서지주요정보
Development of the aqueous $CO_2$ curing and treatment for cement-based materials using $CO_2$ solvent = 이산화탄소 흡수제를 활용한 시멘트 기반 재료의 액상 탄산화 양생 및 처리 방법 개발
서명 / 저자 Development of the aqueous $CO_2$ curing and treatment for cement-based materials using $CO_2$ solvent = 이산화탄소 흡수제를 활용한 시멘트 기반 재료의 액상 탄산화 양생 및 처리 방법 개발 / Seong Ho Han.
발행사항 [대전 : 한국과학기술원, 2022].
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8039449

소장위치/청구기호

학술문화관(문화관)B1층 보존서고

DCE 22020

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As $CO_2$ has increased significantly in recent years, the Earth's greenhouse effect is occurring more than necessary. Research is underway to reduce and utilize carbon dioxide emitted worldwide and is also establishing a carbon-neutral policy. In particular, cement production is the part that emits the most $CO_2$ in the construction industry. The amount of $CO_2$ generated in cement production accounts for about 10% of the total amount of the emitted $CO_2$. Among them, the amount of the emitted $CO_2$ during the firing process in the kiln accounts for 80~90%. Research is underway on the development of construction materials using industrial by-products that do not require a firing process to reduce the amount of $CO_2$ from cement production. Meanwhile, $CO_2$ curing is being studied in terms of $CO_2$ capture to construction materials and the development of mechanical properties using the emitted $CO_2$. This curing method initially promotes carbonation as well as a hydration reaction, developing initial strength, and also has the effect of capturing carbon in terms of mineral carbonization. Conventional $CO_2$ curing technology performs curing by injecting $CO_2$ gas by putting a specimen into a chamber. However, there is a limitation because a closed space such as a chamber is required to be used directly on a construction site. In addition, there are limitations in terms of transportation and energy to utilize $CO_2$ gas directly. Therefore, in this study, aqueous $CO_2$ curing technology was developed. It is a technology that utilizes the existing $CO_2$ capture process as liquid form and utilizes $CO_2$-dissolved solution as curing water. In the $CO_2$ capture process using $CO_2$ solvent, the captured $CO_2$ was regeneration to separately collect pure $CO_2$ gas. In this case, a $CO_2$ solvent (alkanolamine or an alkaline solution) is used, and heat energy is required to decompose the collected $CO_2$. Therefore, there are bound to be limitations in terms of energy efficiency. However, in the aqueous $CO_2$ curing technology developed in this study, the $CO_2$ solvent is directly used as curing water, so the existing $CO_2$ regeneration process is not required. Therefore, this study attempts to evaluate the $CO_2$ capture effect and curing performance by the aqueous $CO_2$ curing in construction materials using cement-based materials or industrial by-products. Furthermore, as a method for improving the modification of the recycled aggregate, the $CO_2$-dissolved is used. And also, the mechanical properties and $CO_2$ efficiency were evaluated.

최근 이산화탄소량이 큰폭으로 증가함에 따라 지구의 온실 효과가 필요 이상으로 일어나고 있다. 전 세계적으로 배출된 이산화탄소의 저감과 활용을 위한 연구를 진행 중이며 또한 그에 관한 탄소 중립 정책을 수립 중이다. 특히, 건설업에 있어서 가장 많은 이산화탄소를 배출하는 부분은 시멘트 생산이다. 시멘트 생산에서 발생하는 이산화탄소 발생량은 전체 이산화탄소 발생량의 약 10%를 차지한다. 그 중 킬른 내 소성 과정에서의 이산화탄소 발생량이 80~90%를 차지한다. 시멘트 생산에서 발생하는 이산화탄소 양을 줄이기 위하여, 소성 과정이 필요없는 산업 부산물을 활용한 건설재료 개발에 관한 연구가 진행 중이다. 한편으로는 발생하는 이산화탄소를 활용하여 건설재료 내 포집 및 역학 성능 발현이라는 측면에서는 이산화탄소 양생이 연구 중이다. 이산화탄소 양생은 수화반응과 더불어 탄산화 반응을 초기에 촉진하여 초기 강도를 발현시키고 또한 광물탄산화 측면에서 탄소 포집의 효과도 있다. 기존 이산화탄소 양생 기술은 챔버 내에 시편을 넣어 이산화탄소 기체를 주입하여 양생을 진행한다. 하지만, 건설 현장에 직접적으로 사용되기에는 챔버와 같은 닫힌 공간이 필요로 하기에 한계점이 존재한다. 또한, 이산화탄소 기체를 활용하기에 운반이나 에너지 측면에서도 한계가 존재한다. 따라서 본 연구에서는 액상 탄산화 양생 기술을 개발하였다. 기존 이산화탄소 액상 포집 기술을 활용하여, 액상 상태로 포집된 이산화탄소를 양생 수로써 활용하는 기술이다. 기존 이산화탄소 액상 포집 기술에서는 포집된 이산화탄소를 다시 재 분해하여 순수 이산화탄소 기체를 따로 포집을 하였다. 이때, 이산화탄소 용매제(알칸올아민 또는 알칼리 수용액)를 활용하는데, 포집된 이산화탄소를 분해하기위해서는 열에너지가 필요로 하게된다. 따라서 에너지 효율 측면에서 한계가 존재하기 마련이다. 하지만, 본 연구에서 개발한 액상 탄산화 양생 기술은 이산화탄소가 용해된 이산화탄소 용매제를 직접 양생 수로 활용함으로써 기존의 이산화탄소 분해 과정이 필요 없게 된다. 따라서 본 연구에서는 액상 탄산화 양생 방법을 시멘트 기반 재료 및 산업부산물을 활용한 건설 재료에 수중양생의 방법으로 양생함으로써 이산화탄소 포집 효과 및 양생 성능 평가를 하려고 한다. 더 나아가, 순환골재의 개질 개선을 위한 방법으로 이산화탄소가 용해된 수용액을 활용하고자 한다.

서지기타정보

서지기타정보
청구기호 {DCE 22020
형태사항 v, 159 p. : 삽도 ; 30 cm
언어 영어
일반주기 저자명의 한글표기 : 한성호
지도교수의 영문표기 : Jae Hong Kim
지도교수의 한글표기 : 김재홍
수록잡지명 : "The use of alkaline CO2 solvent for the CO2 curing of blast-furnace slag mortar.". Construction and Building Materials, v. 342, Part A, (2022)
수록잡지명 : "CO2 curing efficiency for cement paste and mortars produced by a low water-to-cement ratio". Materials, v.13 no.17, (2020)
학위논문 학위논문(박사) - 한국과학기술원 : 건설및환경공학과,
서지주기 References: p. 137-54
주제 $CO_2$ curing
Carbonation pre-treatment
Aqueous carbonation
$CO_2$ solvent
CCUS
이산화탄소 양생
탄산화 처리
액상 탄산화
이산화탄소 흡수제
탄소 포집 및 저장 기술
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Schematic ofCO2 curing (Monkman and Shao,2006)

C02 uptakes according to bindertypes

Properties of alkanolamines

Schematic ofthe new CCUS process suggested in this research

Flow chart ofPh.D. dissertation

Chemical composition of ordinary Portland cement (wt.%)

Mix proportion of samples

condition and schedule forsamples Fabrication Initial Curing for 24h Time 3h 21h

Pressure vessel

Pressure loss and CO2 uptake ofMortar(W/C=0.35) and Mortar(W/C=0.5) (a) Decrease ofCOzpressure, (b) Carbonation rate, (c) CO2 uptake

of CO2 uptake

Strength of1-day samples fabricated by (a) compacting and(b) consolidating-in- mold method

Strength development ofMortar (W/C = 0.5)

CO2 uptake depending on sealed time

Carbonation depth ofMortar (W/C=0.5) curedin 20% concentration CO2 for28 days

Comparison ofthe size effect on the strength development ofmortar (W/C=0.5)

Chemical composition (oxides in wt.%) of GGBFS

XRD patterns ofraw GGBFS

proportions of samples

conditions of samples

Compressive strengths of the paste samples

Compressive strengths at 4h (a) and 24h (b)

Pressure loss in the pressure vessel during CO2 curing

Compressive strength developments ofpaste samples cured under different curing conditions with curing time

Calcite concentration of the samples

XRD patterns ofsamples with curing time (a) Control; (b) detailed XRD figure of the control sample in the 29-30이 20 range with reference patterns ofcalcite and calcium silicate hydrate (C-S-H);(c) CO2P-T1;(d)CO2P-T2, (e) CO2P-T3;(f) CO2-HC. 1: calcite (PDF 98-005-2151),2:C-S-H(PDF 00-033-0306),3:C- S-H(I) (PDF 00-029-0331), and 4: vaterite (PDF 98-018-1959)

TG and DTG curves of(a) control, (b) CO2P-T1,(c)CO2P-T2, and (d) CO2-HC samples with curing time

Chemical composition (oxides in wt.%) of GGBFS

XRD patterns ofraw blast furnace slag

proportions of samples

condition and sequence forsamples after demolding

Compressive strengths ofsamples (a) N100, (b)N90W10, (c)N50W50, and (d) K100 with different curing conditions (water bath curing, CO2curing, and CO2curing after 3 h ofdry pre-conditioning)

Mass change before and after each dry-preconditioning before CO2 curing for alkali-activated samples

Compressive strengths ofsamples (a)N100, (b)N90W10, (c)N50W50, and (d) K100 with different curing conditions (water bath curing, CO2 curing, and CO2 curing after3, 12, and 24h ofdry pre-conditioning)

XRD patterns ofN100 with different curing conditions. C: calcite (ICSD code 169919); CSH: C-S-H (ICDD file no. 33-0306); CASH: C-A-S-H (ICDD file no. 46-1405); CSH (I): C-S-H(I) (ICDD file no. 34-0002); C4AH13: C4AH13 (ICDD file no. 11-0203); HT: hydrotalcite (ICDD file no. 14-0191); G: gaylussite (ICDD file no. 21-0343); pirssonite (ICDD file no. 24-1065)

XRD patterns ofN90W10 with differentcuring conditions. C: calcite (ICSD code 169919); CSH: C-S-H (ICDD file no. 33-0306); CASH: C-A-S-H (ICDD file no. 46-1405); CSH(I): C-S-H(I) (ICDD file no. 34-0002); C4AH13: C4AH13 (ICDD fileno. 11-0203); HT: hydrotalcite (ICDD file no. 14-0191); CcH: C4AcHII (ICDD file no. 54-0848); HG: hydrogarnet (ICSD code 158019); >: akermanite in raw blast furnace slag

XRD patterns ofN50W50 with different curing conditions C: calcite (ICSD code 169919); CSH: C-S-H (ICDD file no. 33-0306)

XRD patterns ofK100 with different curing conditions. C: calcite (ICSD code 169919); CSH: C-S-H (ICDD file no. 33-0306); CASH: C-A-S-H (ICDD fileno. 46-1405); CSH(I): C-S-H(I) (ICDD file no. 34-0002); C4AH13: C4AH1 (ICDD fileno. 11-0203); HT: hydrotalcite (ICDD fileno. 14-0191);HC: hydrocalumite (ICDD file no. 14-0083)

Comparison of the relative quantities ofeach reaction productin Figure2.17

Comparison of the relative quantities ofeach reaction productin Figure2.18

Comparison of the relative quantities of each reaction productin Figure2.19

Comparison of the relative quantities of each reaction productin Figure 2.20

TG and DTG curves forsamples (a) N100, (b)N90W10, (c)N50W50, and(d) K100 with different curing conditions (water bath curing, CO2 curing, and CO2 curing after 3 12, and 24h ofdry pre-conditioning)

Chemical composition of materials (wt.%)

Particle size distribution ofbottom ash

(a) pH and (b) temperature variations ofthe aqueous MEA solutions

Reactions between the CO2-dissolved MEA solutions and the CaCl2 aqueous solution

Correlation between the molarity ofCO2 and thepHin the MEA solutions

Elements in pore solution (ppm)

XRD patterns of salts

Compressive strength development of(a) cement paste and (b) bottom ash mortar

XRD patterns ofcement paste as 28 days CSH: C-S-H (ICDD file no. 11-0211); CH: Ca(OH)2 (ICDD file no. 44-1481);Cc: calcite (ICDD file no. 05-0586)

TG and DTG curves ofcement paste samples at 28 days

Pore structure ofcement paste with different curing conditions: (a) pore size distribution and (b) classification

Chemical compositions of the GGBFS (wt.%)

XRD results for raw GGBFS

Alkali-activated slag mortar made with silica sand or ISO sand

Brick compressoi and compactible mold

Mix proportions and cast properties of mortar brick

CO2-dissolved curing water

Correlation between the green strength and air porosity ofthe mortar compacts

Compressive strength ofM5 (a) cured in 1 MKOH and 1 M NaOH solution at3 days,(b) 1 M, 3 M, and 5 MKOH solution at3 days,(c) submerged in 1 MKOH solution until 3 daysand successive moistur curing until 7 days(3d-1M-KOH), and submerged 1 MKOH solution until 7 days(7d-1M- KOH)

3-day compressive strength ofmortar with different activator's properties

3-day compressive strength ofmortar with different activator-to-binder ratios

Compressive strength developmentof(a)Ml and (b) M5 on CO2 curing with different amount ofdissolved CO2

XRD patterns ofthe samples corresponding to (a)Ml and (b)M5 at3 days ■ C-S-H (ICDD file no. 33-0306); ■ Quartz (ICDD file no. 78-1252); ◆ Calcite (ICDD file no. 81-2027); ◇ Monohydrocalcite (ICDD file no. 22-0147); 0 Potassium sulfate (ICDD file no. 83-0681); ㅇ Akermanite (ICDD file no. 79-2424)

TG and DTG curves ofthesamples corresponding to (a) M1 and (b)M5 at3 days

CO2 uptake

Chemical compositions of the OPC and HCP (wt.%)

XRD patterns ofOPC and HCP

Size distribution ofHCP

of solutions for CO2 treatment

Rotary chamber for carbonation treatment

The variation of pH and the decreased amountof CO2 molecules

CO2 uptakes

XRD patterns ofpre-treated HCP fine aggregate; Portlandite (ICDD file no. 44-1481); ㅁ C-S-H (ICDD file no. 33-0306); / Calcite (ICDD file no. 72-1937); V Vaterite (ICDD file no.24-0030); Hydrotalcite (ICDD file no. 89-0460)

SE ofthe surface ofpre-treated HCP fine aggregate (a)DI. boDICO2 (c)MEA 1% (d) MEA 10% (e) MEA 30%

SE ofthe cross-sectioned HCP; (a) pre-treatment ofDI, and (b) MEA 10%

Compressive strength ofmortar samples