최종 보고서(완결본) 082-091-078

폐기물 자원화기술

Recycling technology of waste

Steam Plasma를 이용한 열경화성수지의 가스화 기술 개발

A Study on the gasification of thermosetting resin by steam plasma

전주대학교

환 경 부

제 출 문

환경부장관 귀하

본 보고서를 “Steam plasma를 이용한 열경화성수지의 가스화 기술 개발에 관한

연구”과제의 최종보고서로 제출합니다.

2011년 8월 31일

주관연구기관명 : 전주대학교 산학협력단

연구책임자 : 박현서

연 구 원 : 이환노, 유병수

〃 : 안용성, 노성기

〃 : 임경완, 이 훈

- 1 -

사업명 차세대 핵심환경기술개발사업 기술분류 실용

연구과제명 steam plasma를 이용한 열경화성수지의 가스화 기술 개발

최종성과품 스팀 플라즈마 토치, 폐기물 가스화 처리설비

수행기관

(주관기관)

기관

(기업)명전주대학교 산학현력단 설립일 2004.03.01

주소 전북 전주시 완산구 효자 3가 1200

대표자

(기관장)심 동 희 연락처 063-220-2461

홈페이지 http://www.jj.ac.kr 팩스 063-220-2367

연구과제

개요

주관연구책임자 박현서 소속부서 환경보건전화

E-mail

063-220-2308

hnsepark@unitel.c

o.kr

실무담당자 유병수전화

E-mail

063-229-2920

yoobsone@hanmail

.net

참여기업 (주)리뉴에너지, (주)아름다운세상

총사업비

(천원)

정부출연금민간부담금

합계현금 현물

725,000 54,000 190,000 969,000

총연구기간 2009. 3. 1. ～ 2011. 8. 31. (30 개월)

연구개발

결과

최종목표

본 연구의 최종목표는 폐열경화성수지(FRP등)를 대상으로 steam

plasma를 이용한 가스화 처리 후 생성되는 syn-gas (CO(g)+H2(g)+

CH2(g)) 농도를 용적률로 80%이상을 확보하는 기술 및 처리 후 환경오

염물질을 최소화하는 기술을 개발하는데 있으며, 이를 위하여 steam

plasma torch 및 plasma 가스화 설비에 대한 설계기술 확보, 운전기술

확보, 처리기술 표준화하는데 있다.

개발내용 및

결과항 목

No of Assembly

Drawing

Detailed

DrawingTotal No

Anode 1 1 2

Cathode 1 1 2

Watersupply 1 7 8

1. steam을 plasma gas로 사용하는 steam plasma system 상세설계/

제작/운전기술 확보

보고서 초록

- 2 -

Waterdraw 1 5 6

Airduct 1 6 7

Case 1 5 6

기타부품류 - 14 14

Torch전체 1 - 1

(Spec.) - 3 3

합 계 7 42 49

항 목　 A1 A2 A3 A4 합계

After burner 1 7 4 77 89

Cooler 1 0 3 5 9

Gasifier 11 9 61 61 142

Hopper 1 0 2 26 29

Loader 5 0 4 30 39

Plasma torch 0 0 3 2 5

Power Supply 1 0 1 2 4

기타 4 0 3 2 9

합계 24 16 81 205 326

FRP/steam

ratio 0.5 1.0 1.5

H2 45.48 57.21 54.93

CO 24.51 32.75 35.27

syn-gas 69.99 89.96 90.2

발열량(kcal/m3) 2128 2734 2741

FRP/steam

ratio 2.0 2.5 3.0

H2 54.19 53.94 53.05

CO 35.81 36.05 36.95

syn-gas 90 89.99 90

발열량(kcal/m3) 2734 2734 2734

항 목소각로

기준치측정치 항 목

소각로

기준치측정치

황산화합물 (ppm) 30~100(12) ND 카드뮴 (mg/Sm3) 0.5(12) 0.031

질소산화물 (ppm) 80~150(12) 6.5 납 (mg/Sm3) 10 0.688

일산화탄소 (ppm) 50~300(12) 1.0 크롬 (mg/Sm3) 20 0.009

먼지 (mg/Sm3) 30~100(12) 6.87 구리 (mg/Sm3) 5 ND

매연 (도) 2도 0 니켈 (mg/Sm3) 30 ND

암모니아 (ppm) 100 2.9 브롬 (ppm) 10 ND

이황화탄소 (ppm) 30 ND 벤젠 (ppm) 10 0.212

염화수소 (ppm) 30~50(12) ND 페놀 (ppm) 0.1(12) ND

시안화수소 (ppm) 10 ND포름알데히드

(ppm) 0.5(12) 0.002

2. steam torch를 이용한 폐열경화성수지(FRP) 가스화 처리 system 설

계/제작/운전기술 확보

3. 열경화성 수지(FRP) 가스화 처리 후 syn-gas 생성률 80% 확보

4. 폐열경화성 수지(FRP) 가스화 처리시 배가스 측정 결과 환경기준치

이내 처리가능

○ 배가스 측정결과

- 3 -

황화수소 (ppm) 2~10(12) ND 수은 (mg/Sm3) 10 0.814

염소 (ppm) - ND 비소 (ppm) 0.1(신설비) 0.025

불소화합물 (ppm) 2~3(12) 1.3 아연 (mg/Sm3)

다이옥신

(ng-TEQ/Nm3) 5.0 0.025

○ 중금속 측정결과

구분Cd Hg Pb Cr

+6As Cu

≤0.3 ≤0.005 ≤3.0 ≤1.5 ≤1.5 ≤3.0

sample 1 ND ND ND ND ND ND

sample 2 ND ND ND ND ND ND

sample 3 ND ND ND ND ND ND

개발기술의

특징․장점

폐수지를 가스화 처리하기 위해서는 가스화제로 공기(air), 산소(O2),

steam(H2O)등이 사용되고 있으나, 공기를 사용하는 경우 생성가스 중 N2

농도가 높아 syn-gas 용적률이 낮고 산소를 사용하는 경우 완전연소에

의해 syn-gas 생성율이 낮다. 본 기술의 특징은 가화제로 steam을 사용

하여 steam의 열분해에 따라 syn-gas 생성율을 최대 90%이상 확보할

수 있는 기술이며, 국내외적으로 최초로 열경화성수지를 대상으로 연구된

기술이며, 이에 따른 설계기술, 운전기술, 제작기술이 100%확보 되었으

며, 세계적으로 최고 수준의 기술로 실증단계 후 수출전략 상품화가 가능

하다.

기대효과

(기술적 및

경제적 효과)

- steam plasma 기술을 이용하여 폐 열경화성수지(FRP)를 대상으로 가

스화 처리를 하는 경우 설계 및 처리기술 확보, 폐열경화성 수지 가스화

설비 국내외 판매효과 및

- 폐열경화성 수지의 가스화 처리에 따른 경제적 효과가 있을 것으로 예

상됨.

- 폐 plastic 발생량 : 400만톤/년

- 가스화 처리비율 : 10%(년간 40만톤/년)

- Steam plasma 가스화 설비비(30ton/day급) : 35억/기

- 소요기수 ; 45기

- 설비시장 : 45기*35억/기1575억원

적용분야

steam plasma torch를 이용하여 폐기물 가스화하는 경우 syn-gas의 생

성율이 다른 가스화 system에 비하여 최대 50%이상 높기 때문에 다양한

유기성 물질에 대하여 가스화 처리 적용 가능함. 대상물질로는 도시폐기

물 및 산업폐기물에 적용가능하며, 특히 폐목재, 저급 석탄, 유기성

sludge류, 폐합성고무류 등의 가스화 처리에 유리할 것으로 예상됨.

과학기술적

성과특허 국내

출원일 명칭 출원번호

2011.05.11 폐기물가스화 처리장치 10-2011-0043770

2011.06.08 스팀 플라즈마 토치 10-2011-0054902

○ 특허 2건

- 4 -

국외

논문

게재

SCI

비SCI

게재연월논문명 학술지명 Vol.(No.)

연 월

2011 6스팀플라즈마 가스화반응기에서

열유동 특성한국열환경공학회 8(2)

2011 6스팀플라즈마를 이용한 폐

멜라민수지의가스화연구(Ⅰ)한국열환경공학회 8(2)

2011 8열경화성수지(FRP)의 열분해 가스화

특성 연구전주대학교자연과학연구소 21(1)

2011 8열경화성수지(멜라민)의 열분해 가스화

특성 연구전주대학교자연과학연구소 21(1)

○ 논문 : 4건

기 타

게재연월제목 학술지명

연 월

2009 11 열경화성수지의 열분해가스화 특성연구 (사)한국열환경공학회

2009 11 열가소성수지의 열분해가스화 특성 연구 한국폐기물학회

2009 11 열가소성수지의 가스화 특성 연구 한국신재생에너지학회

2010 05steam plasma를 이용한 열경화성 폐plastic의

가스화 연구(Ⅱ)한국열환경공학회

2010 11steam plasma를 이용한 열경화성 폐plastic의

가스화 연구(Ⅲ)한국열환경공학회

2010 11steam plasma를 이용한 혼합플라스틱 가스화

처리기술

2010폐기물관리 및

처리기술발표회

2011 03ELECTRIC-ARC PLASMATORCHES FOR

PLASMA-THERMAL TECHNOLOGIES

Khristianovich's Institute

of Theoretical and

Applied Mechanics SB

RAS

2011 05steam plasma를 이용한 열경화성수지의(멜라민수지) 가스화 처리 연구

한국자원리싸이클링학회

2011 05 멜라민수지의 가스화 연구(Ⅱ) 한국열환경공학회

2011 05steam plasma를 이용한 열경화성수지(Phenolic resin)의 가스화 연구Ⅱ

한국열환경공학회

제목 내용

plasma torch / power supply 이론 및 실무교육

- steam plasma torch 설계 및 제작 이론교육- steam plasma torch 현장 실무교육 - power supply 이론교육 - power supply 현장 실무교육

○ 학술발표 10건

○ 교육 1건

사업화

성과

매출액개발후 현재까지 억원

향후 3년간 매출 100억원

시장

규모현재의 시장규모

국내 : 1000억원

세계 : 10000억원

- 5 -

향후(3년) 예상되는 시장규모 국내 : 1500억원

세계 : 15000억원

시장

점유율

개발후 현재까지 국내 : 90%

세계 : 30%

향후 3년 국내 : %

세계 : %

세계시장

경쟁력

순위

현재 제품 세계시장 경쟁력 순위 2위 (60%)

3년 후 제품 세계시장 경쟁력 순위 1위 (60%)

- 6 -

① Steam plasma을 이용한 열경화성 수지의 가스화 System 설계기술 확보

② 상기 설비를 이용한 가스화 처리 기술 표준화

③ Syn-gas 농도 (CO+H2+CxHy vol%) 80%이상 제조기술 확보

① 전용 열경화성 수지의 가스화 System 설계

② 상기설비를 이용한 가스화 처리기술 표준화

- 중금속 처리기술 확보

- 대기오염농도 기준 확보

③ Syn-gas 농도 (CO+H2+CxHy vol%) 80%이상 제조 기술

요 약 문

Ⅰ. 연구개발의 목표

1. 연구개발의 최종목표

2. 최종 처리목표 조건

Ⅱ. 연구개발의목적 및 필요성

환경을 염두에 둔 재료(Environmentally conscious materials) 또는 생태계와 조화된 재료

(Ecological materials)의 개념이 대두되면서 가장 가까운 장래에 모든 재료는 Recycling을 전

제로 설계되지 않으면 안 되며, 기존 사용되고 있는 물질에 대해서는 Recycling 기술의 개발이

Green round에 대비하여 절대적으로 필요하다. 산업 폐기물은 산업의 발달에 따라 증가되고

대부분은 플라스틱 폐기물로 이루어져, 이를 매립이나 단순 소각을 할 경우 환경, 경제적인 측

면에서 매우 불리하므로 재활용이 불가한 혼합플라스틱을 에너지로 재활용하는 것이 환경과

경제적인 측면에서 아주 유리하다. 또한, 선진국에서는 플라스틱의 재활용기술을 개발하였거나

개발이 진행 중에 있으므로 플라스틱의 생산과 수요는 계속적으로 급신장할 것으로 예상되며,

이에 따라 고발열량인 플라스틱폐기물의 에너지화 역시 급신장할 것이 분명하다. 폐열경화성

수지의 경우 수분, 회분이 적고 발열량이 높은 장점을 가지고 있는 반면, 중금속 소멸문제, 처리 시

- 7 -

Dioxin 또는 Fume의 발생문제, 기타 유독 화학물질의 노출문제 등의 단점을 가지고 있다. 따라서

에너지 문제가 심각한 지금에 이르러, 폐열경화성수지의 에너지화 및 무해하게 처리하는 방법이

동시에 요구되고 있으며, 이의 대표적인 방법이 열분해 가스화 기술이고 이에 대한 연구가 전

세계적으로 다양한 방법으로 진행되고 있는 실정이다. 폐열경화성수지로 고온 가스화 기술을 통

하여 에너지를 회수하는 경우 Syn-gas 농도를 (CO + H2 + CH4 vol%) 최대 80%까지 제조가능하

며, 기타 중금속 문제, 대기오염 문제가 쉽게 해결 될 수 있다. 우리나라의 산업폐기물 중 플라스

틱 생산량은 미국, 일본, 독일에 이어 세계 4위 생산국이다. 전 세계 플라스틱 소요량 1억 2940

만톤 중 미국에서 29%를, 일본이 11%를, 독일이 8%를, 그리고 우리나라는 전 세계의 6%인

약 8만톤을 생산하고 있다. 국내 합성수지 수요량은 444만톤 이고 이는 단지 압출, 사출, 캘린

더 등의 성형방법으로 만든 플라스틱제품에만 해당하는 것이다. 반면, 우리나라의 폐플라스틱

의 발생량 현황을 분석하여보면 다음과 같다.

그림 1.1 폐플라스틱 현황

표 1.1 플라스틱류 재활용품 발생, 선별, 처리량

(단위 : 톤/년)

구분 발생량 선별량 처리량

추정량 1,643,758 360,747 603,633

- 8 -

플라스틱류의 발생총량은 1,644천톤으로 추정되는데 이는 재활용품으로 분리하여 배출된 플라

스틱류의 발생원단위(46.7g/일/인)에 인구수를 대입하여 산출한 플라스틱류 재활용품 839천톤

과 종량제봉투 내 플라스틱류의 발생원단위(44.8g/일/인)에 인구수를 적용하여 산출한 재활용

가능한 플라스틱류 805천톤을 합한 것이다. 종이류, 고철류과 달리 재활용 가능한 플라스틱류

의 경우 총 발생량의 절반정도가 재활용품으로 분리되고, 나머지 절반은 폐기된다. 분리수거된

839천톤의 플라스틱류 중 약 30%는 민간수집상에서 선별되고 13%는 지자체 선별장에서 선별

되며 선별과정에서 폐기되는 플라스틱류는 57%이다. 폐기되는 플라스틱은 주로 재활용품으로

지정되어 있으나 많은 부분이 재생원료로 이용되지 못하는 필름류이다. 플라스틱류 재활용 업

체의 연간 재생원료 이용량은 603천톤이며, 생활폐기물 경로에서 회수된 플라스틱류가 국내 플

라스틱처리업체의 재생원료로 투입되는 양은 60%정도이며 40%는 별도의 수급경로를 통해 확

보된다. 플라스틱류는 종류가 다양하고, 복합재질인 경우도 많아서 이론상으로는 재활용이 가

능하지만 경제성이 떨어지거나, 현재까지 재활용기술이 부족하여 재활용품으로 분리되지 않고

폐기처분되는 양이 많으며, 분리되더라도 처리시설에서 재생원료로서 기여하는 부분이 다소 적

다. 특히 열경화성 수지의 경우 강화제로 많은 물질이 사용되기 때문에 재활용 처리가 더욱더

어려운 실정이다.

Ⅲ. 연구개발 결과

열경화성 수지를 대상으로 Steam plasma system을 이용한 Pilot plant 가스화 처리 실험결과 다음

과 같은 결론이 얻어졌다.

1. 열경화성 수지 가스화 처리에 대한 열역학적 분석, 기초실험이 완료되었다.

2. Steam plasma torch가 설계/제작이 완료 되었다.

3. Steam torch를 이용한 Pilot plant 가스화 설비가 설계/제작 완료되었다.

4. Steam torch를 이용한 열경화성수지에 대한 연속실험결과 가스화 생성물이 다음과 같이 분석되

었다.

- 9 -

○ Melamin resin (Unit : Vol%)

구분 30min 60min 90min 120min 150min 180min 210min 240min 평균

H2 49.73 48.94 49.44 50.86 50.42 50.96 50.36 50.80 50.19

N2 13.75 14.06 13.49 11.32 11.86 11.81 10.79 11.56 12.33

CO 26.52 27.00 27.06 27.82 27.71 27.23 28.67 27.81 27.48

H2/CO ratio

1.88 1.81 1.83 1.83 1.82 1.87 1.76 1.83 1.83

Syn-gas 76.25 75.94 76.50 78.68 78.13 78.19 79.03 78.61 77.67

발열량(kcal/m3)

2318 2308 2325 2391 2375 2377 2402 2389 2361

○ FRP (Unit : Vol%)

FRP/Steam ratio H2 CO H2/CO ratio Syn-gas발열량

(kcal/m3)

0.5

Sample 1 62.33 25.52 2.44 87.85 2672

Sample 2 61.38 26.51 2.32 87.89 2673

Sample 3 61.14 26.77 2.28 87.91 2671

평 균 61.62 26.27 2.35 87.89 2673

1.0

Sample 1 57.87 30.18 1.92 88.05 2677

Sample 2 58.31 29.81 1.96 88.12 2679

Sample 3 57.33 30.79 1.86 88.12 2678

평 균 57.84 30.26 1.91 88.10 2678

1.5

Sample 1 55.88 32.32 1.73 88.2 2680

Sample 2 55.56 32.62 1.70 88.18 2680

Sample 3 55.39 32.78 1.69 88.17 2679

평 균 55.61 32.57 1.71 88.18 2680

2.0

Sample 1 54.74 33.47 1.64 88.21 2680

Sample 2 54.72 33.55 1.63 88.27 2682

Sample 3 54.84 33.42 1.64 88.26 2682

평 균 54.77 33.48 1.64 88.25 2681

- 10 -

○ Urea resin (Unit : Vol%)

구분 10min 20min 30min 40min 50min 60min 70min 80min 평균

H2 51.85 52.44 53.9 50.05 52.49 51.77 52.88 52.94 52.29

N2 8.87 7.86 6.05 7.67 7.82 8.11 7.39 7.32 7.64

CO 29.03 29.69 30.04 29.43 29.68 28.28 29.73 29.97 29.48

H2/CO

ratio1.79 1.77 1.79 1.70 1.77 1.83 1.78 1.77 1.77

Syn-gas 80.88 82.14 83.94 79.48 82.49 80.06 82.61 82.91 81.81

발열량(kcal/m

3)

2458 2496 2551 2415 2497 2433 2511 2518 2485

○ Phenol resin (Unit : Vol%)

구분 20min 40min 60min 80min 100min 120min 평균

H2 52.51 52.02 53.59 53.38 53.73 54.36 53.27

N2 0.79 2.18 0.65 0.76 2.02 0.09 1.08

CO 36.48 34.45 35.55 35.64 33.73 35.51 35.23

H2/CO

ratio1.44 1.51 1.51 1.50 1.59 1.53 1.51

Syn-gaas 88.99 86.47 89.14 89.02 87.46 89.87 88.49

발열량

(kcal/m3)2703 2627 2708 2704 2657 2730 2688

5. Steam plasma torch의 효율이 Anode : 75%, Cathode : 95%로 Air torch와 비교하여 큰 차이는

나타나지 않았다.

6. Steam plasma torch의 수명은 음극의 경우 8.79 E-9kg/s, 양극의 경우 2.25 E-5kg/s로 나타났다.

7. 열경화성 수지의 처리 후 배기가스 분석결과 표에 나타난 바와 같이 환경기준치 이내에서 관리

되었다.

- 11 -

C(resin) + 1/2O2 → CO ....................................................... ① C(resin) + O2 → CO2 ...................................................... ② C + CO2 →2CO ...................................................... ③ C(resin) + 2H2 → CH4 C + H2O(steam) → CO + H2 ............................................... ④ C + 2H2O → CO2 + 2H2 ...................................................... ⑤ H2O →(2000℃)→ H2 + 1/2O2 .................................................... ⑥ 2H + 1/2O2 → H2O .................................................................... ⑦

항 목 소각로 기준치 측정치 항 목 소각로 기준치 측정치

황산화합물 (ppm) 30~100(12) ND 카드뮴 (mg/Sm3) 0.02~0.2(12) ND

질소산화물 (ppm) 80~150(12) 6.5 납 (mg/Sm3) 0.2~5(12) 0.003

일산화탄소 (ppm) 50~300(12) 1.0 크롬 (mg/Sm3) 0.5(12) 0.031

먼지 (mg/Sm3) 30~100(12) 6.87 구리 (mg/Sm3) 10 0.688

매연 (도) 2도 0 니켈 (mg/Sm3) 20 0.009

암모니아 (ppm) 100 2.9 브롬 (ppm) 5 ND

이황화탄소 (ppm) 30 ND 벤젠 (ppm) 30 ND

염화수소 (ppm) 30~50(12) ND 페놀 (ppm) 10 ND

시안화수소 (ppm) 10 ND포름알데히드

(ppm) 10 0.212

황화수소 (ppm) 2~10(12) ND 수은 (mg/Sm3) 0.1(12) ND

염소 (ppm) - ND 비소 (ppm) 0.5(12) 0.002

불소화합물 (ppm) 2~3(12) 1.3 아연 (mg/Sm3) 10 0.814

다이옥신 (ng-TEQ/Nm3)

5.0 0.025

8. FRP를 대상으로 가스화 처리 후 생성된 Slag 중금속 용출분석결과 기준치에 만족하였다.

9. 실증화를 위한 주요 설계인자 및 Steam plasma 가스화 반응로의 개념도가 설정되었다.

Ⅳ. 연구개발 특징 및 장점

1. Steam plasma 가스화의 장점

열경화성 수지를 대상으로 가스화 처리하는 경우 다음과 같은 반응이 예상될 수 있다.

- 12 -

조건 가스화제 H2 CO N2 CO2 H2O Syn-gas발열량

(kcal/kg)

온도 : 1000℃, 가스화제/Resin:1.0

Air 14.85 29.96 55.04 0.07 0.05 44.8 1359

O2 32.19 67.13 2.00 0.32 0.26 99.33 3017

Steam 56.84 42.43 0.00 0.13 0.29 99.27 3044

상기의 대표적인 가스화 반응을 통하여 Syn-gas(CO, H2O, CH4)를 얻기 위하서는 가스화제가

필요하며, 가스화제로는 공기, 산소, Steam 등이 사용되고 있다. 그러나 가스화제로 공기를 사

용하는 경우 수지 중에 탄소(C)원소가 ①식과 ②식의 반응으로 유도되나, 열역학적으로 공기비

율이 작아도 CO2와 H2O가 안정적으로 생성되며, Syn-gas 비율이 작아지며 또한 공기 중에

N2성분으로 인하여 얻어지는 Syn-gas 중 CO+H2O+CH4 비율이 낮아진다. 반면에 산소를 가스

화제로 선정하는 경우 O2 생산설비가 추가로 소요되며, 반응로 온도에 따라 차이는 있지만 반

응 ① 보다도 반응 ② 또는 반응 ⑧이 안정적으로 생성된다. 따라서 얻어지는 Syn-gas의 생성

율이 작아지는 원인이 된다. 가스화제로 Steam을 사용하는 경우 우선적으로 H2O의 열분해 속

도가 주요한 변수이며, ⑦식의 분해반응이 일어나기 위해서는 최소 2000℃이상의 열분해 온도가 필요하다. Plasma torch 내부장 온도를 10,000℃ 정도로 분석했을 경우 Steam을 Plasma gas로 사용하는 경우 거의 100% O, OH, H, H2, O2로 분해된다. 따라서 Steam을 가스화제로

사용하는 경우 Syn-gas 생성 시 열역학적인 생성율은 물론 반응속도론적인 측면에서도 ⑤식

의 반응이 유리하게 진청될 수 있다.특히 Steam plasma를 이용하는 경우 Syn-gas 생성 속도

가 타 가스화제를 사용하는 경우보다 훨씬 유리한 장점이 있다.

다음 표는 반응온도 1000℃에 대한 가스화제/Resin=1.0에서 가스화제 사용에 따른 Syn-gas 생성율에 대한 비교표이다. 표에 분석된 바와 같이 Syn-gas 생성율이 Air를 사용하는 경우보다

50%이상 높게 생성 가능하다.

[가스화제 변화에 따른 Syn-gas 생성율 비교]

(Unit : Vol%)

2. Steam plasma 가스화 System의 특징 및 장점

본 연구를 통하여 설계 개발된 Steam plasma 가스화로의 경우 열경화성 수지의 가스화 반응

속도를 어떻게 높이느냐가 주요한 변수이며, 이를 위하여 Steam plasma torch의 위치, 장입

System의 위치, 반응시간, 반응온도, 로 내 압력제어 등을 고려하였다. Steam plasma 가스화

System 개략도는 다음과 같다.

- 13 -

그림에 나타난 바와 같이 Steam plasma 가스화로의 경우 완전 가스화 반응을 위한 1차 유동

상 가스화로와 2차 Cyclone type 가스화로로 구성되어 있으며, 1차 유동상 가스화로에서 미가

스화 입자는 2차 Cyclone type 가스화로에서 완전 가스화가 되도록 체류시간을 최대화 하였다.

이에 따른 설비의 특징 및 장점은 다음과 같다.

① 가스화제로 Steam을 사용함으로써 Syn-gas 농도를 80%이상 유지 가능하다.

② FRP등에 함유된 무기물(Glass fiber)에 대한 용융 무해화 처리가 가능하다.

- 14 -

③ 가스화로 내 O2농도를 Zero화하여 Dioxin생성이 극소화 배출된다.

④ Plasma gas로 Steam을 사용함으로써 Thermel NOx 생성이 극히 적다.

⑤ 체류시간을 최대 4sec이상 유지시킴으로써 폐plastic의 완전 가스화 처리가 가능하다.

⑥ Steam의 Ion화에 따른 가스화 반응속도가 빠르다.

⑦ 로 내 가스화 온도의 조정이 용이하며 폐기물 투입량 조정이 용이하다.

3. Steam plasma torch의 장점

본 연구에서 설계 개발된 Steam plasma torch의 경우 국내외적으로 독창적으로 개발되었으며,

다른 Torch에 비하여 다음과 같은 특징 및 장점을 가지고 있다. 표에 나타난 바와 같이 가장

주요한 특징은 Plasma gas로 Steam을사용하여 Syn-gas 농도를 최대한 얻을 수 있는 것이다.

항목 본 연구 삼성중공업 프랑스(Aerospatial)

Torch type Non-trans Trans-type Trans-type

음극부 Button Hollow Hollow

음극 재질 W +Hf Cu Cu

양극부 Hollow Hollow Hollow

양극재질 Cu+Sn Cu Cu

Plasma gas Steam Air Air

Torch 효율 70~75% 70% 70%

Torch 수명 500~1000hr 500~1000hr 500~1000hr

전류(A) 800A 900A 1000A

전압(V) 1300V 1200V 1000V

Thermal NOx 1ppm 미만 10000이상 10000ppm이상

Elec. field EH2O=25V/cm EH2O=15V/cm EH2O=15V/cm

- 15 -

Ⅴ. 기대 효과Steam plasma 기술을 이용하여 폐열경화성 수지를 가스화 처리하는 경우 Syn-gas 농도

(CO+H2+CH4)를 80%이상 생성하는 것이 가능하며, 또한 처리 후 생성물의 환경 친화적 처리

가 가능한 것으로 기대된다. 폐열경화성 수지 처리시 Steam을 가스화제로 사용하기 때문에 고

온 가스화 반응시 발생될 수 있는 NOx의 생성도 제어 가능하며, 생성된 Syn-gas를 이용하여

부가가치가 높은 F-T process를 이용한 Methanol 제조, WGS를 이용한 H2 gas 제조가 가능

하여 폐합성수지로부터 Syn-gas 생성기술은 향후 다방면으로 적용 가능한 것으로 사료된다.

본 연구를 통하여 개발된 Steam torch 설계기술은 세계적으로 우수한 기술로써 단품으로도 시

장성이 충분히 있을 것으로 사료되며, 또한 이 Steam torch를 이용한 가스화 제조 System도

실증화 공정을 통하여 수출전략 상품화가 가능하다.

Ⅵ. 적용 분야

Steam plasma torch를 이용하여 가스화 처리가 가능한 폐기물 및 자원의 경우 다음과 같다.

대상폐기물/자원

- 생활폐기물

- 유기성 Sludge

- 폐합성 수지

- 열경화성/가소성 수지

- 산업 가연성 폐기물

- Shredder dust

- 폐합성 고무류

- 폐목재류

- 저급 석탄류

- 폐유

- 기타

- 16 -

Summary

Ⅰ. Objective of Research and Development

1. Ultimate Objective of Research and Development

① Obtain design technology of a system that gasifies thermosetting resin using steam

plasma

② Standardize a technique of gasification treatment using the above system.

③ Obtain a manufacturing technique resulting in a minimum 80% syn-gas concentration

(CO+H2+CxHy vol%)

2. Conditions of Ultimate Objective

① Design a system that gasifies designated thermosetting resin.

② Standardize a technique of gasification treatment using the above system.

- Obtain a technique in disposing of heavy metal

- Obtain standard of air pollution concentration

③ A manufacturing technique of a minimum 80% syn-gas concentration (CO+H2+CxHy

vol%)

Ⅱ. Objective and Demand of Research and Development

As more awareness on environmentally conscious or ecological materials has been raised,

in the near future it will expected that all materials are designed on recycling. And

existing materials critically require development of their recycling techniques in preparation

for Green Round. Industrial wastes build up as industries grow, and they are composed of

mostly plastic wastes, causing negative effects on the environment and on the economy

when they are landfilled or incinerated. Consequently, turning non-recyclable compound

plastics into energy can be very beneficial to the environment as well as the economy. As

many of the developed countries either have developed or are in process of developing

such recycling technology of plastics, production and demand of plastics are expected to

grow rapidly and continuously. This in turn will result in high demand of energy recovery

- 17 -

from plastic wastes with high caloric power. In case of thermosetting plastic wastes, they

have advantages of having low water content and resulting in low ash and high heat

generation. However, they also have problems with disposing of heavy metals, generating

dioxin or fume and exposing other toxic chemical substances. In the time of many resource

issues, turning thermosetting plastic wastes into energy and disposing them without

causing any harm are being demanded concurrently. As one of the typical techniques of

such, the pyrolyzed gasification technology is now being studied around the world in

various ways. In turning thermosetting plastic wastes into energy through high

temperature gasifying system, a maximum 80% concentration of syn-gases (CO + H2 + CH4

vol%) can be produced, solving the problems with heavy metals and air pollution. Korea is the

fourth country behind US, Japan, and Germany that produce the most Industrial plastic wastes

in the world. From 129.4 million tons of plastic demand in the world, 29% of it produced in US,

11% in Japan, 8% in Germany, and 6% in Korea, which is equivalent to 80,000 tons. The

domestic demand for synthetic resin is 4.4 million tons, counting only the molded plastics by

methods such as extrusion and injection molding. The following illustrates the present overview

of plastic wastes in Korea.

Figure 1.1 Overview of plastic wastes

- 18 -

[Quantity of plastic wastes - formed, selected, and processed]

(Unit: ton/year)

Formed Quantity Selected Quantity Processed Quantity

estimation 1,643,758 360,747 603,633

The total amount of plastic waste is estimated at 1.644 million tons - This was calculated

by adding 839,000 tons derived from 46.7g/day/person of plastics getting recycled and

805,000 tons derived from 44.8g/day/person of recyclable plastics found in garbage. Unlike

metal or paper products, only half of recyclable plastics end up getting recycled, the other

half being discarded. Of the 839,000 tons of recycled plastics, approximately 30% is sorted

at residential collectors, while 13% is sorted at municipal recycling facilities. 57% of

plastics is discarded during the sorting process. Among the discarded plastics are film

products, which are usually designated as recyclable, but the majority of the components

cannot yield recycled material. Industrial usage of recycled materials from recycled plastics

is 603,000 tons yearly. 60% of it comes from consumer waste recycling, while 40% is

provided through other sources. Although theoretically recyclable, plastics are not as

economically feasible to be recycled, because there are many different types of plastics,

many of which are compound plastics. Furthermore, the insufficient recycling technology

results in more plastics being discarded than recycled. Even when recycled, plastics play

small roles as recycled materials. thermosetting resin, especially, have more difficulties wth

recycling due to the presence of many reinforcing agents.

Ⅲ. Results of Research and Development

The following conclusions have been obtained from experiments on pilot plant gasification

treatment using steam plasma system against thermosetting resin:

1. Thermodynamical analysis and fundamental experiments on gasification of thermosetting

resin.

2. Design and construction of steam plasma torch are completed.

3. Design and construction of gasification pilot plant using steam torch are completed.

4. After continuous experiments on thermosetting resin using steam torch, the gaseous products

have been analyzed as the following:

- 19 -

구분 30min 60min 90min 120min 150min 180min 210min 240min Average

H2 49.73 48.94 49.44 50.86 50.42 50.96 50.36 50.80 50.19

N2 13.75 14.06 13.49 11.32 11.86 11.81 10.79 11.56 12.33

CO 26.52 27.00 27.06 27.82 27.71 27.23 28.67 27.81 27.48

H2/CO ratio

1.88 1.81 1.83 1.83 1.82 1.87 1.76 1.83 1.83

Syn-gas 76.25 75.94 76.50 78.68 78.13 78.19 79.03 78.61 77.67

Caloric Value

(kcal/m3)

2318 2308 2325 2391 2375 2377 2402 2389 2361

FRP/Steam ratio H2 CO H2/CO ratio Syn-gasCaloric Value

(kcal/m3)

0.5

Sample 1 62.33 25.52 2.44 87.85 2672

Sample 2 61.38 26.51 2.32 87.89 2673

Sample 3 61.14 26.77 2.28 87.91 2671

Average 61.62 26.27 2.35 87.89 2673

1.0

Sample 1 57.87 30.18 1.92 88.05 2677

Sample 2 58.31 29.81 1.96 88.12 2679

Sample 3 57.33 30.79 1.86 88.12 2678

Average 57.84 30.26 1.91 88.10 2678

1.5

Sample 1 55.88 32.32 1.73 88.2 2680

Sample 2 55.56 32.62 1.70 88.18 2680

Sample 3 55.39 32.78 1.69 88.17 2679

Average 55.61 32.57 1.71 88.18 2680

2.0

Sample 1 54.74 33.47 1.64 88.21 2680

Sample 2 54.72 33.55 1.63 88.27 2682

Sample 3 54.84 33.42 1.64 88.26 2682

Average 54.77 33.48 1.64 88.25 2681

○ Melamin resin (Unit : Vol%)

○ FRP (Unit : Vol%)

- 20 -

10min 20min 30min 40min 50min 60min 70min 80min Average

H2 51.85 52.44 53.9 50.05 52.49 51.77 52.88 52.94 52.29

N2 8.87 7.86 6.05 7.67 7.82 8.11 7.39 7.32 7.64

CO 29.03 29.69 30.04 29.43 29.68 28.28 29.73 29.97 29.48

H2/CO

ratio1.79 1.77 1.79 1.70 1.77 1.83 1.78 1.77 1.77

Syn-gas 80.88 82.14 83.94 79.48 82.49 80.06 82.61 82.91 81.81

Caloric Value

(kcal/m3)

2458 2496 2551 2415 2497 2433 2511 2518 2485

○ Urea resin (Unit : Vol%)

10min 20min 30min 40min 50min 60min 70min 80min Average

H2 51.85 52.44 53.9 50.05 52.49 51.77 52.88 52.94 88.21

N2 8.87 7.86 6.05 7.67 7.82 8.11 7.39 7.32 88.21

CO 29.03 29.69 30.04 29.43 29.68 28.28 29.73 29.97 88.21

H2/CO

ratio1.79 1.77 1.79 1.70 1.77 1.83 1.78 1.77 88.21

Syn-gas 80.88 82.14 83.94 79.48 82.49 80.06 82.61 82.91 88.21

Caloric Value

(kcal/m3)

2458 2496 2551 2415 2497 2433 2511 2518 2485

○ Phenol resin (Unit : Vol%)

5. The efficiency of steam plasma torch, with a result of 75% Anode and 95% Cathode, did not

indicate a significant difference from air torch.

6. Lifetime of steam plasma torch is 8.79 E-9kg/s with a cathode and 2.25 E-5kg/s with an

anode.

7. Air pollutants created while treating thermosetting resin are analyzed to be within the

environmental standards as illustrated below:

- 21 -

ItemsIncinerator

thresholds

Measured

valuesItems

Incinerator

thresholds

Measured

values

Sulfur oxides

(ppm)30~100(12) ND

Cadmium

(mg/Sm3)0.02~0.2(12) ND

Nitrogen oxides

(ppm)80~150(12) 6.5 Lead (mg/Sm3) 0.2~5(12) 0.003

Carbon monoxide

(ppm)50~300(12) 1.0

Chromium

(mg/Sm3)0.5(12) 0.031

Ashes (mg/Sm3) 30~100(12) 6.87 Copper (mg/Sm3) 10 0.688

Emission (Index) 2 0 Nickel (mg/Sm3) 20 0.009

Ammonia (ppm) 100 2.9 Bromine (ppm) 5 ND

Carbon bisulfide

(ppm)30 ND Benzene (ppm) 30 ND

Hydrogen

chloride (ppm)30~50(12) ND Phenol (ppm) 10 ND

Hydrogen

cyanide (ppm)10 ND

Formaldehyde (ppm)

10 0.212

Hydrogen sulfide

(ppm)2~10(12) ND

Mercury

(mg/Sm3)0.1(12) ND

Chlorine (ppm) - ND Arsenic (ppm) 0.5(12) 0.002

Fluoride (ppm) 2~3(12) 1.3 Zinc (mg/Sm3) 10 0.814

Dioxin (ng-TEQ/Nm3)

5.0 0.025

8. Heavy metals in slag produced in gasification of FRP have been found to satisfy the

standard according to the elution analysis.

9. The major design factors and the schematic diagram of steam plama gasification reactor

have been established for substantiation process.

Ⅳ. Characteristics and Advantages of Research and

Development

1. Advantage of steam plasma gasification

The following reactions can be anticipated when gasifying thermosetting resin:

- 22 -

C(resin) + 1/2O2 → CO ....................................................... ① C(resin) + O2 → CO2 ...................................................... ② C + CO2 →2CO ...................................................... ③ C(resin) + 2H2 → CH4 C + H2O(steam) → CO + H2 ............................................... ④ C + 2H2O → CO2 + 2H2 ...................................................... ⑤ H2O →(2000℃)→ H2 + 1/2O2 .................................................... ⑥ 2H + 1/2O2 → H2O .................................................................... ⑦

Gasifying agents, such as air, oxygen, and steam, are required to obtain syn-gases (CO,

H2O, CH4) through the above typical gasifying reactions. Using air as a gasifying agent

leads to carbon elements in plastics going through reactions ① and ②. However, with

small ratio of air in terms of thermodynamics, CO2 and H2O are created stably, the ratio of

syn-gases decreases, and the ratio of CO+H2O+CH4 in syn-gases also decreases due to the

presence of N2 in the air. Choosing oxygen as the gasifying agent on the other hand will

add the cost of O2 production equipment. Although reactor temperatures can cause

differences, reaction ② or ⑧ is established more stably than reaction ①. Therefore it may

cause a decrease in syn-gas formation rate. With steam as the gasifying agent, the

pyrolysis rate of H2O is the major variable - for reaction ⑦, at least 2000℃ of pyrolysis temperature is required. On estimating the internal temperature of plasma torch at 10,000℃, using steam as plasma gas will almost always yield O, OH, H, H2, O2. Therefore, steam as

the gasifying agent will favor reaction ⑤ in terms of thermodynamic production rate as

well as reaction rate. Especially, steam plasma has an advantage in the syn-gas formation

rate compared to other gasifying agents.

The following table is a comparison of syn-gas formation rate between different gasifying

agents at gasifying agent/resin=1.0 with respect to reaction temperature of 1000℃. As illustrated, syn-gas formation rate can be 50% faster than using air.

- 23 -

[Comparison of syn-gas formation rate between gasifying agents]

(Unit : Vol%)

ConditionGasifying

agentsH2 CO N2 CO2 H2O Syn-gas

Caloric

Values

(kcal/kg)

Temperature:

1000℃, Gasifying agent/

resin:1.0

air 14.85 29.96 55.04 0.07 0.05 44.8 1359

O2 32.19 67.13 2.00 0.32 0.26 99.33 3017

Steam 56.84 42.43 0.00 0.13 0.29 99.27 3044

2. Characteristics and Advantages of steam plasma gasification system

With the steam plasma gasification furnace designed and developed by this research, means

to increase the gasification reaction rate of thermosetting resin plays an important role. For

this reason, the location of steam plasma torch, location of charging system, reaction time,

reaction temperature, and pressure control inside the furnace have been considered. The

schematic diagram of steam plasma gasification system is as follows:

- 24 -

Steam plasma gasification furnace, as shown above, is made of a primary fluidized

gasification furnace and a secondary cyclone-type gasification furnace for the complete

gasification. Particles that do not gasify in the primary fluidized gasification furnace are

put in the secondary cyclone-type gasification furnace at a maximum duration for the

complete gasification. The characteristics and advantages of other apparatus are:

① Using steam as the gasifying agent makes it possible to maintain a minimum 80%

concentration of syn-gas.

② Innocuous fusion treatment is possible for glass fiber in plastics such as FRP.

③ Formation of dioxin is minimal by eliminating O2 concentration in the gasification

furnace.

④ Formation of thermal NOx is minimal by using steam as plasma gas.

⑤ By allowing a maximum 4 seconds of duration, the complete gasification of plastic

wastes is possible.

⑥ Gasification reaction rate is fast due to the ionization of the steam

⑦ It is convenient to control the gasification temperature inside the furnace and to control

the amount of wastes being inserted.

- 25 -

3. Advantages of steam plasma torch

The steam plasma torch designed and developed in this research has been established

internationally exclusively and claims the following characteristics and/or advantages

compared to other torches, the foremost being the maximum concentration of syn-gas

using steam as plasma gas.

In this researchSamsung Heavy

IndustriesAerospatial(France)

Torch type Non-trans Trans-type Trans-type

Cathodic Part Button Hollow Hollow

Cathodic material W +Hf Cu Cu

Anodic Part Hollow Hollow Hollow

Anodic material Cu+Sn Cu Cu

Plasma gas Steam Air Air

Torch efficiency 70~75% 70% 70%

Torch Lifetime 500~1000hr 500~1000hr 500~1000hr

Current(A) 800A 900A 1000A

Voltage(V) 1300V 1200V 1000V

Thermal NOx less then 1ppm 10000이상 10000ppm or higher

Elec. field EH2O=25V/cm EH2O=15V/cm EH2O=15V/cm

Ⅴ. Anticipated Effects

When gasifying thermosetting resin wastes using steam plasma technology, it is possible

to generate more than 80% concentration of syn-gas (CO+H2+CH4), and

environmental-friendly disposal of the products is also expected. Since steam is used as

the gasifying agent treating thermosetting resin wastes, the formation of NOx, which can

occur during high-temperature gasification reactions, can be controlled. Using the syn-gas

- 26 -

products, high-value Methanol using F-T process and H2 gas using WGS can be

manufactured. All in all, the technology generating syn-gases from resin wastes is

expected to be applicable in many ways.

The technology of steam torch developed by this research is an outstanding technology

and is expected to be highly marketable even as a stand-alone. Additionally, gasification

system using this steam torch can be strategized on export through substantiation process.

Ⅵ. Applicable Areas

The following wastes and resources can be treated through gasification using steam

plasma torch

Target wastes

and resources

- Consumer wastes

- Organic sludge

- Resin waste

- Thermosetting/plasticized resin, plastics

- Industrial combustible wastes

- Shredder dust

- Synthetic rubber wastes

- Lumber wastes

- Low-grade coal

- wasted oil

- Others

- 27 -

목 차

1장 서론 ······························································································ 39

1-1절 연구개발의 중요성 및 필요성 ······················································ 40

1-2절 연구개발의 국내외 현황 ···································································· 431. 해외 기술개발 동향 • 시장 ························································································ 43

2. 국내 기술개발 동향 • 시장 ························································································ 44

1-3절 연구개발대상 기술의 차별성 ························································· 45

2장 연구개발 목표 및 내용 ··················································· 46

2-1절 연구의 최종목표 ······················································································· 471. 연구개발의 최종목표 및 성격 ·················································································· 47

가. 연구개발의 최종목표 ···························································································· 47

2-2절 연도별 연구개발 목표 및 평가방법 ········································ 491. 1차년도 ·························································································································· 49

2. 2차년도 ·························································································································· 50

2-3절 연도별추진 체계 ····················································································· 511. 연구개발 추진전략 ······································································································ 51

2. 연차별 추진체계 ·········································································································· 52

3장 연구개발 결과 및 활용계획 ········································· 53

3-1절 연구개발결과 및 토의 ········································································· 54

1. 열경화성 폐 Plastic의 물리화학적 특성 분석 ······················································ 54

가. 열경화성 수지의 물리적 성질 ············································································ 54

나. 열경화성 수지의 성질과 특징 ············································································ 56

다. 열경화성 수지 별 물리화학적 특성분석 ·························································· 62

2. 폐 Plastic의 발생 및 처리현황 분석 ······································································ 74

가. 폐플라스틱의 발생현황 ························································································ 74

나. 폐플라스틱 처리현황 ···························································································· 75

다. 폐플라스틱 처리기술 및 기술동향 ···································································· 76

3. 열역학적 가스화반응 이론 ························································································ 90

- 28 -

가. CO, CO2, H2O(g)와 CO, CO2,, H2, H2O(g) 혼합가스의 해리 O2압 ··········· 90

나. CO2의 해리 O2압 ··································································································· 91

다. H2O(g)의 해리압 ··································································································· 96

라. CO, CO2, H2, H2O(g) 수성 가스의 해리 O2압 ··············································· 98

마. CO, CO2, CH4, H2 ,H2O(g) 혼합가스의 해리 C압 또는 C활량 ·············· 101

4. 열경화성 수지의 Syn-gas 전환에 대한 열역학적 분석 결과 ························ 119

가. 멜라민수지의 열역학적 분석 결과 ·································································· 119

나. 페놀수지의 열역학적 분석 ················································································ 131

다. 요소수지의 열역학적 분석 ················································································ 142

라. FRP의 열역학적 분석 ························································································ 153

마. 결과 요약 ·············································································································· 164

5. Plasma 설비 설계를 위한 Heat/Mass balance 설정 ······································· 165

가. Steam plasma 설비 제작을 위한 Heat/Mass balance 설정결과 ············· 165

6. Steam plasma torch 설계/제작 ············································································· 183

가. Steam torch 기본 특성 ······················································································ 183

나. Power supply system 구성 및 특성 ······························································ 184

다. Steam plasma torch 설계도 ············································································· 184

라. Steam plasma torch/Power supply 제작 ······················································ 188

마. Steam plasma torch 운전 ················································································· 189

바. Steam torch 설계기술 비교 ·············································································· 190

7. Plasma 가스화 반응로 System 설계/제작/설치/시운전 ··································· 192

가. 반응로 설계 특성 ································································································ 192

나. Plasma 가스화 System 설계도 ········································································ 194

다. Plasma 가스화 System 제작 ············································································ 199

라. 제어 System 구성 ······························································································· 203

마. 반응로 설계기술 비교 ························································································ 204

바. 파쇄 설비 설계/제작 ··························································································· 206

8. 열경화성 수지 가스화 기초 실험 ·········································································· 208

가. 실험 장치 및 방법 ···························································································· 208

나. 실험 결과 및 고찰 ······························································································ 211

9. Steam plasma를 이용한 열경화성 수지의 가스화 실험 ·································· 224

가. 실험 방법 및 조건 ······························································································ 224

나. 폐 멜라민 수지(Melamine Resin)의 가스화 실험결과 ······························ 229

다. FRP의 가스화 실험결과 ·················································································· 252

라. 요소수지(Urea resin)의 가스화 실험결과 ···················································· 270

마. 페놀수지(Phenol resin)의 가스화 실험결과 ················································ 287

바. Steam plasma torch 효율 분석 ······································································· 302

- 29 -

사. Steam plasma torch 수명 분석 ······································································· 305

아. 배기가스 성분 분석 및 Dioxine 분석 ···························································· 306

자. 중금속 용출분석 ·································································································· 307

10. 가스화 System 설계인자 도출 및 실증개념설계 ············································ 307

가. 기본 개념 ·············································································································· 307

나. 가스화 반응으로 설계이론 ················································································ 307

다. 열교환기 설계이론 ······························································································ 308

라. 설계인자 도출 ···································································································· 309

마. Steam plasma 실증설비의 개념도 ·································································· 310

3-2절 연구개발 결과(요약) 및 결론(제언) ······································ 312

3-3절 연도별 연구개발목표의 달성도 ················································· 315

3-4절 연도별 연구성과 ····················································································· 3171. 1차년도(2009.3~2010.2) ··························································································· 317

가. 학술(세미나) 발표 ······························································································· 317

2. 2차년도(2010.3~2011.8) ····························································································· 317

가. 논문게재 ················································································································ 317

나. 학술(세미나) 발표 ······························································································· 318

다. 특허 ························································································································ 318

라. 기타(교육) 성과 ··································································································· 318

3-5절 관련분야의 기술발전 기여도 ······················································· 319

3-6절 연구개발 결과의 활용계획 ···························································· 3201. 연구성과 활용계획 ···································································································· 320

2. 기대효과 ······················································································································ 320

4장 참고문헌 ·················································································· 323

부 록 ·································································································· 327

- 30 -

표 목차

표 1.1 플라스틱류 재활용품 발생, 선별, 처리량2) ··························································· 41

표 1.2 열경화성 수지의 종류 및 특성3)4) ··········································································· 41

표 1.3 해외 열분해/가스화/용융 설비 현황 ······································································ 43

표 1.4 국내 열분해/가스화/용융 설비 현황 ······································································ 44

표 1.5 기존기술과의 차별성 분석 ······················································································· 45

표 3.1 불포화 폴리에스테르 수지의 종류5) ······································································· 64

표 3.2 FRP의 종류5) ··············································································································· 66

표 3.3 국내 폐플라스틱의 발생량6) ····················································································· 74

표 3.4 국내 폐플라스틱의 처리현황6) ················································································· 75

표 3.5 반응온도에서의 열분해공정8) ·················································································· 80

표 3.6 온도에 따른 유기성 물질들의 열분해 공정9) ······················································· 81

표 3.7 국내의 폐플라스틱 열분해 기술개발 현황9) ························································· 82

표 3.8 가스화 반응9) ··············································································································· 83

표 3.9 플라스틱에 따른 재활용 기술7) ··············································································· 85

표 3.10 폐플라스틱의 처리7) ································································································· 87

표 3.11 기체반응의 표준에너지 변화10) ·············································································· 91

표 3.12 1000K에서의 log ,와 PCO2/PCO의 관계10) ························································· 95

표 3.13 p H 2O / p H 2와 logp O 2의 관계10) ·············································································· 98

표 3.14 C(s) + CO2 ⇄ 2CO반응에서 가스 평행 상태와 압력의 관계10) ················· 106표 3.15 C(S) + 2H2 = CH4 반응에서 가스평행상태와 압력의 관계

10) ····················· 113

표 3.16 C(g) + 2H2 = CH4 반응에서 가스평행과 의 관계10) ····································· 115

표 3.17 열경화성 수지 분석조건 ······················································································· 119

표 3.18 멜라민 수지의 열역학적 거동 분석 결과 (가스화제 : Air) ························· 122

표 3.19 멜라민 수지의 열역학적 거동 분석 결과 (가스화제 : O2) ··························· 124

표 3.20 멜라민 수지의 열역학적 거동 분석 결과 (가스화제 : Steam) ···················· 126

표 3.22 페놀 수지의 열역학적 거동 분석 결과 (가스화제 : O2) ······························· 135

표 3.23 페놀수지의 열역학적 거동 분석 결과 (가스화제 : Steam) ·························· 137

표 3.24 요소 수지의 열역학적 거동 분석 결과 (가스화제 : Air) ····························· 144

표 3.25 요소 수지의 열역학적 거동 분석 결과 (가스화제 : O2) ······························· 146

표 3.26 요소 수지의 열역학적 거동 분석 결과 (가스화제 : Steam) ························ 148

표 3.27 FRP의 열역학적 거동 분석 결과 (가스화제 : Air) ······································· 155

표 3.28 FRP의 열역학적 거동 분석 결과 (가스화제 : O2) ········································· 157

표 3.29 FRP의 열역학적 거동 분석 결과 (가스화제 : Steam) ·································· 159

표 3.30 플라스틱 및 FRP 성분 ························································································· 165

- 31 -

표 3.31 FRP의 플라즈마 가스화를 위한 조건 ······························································· 167

표 3.32 FRP의 스팀 가스화시 가스 생성물 ··································································· 168

표 3.33 가스화 생성물의 조성 ··························································································· 168

표 3.34 물질수지와 열수지 ································································································· 169

표 3.35 가스화 생성물 ········································································································· 170

표 3.36 배가스 성분 ············································································································· 171

표 3.37 2차 연소실 열수지 ································································································· 172

표 3.38 배가스 성분 ············································································································· 173

표 3.39 2차 연소시 물질수지 ····························································································· 175

표 3.40 배가스 열수지 ········································································································· 176

표 3.41 배가스 성분조성 ····································································································· 177

표 3.42 배가스 물질수지 ····································································································· 179

표 3.43 배가스 계산 결과 ··································································································· 180

표 3.44 Steam plasma torch 기본사양 ············································································ 183

표 3.45 Power supply 특성 ································································································ 184

표 3.46 Plasma torch 설계 관련 주요 항목 ································································· 184

표 3.47 Plasma torch의 상세 설계도면 List ·································································· 185

표 3.48 Steam torch 비교 ································································································ 190

표 3.49 Plasma 가스화 반응로 주요사양 ········································································ 192

표 3.50 Plasma 가스화 System 상세설계도면 ······························································ 194

표 3.51 Plasma 가스화 반응로 비교 ················································································ 204

표 3.52 파쇄 설비 설계사양 ······························································································· 206

표 3.53 가스분석기 분석조건 ····························································································· 209

표 3.54 실험조건 ··················································································································· 210

표 3.55 열경화성수지의 원소분석 결과 ··········································································· 211

표 3.56 열경화성수지의 무기물분석 결과 ······································································· 211

표 3.57 FRP의 열분해 가스화 거동 실험결과 ······························································· 213

표 3.58 잔류물의 원소분석 결과 ······················································································· 213

표 3.59 FRP의 합성가스량 및 발열량분석 결과(m=0.0) ············································· 214

표 3.60 FRP의 합성가스량 및 발열량분석 결과(m=0.6) ············································· 216

표 3.61 FRP의 합성가스량 및 발열량분석 결과(m=1.0) ············································· 217

표 3.62 멜라민수지의 열분해 가스화 거동 실험결과 ··················································· 218

표 3.63 멜라민수지의 합성가스량 및 발열량분석 결과(m=0.0) ································· 219

표 3.63 멜라민수지의 합성가스량 및 발열량분석 결과(m=0.0) ································· 220

표 3.64 멜라민수지의 합성가스량 및 발열량분석 결과(m=0.6) ································· 221

표 3.65 멜라민수지의 합성가스량 및 발열량분석 결과(m=1.0) ································· 222

표 3.66 가스화 System 주요사양 ······················································································ 225

- 32 -

표 3.67 멜라민 수지 가스화 실험조건 ············································································· 229

표 3.68 Steam plasma torch 운전 조건 ·········································································· 230

표 3.69 멜라민 성분 분석결과 ··························································································· 230

표 3.70 멜라민 수지 Syn-gas 분석결과 ········································································· 242

표 3.71 멜라민 가스화 시 온도변화에 따른 Syn-gas 분석결과 ······························· 245

표 3.72 멜라민수지 연속운전시 Syn-gas 분석결과 ····················································· 251

표 3.73 FRP 가스화 실험조건 ··························································································· 252

표 3.74 Steam plasma torch 운전 조건 ·········································································· 253

표 3.75 FRP 성분 분석결과 ······························································································· 253

표 3.76 FRP Syn-gas 분석결과 ······················································································· 261

표 3.77 FRP Syn-gas 분석결과 ······················································································· 268

표 3.78 요소 수지 가스화 실험조건 ················································································· 271

표 3.79 Steam plasma torch 운전 조건 ·········································································· 271

표 3.80 요소수지 원소 분석결과 ······················································································· 272

표 3.81 요소수지 Syn-gas 분석결과 ··············································································· 277

표 3.82 요소수지 Syn-gas 분석결과 ··············································································· 282

표 3.83 요소수지 Syn-gas 분석결과 ··············································································· 286

표 3.84 페놀 수지 가스화 실험조건 ················································································· 287

표 3.85 Steam plasma torch 운전 조건 ·········································································· 288

표 3.86 페놀수지 분석결과 ································································································· 288

표 3.87 페놀수지 Syn-gas 분석결과 ··············································································· 294

표 3.88 페놀수지 Syn-gas 분석결과 ··············································································· 301

표 3.89 운전시간에 따른 전극 소모 측정결과 ······························································· 305

표 3.90 배기가스 분석결과 ································································································· 306

표 3.91 FRP 잔재물 중금속 용출분석결과 ····································································· 307

표 3.92 가스화 System 설계인자 ······················································································ 309

표 3.93 Steam plasma system 활용분야 ········································································ 312

- 33 -

그림 목차

그림 1.1 폐플라스틱 현황1) ··································································································· 40

그림 3.1 온도에 따른 플라스틱 강도5) ··············································································· 54

그림 3.2 비체적의 온도특성5) ······························································································· 55

그림 3.3 유동성의 대강 (목분 충전 페놀 수지)5) ···························································· 55

그림 3.4 플라스틱 재료의 열변형 온도5) ··········································································· 58

그림 3.5 플라스틱 재료의 내열온도5) ················································································· 59

그림 3.6 공업 재료의 열팽창률5) ························································································· 60

그림 3.7 플라스틱 재료의 열팽창률5) ················································································· 60

그림 3.8 공업재료의 열전도율5) ··························································································· 61

그림 3.9 플라스틱 재료의 열전도율5) ················································································· 61

그림 3.10 플라스틱 재료의 중량비열5) ··············································································· 62

그림 3.11 불포화 폴리에스텔 수지의 화학반응5) ····························································· 65

그림 3.12 노블락 페놀수지의 화학반응5) ··········································································· 67

그림 3.13 레졸 페놀수지의 화학반응5) ··············································································· 68

그림 3.14 멜라민 수지의 화학반응5) ··················································································· 70

그림 3.15 우레아 수지의 화학반응5) ··················································································· 72

그림 3.16 와 의 평행상태10) ································································································ 100

그림 3.17 P(Pco +Pco2)와 boundouard 평행곡선의 관계10) ········································ 104

그림 3.18 ac와 boundouard 평행곡선의 관계10) ····························································· 105

그림 3.19 C(s) + CO2 ⇄ 2CO반응에서 가스 상태와 압력의 관계10) ······················· 106그림 3.20 CO+CO2+A = 100%에서 CO, CO2, A의 관계

10) ········································· 108

그림 3.21 GT°와 T와의 관계10) ······················································································· 109

그림 3.22 C(s) + 2H2 = CH4 반응에서의 평행곡선10) ·················································· 112

그림 3.23 C(s)+2H2 = CH4 반응에서의 평행곡선10) ······················································ 113

그림 3.24 C(s)+2H2 = CH4 반응에서의 가스평행과 압력의 관계10) ·························· 114

그림 3.25 온도변화에 따른 H2, CH4 가스의 평행과 10) ··············································· 114

그림 3.26 열분해 온도에 따른 C의 가스화 반응10) ······················································· 118

그림 3.27 압력에 따른 C의 가스화 반응10) ····································································· 118

그림 3.28 O/C비에 따른 멜라민 수지의 열역학적 거동 분석 결과 (가스화제 : Air)121

그림 3.29 O/C비에 따른 멜라민 수지의 열역학적 거동 분석 결과 (�