• Title/Summary/Keyword: reactivity ratio

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Shape-Selective Catalysis over Zeolite. An Attempt in the Alkylation of Biphenyl

  • Sugi, Yoshihiro;Komura, Kenichi;Kim, Jong Ho
    • Applied Chemistry for Engineering
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    • v.17 no.3
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    • pp.235-242
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    • 2006
  • Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.

Isothermal Conduction Calorimetry Analysis of Alkali Activated Slag Binder (알칼리 활성 슬래그 결합재의 미소수화열 분석)

  • Choi, Young-Cheol;Cho, Hyun-Woo;Oh, Sung-Woo;Moon, Gyu-Don
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.3 no.3
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    • pp.237-243
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    • 2015
  • In this research, isothermal conduction calorimetry analysis has been conducted to investigate the reactivity of alkali activated slag binders. In order to secure the reactivity and workability of alkali activated slag binders, experiences with various types and concentrations of alkali activators were performed. Isothermal conduction calorimetry were measured with different alkali activators and mass ratio of $SO_3$ to binders as variables, and sodium tripolyphosphate ($Na_2P_3O_{10}$) and hydrated sodium borate ($Na_2B_4O_710H_2O$) were used to control setting time. As a results, alkali activated slag binders required alkali activators with 4 to 5 percent of concentration to accelerate the formation of calcium silicate hydrate(C-S-H) by alkali-activation, and overall heat generation rate delayed as accumulated heat decreased due to the high $SO_3$ contents. Moreover, the use of hydrated sodium borate as setting retarder causes elongated setting time due to delaying heat generation, so it can be considered that setting retarder played an important role in delaying total heat generation rate.

A Study on the Pozzolan Reactivity and Mechanical Characteristic of Blended Portland Cements using CFBC Fly Ash (순환유동층 플라이 애시를 사용한 혼합시멘트의 포졸란 반응성과 역학적 성질에 관한 연구)

  • Park, JongTak;Oh, Hongseob
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.6 no.3
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    • pp.207-213
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    • 2018
  • Nowadays, circulating fluidized bed combustor(CFBC) boilers system that can reduce environmental pollution particles are widely used in electric power plants. But the fly ash generated from CFBC boilers has lower $SiO_2$ and higher MgO and $SO_3$ contents and also has free CaO inducing expansion and abrupt initial setting of concrete. Therefore, revised KSL5405 for CFBC fly-ash as well as pulverized coal combustion(PCC) is introduced in the concrete field. In this study, the chemical properties and mechanical properties of blended cements with PCC and CFBC fly-ash produced in Korea are analyzed. The blended cement with only CFBC fly ash shows a lower length change than OPC but a higher flow change ratio. The compressive strength of blended cement paste with PCC and CFBC fly ash is slightly greater than that of cement paste with only PCC fly-ash. Based on the results, CFBC flyash blended cement products should be used with PCC flyash to ensure the material stability and material properties.

A Comparative Study on Polyurethane Coating Films Prepared Using 4,4'-Methylenebis(2-chloroaniline) and 1,3-Propanediolbis(4-aminobenzoate) as Crosslinking Agents (4,4'-Methylenebis(2-chloroaniline)과 1,3-Propanediolbis(4-aminobenzoate)를 가교제로 사용하여 제조한 폴리우레탄 코팅 필름의 특성 비교)

  • Lee, Youn-Sik;Lee, Sung-Il;Kim, Duk-Bae;Park, Young-Deok;Kim, Jung-Kee;Hahn, Yoon-Bong;Nahm, Kee-Suk
    • Elastomers and Composites
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    • v.39 no.1
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    • pp.71-76
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    • 2004
  • 4,4'-Methylenebis(2-chloroaniline)(MOCA) has been widely used as a crosslinking agent, but classified as a toxic chemical. Thus, its use will be limited in the near future. In this research, polyurethane coating films were prepared using 1,3-propanediolbis(4-aminobenzoate)(PDBA) as an alternative to MOCA. The base part was prepared by melting MOCA or PDBA in polyoxypropylene($M_n$=2000), followed by the addition of the various additives. The NCO-terminated toluene diisocyanate prepolymer was used as a curing agent. The polyurethane coating films were prepared by mixing the base part with the curing agent in an appropriate ratio at room temperature. The polyurethane coatings prepared using PDBA exhibited higher initial viscosity, but much longer pot lift, compared to those prepared using MOCA under the same conditions, due to lower reactivity of PDBA. The tensile strength and tear strength of the coating films were much weaker. However, the pot life, tensile strength, elongation, and tear strength of the coating films, prepared using PDBA in the presence of an increased amount of Pb(II)-octoate, were close to those of the coating films prepared using MOCA. Thus, it was concluded that PDBA can substitute MOCA in the preparation of polyurethane coatings as long as the reactivity of PDBA is enhanced using appropriate amounts of the catalyst or other appropriate catalyst.

Combustion Characteristics for Co-firing of Biomass (Walnut Shell) (바이오매스(호두껍질) 혼소에 대한 연소 특성에 관한 연구)

  • Kim, Jin-Ho;Lee, Byoung-Hwa;Sh, Lkhagvadorj;Kim, Sang-In;Jeon, Chung-Hwan
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.39 no.1
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    • pp.53-59
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    • 2015
  • Combustion characteristics for co-firing of biomass (Walnut Shell) as blending fuel in coal fired boiler have investigated using thermogravimetric analyser (TGA) and drop tube reactor (DTR). The results show that devolatilization and char combustion for WS occurs at lower temperature than those of existing coals and has lower activation energy value, which is resulting in higher reactivity. When the WS is blended with coal, TGA results show linear profiles depending on blending ratio for each fuel. However, DTR results exist the non-additive phenomena for blending of WS. As blending ratio of WS increase, the UBC decrease at BBR 5%, but the UBC rather increase from BBR 10% due to oxygen deficiency formed from rapid combustion of WS. This paper propose that fuel lean condition by oxygen rich lead to higher blending ratio of biomass by solving the oxygen deficiency condition.

Stabilization/Solidification of Radioactive LiCl-KCl Waste Salt by Using SiO2-Al2O3-P2O5 (SAP) Inorganic Composite: Part 2. The Effect of SAP Composition on Stabilization/Solidification (SiO2-Al2O3-P2O5 (SAP) 무기복합체를 이용한 LiCl-KCl 방사성 폐기물의 안정화/고형화: Part 2. SAP조성에 따른 안정화/고형화특성 변화)

  • Ahn, Soo-Na;Park, Hwan-Seo;Cho, In-Hak;Kim, In-Tae;Cho, Yong-Zun
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.10 no.1
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    • pp.27-36
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    • 2012
  • Metal chloride waste is generated as a main waste streams in a series of electrolytic processes of a pyrochemical process. Different from carbonate or nitrate salt, metal chloride is not decomposed into oxide and chlorine but it is just vaporized. Also, it has low compatibility with conventional silicate glasses. Our research group adapted the dechlorination approach for the immobilization of waste salt. In this study, the composition of SAP ($SiO_2-Al_2O_3-P_2O_5$) was adjusted to enhance the reactivity and to simplify the solidification process as a subsequent research. The addition of $Fe_2O_3$ into the basic SAP decreased the SAP/Salt ratio in weight from 3 for SAP 1071 to 2.25 for M-SAP( Fe=0.1). The experimental results indicated that the addition of $Fe_2O_3$ increased the reactivity of M-SAP with LiCl-KCl but the reactivity gradually decreased above Fe=0.1. Also, introducing $B_2O_3$ into M-SAP requires no glass binder for the consolidation of reaction products. U-SAP ($SiO_2-Al_2O_3-Fe_2O_3-P_2O_5-B_2O_3$) could effectively dechlorinate the LiCl-KCl waste and its reaction product could be consolidated as a monolithic form without a glass binder. The leaching test result indicated that U-SAP 1071 was more durable than other SAPs wasteform. By using U-SAP, 1 g of waste salt could generated 3~4 g of wasteform for final disposal. The final volume would be about 3~4 times lower than the glass-bonded sodalite. From these results, it could be concluded that the dechlorination approach using U-SAP would be one of prospective methods to manage the volatile waste salt.

Investigation on Diesel Injection Characteristics of Natural Gas-Diesel Dual Fuel Engine for Stable Combustion and Efficiency Improvement Under 50% Load Condition (천연가스-디젤 혼소 엔진의 50% 부하 조건에서 제동효율 및 연소안정성 개선을 위한 디젤 분무 특성 평가)

  • Oh, Sechul;Oh, Junho;Jang, Hyungjun;Lee, Jeongwoo;Lee, Seokhwan;Lee, Sunyoup;Kim, Changgi
    • Journal of the Korean Institute of Gas
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    • v.26 no.3
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    • pp.45-53
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    • 2022
  • In order to improve the emission of diesel engines, natural gas-diesel dual fuel combustion compression ignition engines are in the spotlight. In particular, a reactivity controlled compression ignition (RCCI) combustion strategy is investigated comprehensively due to its possibility to improve both efficiency and emissions. With advanced diesel direct injection timing earlier than TDC, it achieves spontaneous reaction with overall lean mixture from a homogeneous mixture in the entire cylinder area, reducing nitrogen oxides (NOx) and particulate matter (PM) and improving braking heat efficiency at the same time. However, there is a disadvantage in that the amount of incomplete combustion increases in a low load region with a relatively small amount of fuel-air. To solve this, sensitive control according to the diesel injection timing and fuel ratio is required. In this study, experiments were conducted to improve efficiency and exhaust emissions of the natural gas-diesel dual fuel engine at low load, and evaluate combustion stability according to the diesel injection timing at the operation point for power generation. A 6 L-class commercial diesel engine was used for the experiment which was conducted under a 50% load range (~50 kW) at 1,800 rpm. Two injectors with different spray patterns were applied to the experiment, and the fraction of natural gas and diesel injection timing were selected as main parameters. Based on the experimental results, it was confirmed that the brake thermal efficiency increased by up to 1.3%p in the modified injector with the narrow-angle injection added. In addition, the spray pattern of the modified injector was suitable for premixed combustion, increasing operable range in consideration of combustion instability, torque reduction, and emissions level under Tier-V level (0.4 g/kWh for NOx).

Glycerol Carbonate Synthesis by Glycerol Oxidative Carbonylation over Copper Catalysts (구리 촉매상에서 글리세롤의 산화 카르보닐화 반응에 의한 글리세롤 카보네이트 합성)

  • Choi, Jae Hyung;Lee, Sang Deuk;Woo, Hee Chul
    • Clean Technology
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    • v.19 no.4
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    • pp.416-422
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    • 2013
  • In environmental friendly aspects, the synthesis of glycerol carbonate from glycerol using carbon monoxide and oxygen gases which were produced in petrochemical plants was studied. The oxidative carbonylation of glycerol under batch reaction system was performed on parameter conditions such as effect of various metals (Cu, Pd, Fe, Sn, Zn, Cr), oxidizing agents, mole ratio of carbon monoxide to oxygen, catalyst amount, solvent types, reaction temperature and time and dehydrating agents. In particular copper chloride catalysts showed the excellent activities, and the glycerol carbonate yields over CuCl and $CuCl_2$ catalysts were the maximum of 44% and 64%, respectively at the following reaction conditions: solvent as nitrobenzene, mole ratio of 1:3:0.15 (glycerol:carbon monoxide:catalyst), mole ratio of 2:1 (carbon monoxide:oxygen), the total pressure of 30 bar at 413 K for 4 hr. It was found that reactivity were significantly different depending on the oxidation number of Cu catalysts, and oxygen plays an important role as oxidizing agents in producing H2O during oxidation reaction after carbonylation of glycerol.

Association Between Communication for Chemical Hazards Information and Characteristics of Occupational Safety and Health manager (산업안전보건관리자 특성과 화학물질 유해성 정보전달의 관련성)

  • Kim, Ki-Woong;Park, Jin Woo;Jeong, Mu Soo
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.22 no.2
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    • pp.156-163
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    • 2012
  • Objectives: The aim of the present study was undertaken to investigate the association between communication for chemical hazard information and characteristics of occupational safety and health managers. Subjects and Methods: We surveyed 78 occupational safety and health managers(64 male and 14 female) in 78 chemical manufacturing plants. Data were obtained using a self-reported questionnaire about size and type of company, products, communication system for chemicals and work-related characteristics of occupational safety and health managers. All analyses in this study were performed using SPSS program 12.0. Results: 64.1% of the study participants were occupational health managers aged 39.3 years on average and were graduated from college and university around 90%. 30.0% and of them were majoring in chemistry (engineering chemistry), 18.0% occupational health, 16% nursing and 30.0% others. Occupational safety managers were aged 39.4 years on average, 42.9% of them were majoring in chemistry (engineering chemistry), 21.4% environmental engineering, 10.7% occupational safety and 25% others. 86% of occupational health managers and 71.4% of occupational safety managers were classified as office job. Over 94% of the hazards information for chemicals were delivered by occupational safety and health managers, but about 28.2% workers preferred outside experts who have a profound knowledge about occupational safety and health and understandable. Occupational safety and health managers and workers had difficulties in understanding toxicological information, hazards identification, stability/reactivity, composition/information on ingredients, physical/chemical properties and ecological information. On multiple logistic regression analysis for the 16 heading of material safety data sheet, content of material safety data sheet was significantly associated with education level (odds ratio=0.286, 95% confidence interval=0.105-0.780). The hazard identification (odds ratio=3.947, 95% confidence interval=1.092-14.271) and toxicological information (odds ratio=0.841, 95% confidence interval=0.705-0.998) were significantly associated with type of occupation. Conclusions: This finding implies that the education level, type of occupation and speciality of occupational safety and health managers may affects hazards information delivery.

Anaerobic digestion for food wastewater using HADS Pilot Plant and analysis of microbial community in the digester (HADS Pilot Plant를 이용한 음폐수의 혐기성 소화 및 미생물 군집 변화 분석)

  • Ju, Dong-Hun;Lee, Jung-Min;Park, Seong-Bum;Sung, Hyun-Je;Bae, Jae-Sang;Sang, Byoung-In
    • Journal of the Korea Organic Resources Recycling Association
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    • v.18 no.2
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    • pp.76-83
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    • 2010
  • We(Hansol EME Co. Ltd.) proceeded anaerobic digestion test for domestic food wastewater applying to two operating method for increasing of OLR. The methods are as follows. One was the rapidity operating method which was increasing the OLR continuously and rapidly and the other was the terraced operating method which was increasing the OLR having adaptation period for each step. As a result of this tests, the ratio of VFA/Alkalinity of the process was very unstable under the rapidity operating method then the volume of produced biogas was dramatically decreased. However the process was shown stable performance under the terraced operating method maintaining the ratio of VFA/Alkalinity less than 0.4. Also, the process was performing the biogas recovery of $0.8Nm^3/kgVS_{rem}/d$ and the VS removal ratio of 85%. T-RFLP analysis about the community of bacteria and methanogen is also conducted to check the change of the microbial community according to the methods of OLR increasing operation. The microbial community was changed by the methods of OLR increasing operation according to the result of T-RFLP analysis. Although the anaerobic digestion test was executed by same pilot plant, the reactivity and the tolerance of microbial community for surrounding environment could be considerably changed by the operating method for the process.