts more than 80% from pilot plant operation
o Catalysts performance evaluated under SCR condition simulating actual nitric acid production environments
o System operation based on simulation result of actual nitric acid production plant effluent gas
o Packaging of related catalytic process technologies in connection with removal of total $NO_x$ from nitric acid production
o Suggested methods to improve performance of $DeNO_x\;(NO,\;NO_2,\;N_2O)$ catalysts based on catalysts surface characterization and morphology before and after exposure
2) Scope and contents of present R & D
o Commercialization method based on accumulated research results and packaging of $DeNO_x$ technologies: actual $DeNO_x$ system of nitric acid production facilities, $DeNO_x$ system of fluidized-bed combustion facilities, catalysts for removal of odor/VOC, etc
o Optimization of extrusion process operation of honeycomb catalyst, 1 $cm^3$ size (100CPSI) catalyst support and catalyst coating process
o Pilot plant scale operation of $NO_x\;(NO,\;NO_2,\;N_2O)$ removal test on developed catalyst preform under simulated nitric acid production effluent gas environments and suggested improvements under both activating and deactivating conditions
o Pilot plant process design and optimization to realize simulated effluent gas environments of nitric acid production: Process analysis study using Fluent code, Aspen, etc
o Actual installation of catalyst process pilot plant for efficient control and removal of greenhouse gases emitted from actual nitric acid powder plant: System PFD, P&ID, ASSAY, Instrument Index, etc
o X-ray examination for physico-chemical investigation on surface characterization of zeolite-base $DeNO_x$ catalysts in terms of actual catalysts performance
o Suggested methods to improve performance of $DeNO_x\;(NO,\;NO_2,\;N_2O)$ catalysts based on catalysts surface characteristics and morphology before and after exposure
목차 Contents
- 제출문...1
- 보고서 초록...2
- 요약문...3
- Summary...9
- CONTENTS...17
- 목차...20
- 표 차례...23
- 그림 차례...26
- 제1장 연구개발과제의 개요...34
- 제1절 연구개발의 배경...34
- 제2절 기후변화가스에 대한 국제적 동향 및 대응...36
- 1. 기후변화가스에 의한 세계경제의 변화...36
- 2. 기후변화가스의 배출량 변화...37
- 3. 국내 기후변화협약에 의한 영향...39
- 제3절 국내.외 관련기술 현황...42
- 1. 국외 관련기술 현황...42
- 2. 국내 관련기술 현황...45
- 제2장 국내외 기술개발 현황...46
- 제1절 국내외 기술개발현황...46
- 1. 국내의 탈질시장의 현황...46
- 2. SCR 기술 동향 및 N2O 발생 고려한 촉매설계...48
- 3. 하니컴형 촉매지지체 제조 기술 분야 현황...51
- 4. 다양한 아산화질소 배출원에 대한 기술개발의 방향...55
- 제2절 국내외 특허 분석...57
- 제3장 연구개발 수행내용 및 결과...66
- 제1절 촉매 제조방법 및 실험방법...66
- 1. 촉매의 제조...66
- 2. 실험 장치 및 방법...74
- 제2절 촉매담체 제조공정 최적화...77
- 1. 촉매담체 제조 기술개발 내용...77
- 2. 촉매 담체의 제조 공정별 특성...80
- 제3절 제올라이트 촉매의 활성실험...125
- 1. 제올라이트 촉매의 성분 및 특성분석...125
- 2. DeN2O SCR 실험결과...142
- 3. DeNOx SCR 실험결과...163
- 4. N2O 및 NOx 동시제거 실험결과...169
- 제4절 Pilot Plant 설비 운전연구...183
- 1. Pilot Plant 시스템 운전...183
- 2. 활성평가 및 분석...264
- 3. Pilot Plant 공정 해석...272
- 제5절 제조한 촉매의 현장실험...290
- 1. 이동식 촉매평가 시스템 제작 및 운전방법...290
- 2. 현장실험 결과...315
- 제6절 위탁과제 (제올라이트에 포함된 활성물질의 구조 특성 연구)...337
- 1. X선 흡수 미세 구조 (XAFS)...337
- 2. 방사광을 이용한 실험...340
- 3. 데이터 분석...342
- 4. 촉매의 XAFS 구조 특성 결과...344
- 제4장 목표달성도 및 관련분야에의 기여도...363
- 제1절 과제수행 목표 달성도...363
- 제2절 관련분야에 대한 기여도...370
- 제5장 연구개발결과의 활용계획...373
- 제1절 국내 질산제조사업장 및 N2O 발생현황...373
- 1. 기술의 경쟁력 분석...373
- 2. DeN2O(SCR ) 기술의 시장성 분석...374
- 제2절 실증사업을 통한 사업화 가능성...381
- 제3절 현재 진행사항 및 활용계획...381
- 제6장 연구개발과정에서 수집한 해외과학기술정보...383
- 제1절 아산화질소 저감관련 해외 업체의 기술정보...383
- 제2절 아산화질소 촉매개발 관련 학술 연구현황...384
- 참고문헌...391
- 부록1. 연구성과...395
- 부록2. 홍보(국내 5건)...399
※ AI-Helper는 부적절한 답변을 할 수 있습니다.