Radioactive liquid waste generated during the operation of domestic nuclear power plants is treated through a somewhat different liquid radwaste system (LRS) for each plant. Prior to the introduction of standard nuclear power plants, LRS used a concentrated water dry system (CWDS) to evaporate liquid waste and manage it in the form of dry powder. The boron-containing radioactive liquid waste dry powder was solidified using paraffin from 1995 to 2010, and about 3,650 drums (based on 200 L) of paraffin solidified drums are currently stored in nuclear power plants. Paraffin solidification drums do not meet the acceptance criteria for radioactive waste repositories because it is difficult to secure the homogeneity of the solidified body and there are concerns about leaching of radioactive waste due to the low melting point of paraffin. In order to solve this problem and safely permanently dispose of paraffin solidification drums, the characteristics of dry powder paraffin solidification drums containing boron-containing radioactive liquid waste must be analyzed and appropriate treatment technology utilizing the results must be introduced. This study analyzes the physical properties of paraffin, the chemical properties of boron-containing radioactive waste dry powder, and the physicochemical properties of paraffin solidification powder, and proposes an appropriate alternative technology for treating boron-containing radioactive waste dry drum. When disposing of the paraffin solidification drum with boron-containing radioactive liquid waste dry powder, the solidification body must be effectively withdrawn from the drum and the paraffin must be completely separated from the solidification body. When disposing the drum, the solidified material must be effectively extracted from the drum and the paraffin must be completely separated from the solidified material. Afterwards, the paraffin must be self-disposed, and the radioactive waste must be disposed of in accordance with acceptance criteria of repository. We looked at how each characteristic of the paraffin solidification drum with boron-containing radioactive liquid waste dry powder can be utilized in each of the above treatment processes.

Nuclear power plants in Korea stores approximately 3,800 drums of paraffin solidification products. Due to the lack of homogeneity, these solidification products are not allowed to be disposed of. There is therefore a need for the separation of paraffin from the solidification products. This work developed an equipment for a selective separation of paraffin from the solidification product using the vacuum evaporation and condensational recovery method in a closed system. The equipment mainly consists of a vacuum evaporator and a condensational deposition recovery chamber. Nonisothermal vacuum TGAs, kinetic analyses and kinetic predictions were conducted to set appropriate operation conditions. Its basic operability under the established conditions was first confirmed using pure paraffin solid. Simulated paraffin solidification product fixing dried boric acid waste including nonradioactive Co and Cs were then fabricated and tested for the capability of selective separation of paraffin from the simulated waste. Paraffin was selectively separated without entertainment of Co and Cs. It was confirmed that the developed equipment could separate and recover paraffin in the form of nonradioactive waste.

Domestic NPPs had produced the paraffin-solidifying concentrate waste (PSCW) for nearly 20 years. At that time radioactive waste management policy of KHNP was to reduce the volume and to store safely in site. The PSCW has been identified not to meet the leaching index after introducing the treatment system. PSCW has to be treated to meet current waste acceptance criteria (WAC) for permanent disposal. PSCW consists of dried concentrate 75% and paraffin 25% of volume. When PSCW is separated into a dried concentrate and a paraffin by solubility, total volume separated is increased twice. Final disposal volume of dried concentrate can reach to several times when solidifying by cement even considering exemption. Application of polymer solidification technology is difficult because dried concentrate is hard to make form to pellet. When PSCW is packaged in High Integrity Container (HIC), volume of PSCW is equal to the volume before package. The packaging process of HIC is simple and is no necessary of large equipment. It is important to recognize that HIC was developed to replace solidification of waste. HIC has as design goal a minimum lifetime of 300 years under disposal environment. The HIC is designed to maintain its structural integrity over this period, to consider the corrosive and chemical effects of both the waste contents and the disposal environment, to have sufficient mechanical strength to withstand loads on the container and to be capable of meeting the requirements for a Type A transport Package. The Final waste form is required for facilitating handling and providing protection of personnel in relation to solidification, explosive decomposition, toxic gases, hazardous material, etc. Structural stability of final waste form is required also. Structural stability of the waste can be provided by the waste itself, solidifying or placing in HIC. Final waste form ensure that the waste does not structurally degrade and affect overall stability of the disposal site. The HIC package contained PSCW was reviewed from several points of view such as physicochemical, radiological and structural safety according to domestic WAC. The result of reviewing shows that it has not found any violation of WCP established for silo type disposal facility in Gyeongju city.

Boric acid-containing B-10 is used in a nuclear reactor as a coolant and absorbs thermal neutrons generated during nuclear fission in the primary circuit. Boron-containing coolant water waste is generated from maintenance, floor drain, decontamination, and reactor letdown flows. There are two options for aqueous solution waste of boric acid. One is recycling and discharge through filtration, ion exchange, and reverse osmosis. The other is immobilization after evaporation and crystallization processes. The dry powder of boric acid waste liquid can be immobilized by cement, polymer, etc. Before the mid-1990s, concentrated boric acid waste was solidified with a cement matrix. To overcome the disadvantage of low waste loading of cement waste form, a method of solidifying with paraffin was adopted. However, paraffin solids were insufficient to be disposed of as final waste. Paraffin is a kind of soft solidified material and has low compressive strength and poor leaching resistance. As a result, it was decided as an unsuitable form for disposal. In KOREA, paraffin waste form was adopted for boric acid waste treatment in the 1990s. A large amount of paraffin waste forms about 20,000 drums (200 l drum) were generated to treat boric acid waste and were stored in nuclear power sites without disposal. In this study, we want to obtain high-purity boric acid waste by oxidizing and decomposing solid paraffin waste form through a boric acid catalytic reaction. In this reaction, paraffin is separated in the form of various by-products, which can then be treated through a liquid waste treatment device or an exhaust gas treatment device. The proper temperature for sample decomposition during the catalytic reaction was set through TGA analysis. Compositions of by-products and residues generated at each stage of the reaction could be analyzed to determine the state during the reaction. Finally, the boric acid waste powder was perfectly separated from paraffin waste form with disposable products through this pyrolysis process.

Volatile organic compounds (VOCs) emitted from industrial gas cause equipment failure and fire accidents due to the rapid flow and concentration changes of VOCs. Therefore, it is crucial to attenuate the concentration of VOCs to ensure a constant emission rate before the control process. This study proposed an encapsulation technique to fabricate calcium- alginate gel beads containing paraffin oil as an effective absorbent. The prepared absorbent was physically characterized, and a column test observed its absorption capacity. When the oil content was 30%, the prepared beads showed the best spherical shape, attaining 96% emulsion stability, 0.014 sphericity factor, 62.7% weight variation ratio, and 4.21 ± 0.06mm diameter. In the column test that was packed with the prepared beads, the toluene absorption capacity was 497.6mg/kg. The net effect of the beads was to attenuate the peaks of toluene concentration, and to make the VOC-laden air stream more receptive for the subsequent treatment unit.

In domestic nuclear power plants, drums of concentrated radioactive waste solidified with paraffin that do not meet radioactive waste disposal standards are stored temporarily. In this paper, the design of a machine that separates these paraffin drums into paraffin and concentrated waste using heating vaporization and pressure difference is described. The separation process is as follows. First, the paraffin solid is indirectly heated by heating the outside of the drum. The paraffin solid is partially melted to increase the fluidity and is easily detached from the drum. The detached solid is transferred to the melting tank, and further heated in the melting tank. When the temperature is sufficiently high, paraffin is melted and becomes a mixture of liquid paraffin and concentrated waste homogeneously. The mixed solution is transferred to a paraffin recovery vessel and further heated. The vaporization point of paraffin is 370°C under atmospheric pressure, and becomes lower depending on the pressure decreasing in the vessel. The vaporization point of the paraffin is a relatively low value compared to the radioactive elements in the concentrated waste, and therefore only paraffin would be vaporized. A paraffin transfer pipe is installed on the upper part of the paraffin recovery vessel, and is connected to another tank called the paraffin capture vessel. The pressure of the paraffin capture vessel is reduced (i.e. vacuum condition), only gaseous paraffin is transferred to the paraffin capture vessel by the pressure difference. When the paraffin capture vessel is cooled below the vaporization point of the paraffin, the paraffin is liquefied or solidified, and only the paraffin is recovered. Based on the above process, the solidified paraffin could be separated into pure paraffin and concentrated waste. However, if a radioactive element with a lower vaporization point than paraffin exists in the concentrated waste, it may be mixed with paraffin and separated together. Therefore, it is necessary to measure the radioactivity or radiation dose rate for the separated paraffin, and to verify that it is sufficiently low. If necessary, additional separation process may be considered for removing radioisotopes from the paraffin.

Plasticization is one of the biggest challenges in gas separation polymeric membranes. Mixed matrix membrane (MMM) comprising inorganic nanofiller is the most promising solution for anti-plasticization, however, it requires large amount of nanofillers to achieve desired performance. We adopted 2-D nanocomposite of zeolitic imidazolate framework (ZIF) attached on graphene oxide to effectively prevent plasticization of polyimide membrane under mixed gas condition. ZIF nanofillers, known as suitable additive for olefin/paraffin separation membranes, were grown on graphene oxide 2-D nanotemplates to maximize encounter frequency between gas permeant and nanofillers even in lower concentrations. The prepared MMMs successfully showed an improved mixed gas selectivity compapred to pristine membrane, indicating better anti-plasticization effect.

이전 연구에서 올레핀/파라핀 분리를 위해 poly(ethylene oxide)(PEO)/Ag nanoparicles (AgNPs)(전구체AgBF4)/pbenzoquinone (p-BQ) 복합막이 제조되었으며, 이 복합체 분리막의 성능은 100시간까지 선택도 10과 투과도 15 GPU로 유지 되는 것이 확인되었다. 하지만 전구체인 AgBF4의 가격이 고가이기 때문에, 본 연구에서는 가격 측면에서 경쟁력이 있는 AgNO3를 Ag nanoparticles의 전구체로 사용하여 실험을 진행하였다. 그 결과 이미 존재하고 있는 NO3 -가 AgNPs를 감싸고 있기 때문에 분리 성능이 나오지 않는 것으로 관찰되었다. 이번 연구에서는 AgNO3를 Ag nanoparticles의 전구체로 사용하여도 높은 성능을 내기 위해 전자수용체 7,7,8,8-tetracyanoquinodimethane (TCNQ)를 사용하여 PEO, polyvinyl alcohol (PVA), polyether block amide-1657 (PEBAX-1657) 고분자 복합막을 제조한 결과, 고분자와 전자수용체의 영향과는 무관하게 분리 성능을 내지 못하는 것으로 분석되었으며, 이는 분리성능에 전구체의 음이온이 결정적 역할을 하는 것으로 분석되었다.

올레핀/파라핀 분리를 위해 poly(ethylene oxide)(PEO)/Ag nanoparticles (AgNPs)(전구체: AgBF4)/p-benzoquinone (p-BQ) 복합막이 제조되었으며, 이 복합체 분리막의 성능은 100시간까지 선택도 10과 투과도 15 GPU로 유지되는 것이 관찰 되었다. 분리막의 성능이 100시간까지 유지할 수 있었던 이유는 p-BQ의 첨가로 인해 Ag ion이 안정적으로 Ag nanoparticles 로 형성될 수 있었을 뿐더러 전자수용체인 p-BQ으로 인해 표면이 부분 양극성화 되어 올레핀 운반체로서 역할을 성공적으로 수행한 결과라 생각되었다. 본 연구에서는 Ag nanoparticles의 전구체로 사용된 AgBF4의 가격이 고가이기 때문에 가격 측면에서 유리한 AgNO3 Ag nanoparticles의 전구체로 사용하여 실험을 진행하였다. 그 결과로서 AgNO3의 경우에는 앞선 AgBF4 과는 다르게 안정적으로 은 나노입자가 형성되지 못하고 이로 인하여 좋은 성능을 내지 못하는 것으로 분석되었다.

본 연구에서는 올레핀/파라핀 분리용 NaY 제올라이트 분리막을 제조하기 위해서 알루미나 지지체 표면에 종결정을 진공여과법으로 코팅한 후 NaY 수열용 액을 이용하여 90°C-110°C에서 16-24시간 동안 이차성장 시켰다. 이때 올레핀 과 π-결합을 형성하는 Ag+ 이온을 NaY 결정 구조내에 포함된 Na+ 이온과 이 온교환시킴으로써 올레핀/파라핀 선택도와 안정성을 향상시키고자 하였다. 이온 교환된 NaY 제올라이트 분리막의 올레핀/파라핀 분리성능은 C3H6/C3H8= 90/10의 혼합기체를 이용하여 분석한 결과, 700 GPU의 투과도와 1.13의 선택도를 나타내었다. 낮은 선택도는 제조된 분리막에 비제올라이트 기공이 존재하기 때문으로 판단되었으며 향후 비제올라이트기공을 억제하기 위한 연구를 진행할 계획이다.

올레핀/파라핀 분리는 산업에서 가장 중요하고 도전적인 분리 이슈 중의 하 나이다. 흡착 및 막은 에너지 절약적 분리 기술이기에 올레핀/파라핀 분리를 위한 흡착 및 막 기술의 개발이 많은 관심을 받고 있다. 본 연구에서는 유무기 하이브리드 세공체(metal-organic framework, MOF)의 기공 내부에 올레핀 분자와 π complexation이라는 특별한 인력을 지니는 Cu 1가 이온을 효율적이며 안정적으로 함침하는 방법을 제시하였다. 또한, Cu 1가 이온이 함침된 MOF를 고분자 막과 결합하여 올레핀 선택 분리용 혼합기질막(mixed matric membranes)을 성공적으로 개발하였다.

파라핀 왁스가 녹아있는 왁스오일은 주위 온도가 내려감에 따라 왁스의 침전이 시작된다. 침 전이 시작하는 온도를 왁스생성온도라 부르며, 왁스생성온도는 유동점 측정과 함께 왁스오일의 거동연구 에 중요한 정보를 제공해 준다. 본 연구에서는 왁스가 함유된 모델오일을 제조하여, 왁스의 정량과 정성 적인 차이에 따른 왁스생성온도와 유동점의 변화를 살펴보았다. 물이 포함되지 않은 왁스함유 모델오일 의 경우, 그 투명성으로 인해 ASTM D2500을 통해 왁스생성온도 측정이 가능하다. 또한, 유동점 측정 도 같은 장치를 사용하는 ASTM D97을 사용하여 측정할 수 있다. 물이 함유된 에멀젼 모델오일의 경 우에는 시료의 불투명성으로 인해 우선 유동점을 중심으로 거동을 살펴보았다. 이후 에멀젼 모델오일의 왁스생성온도 측정은 적외선분광법을 활용하여 측정하였으며, 에멀젼을 형성하는 물의 함량에 따른 왁스 생성온도의 경향성은 고찰을 통해 추가적인 실험이 필요할 것으로 판단되었다.

올레핀/파라핀 분리를 위해 Poly(ethylene oxide)(PEO)/AgBF4/Al(NO3)3/Ag2O 복합막이 제조되었으며, Ag2O가 도 입되었을 때, 복합체 분리막의 초기성능은 선택도 13.7과 투과도 21.7 GPU로 관찰되었다. PEO/AgBF4/Al(NO3)3 분리막의 성 능(선택도 13와 투과도 7.5 GPU)에 비해서 초기성능이 증가한 이유는 Ag2O의 첨가로 인한 Ag ion의 활성도 증가로 생각되 었다. 하지만 시간에 따른 성능저하 현상이 관찰되었는데 이는 고분자 matrix인 PEO 때문인 것으로 생각되었다. PEO 고분자 는 Ag2O 입자를 안정화 시킬 수 없기 때문에 용매가 증발하면서 Ag2O 입자끼리 뭉치게 되고, Ag2O가 barrier 역할을 하게 돼서 시간이 지나면 투과도가 감소하는 것으로 분석되었다.

About 130 million tons of ethylene and 55million tons of propylene have been produced every year in the world and thus, olefin production process is very important in the chemical process. Cryogenic distillation process has been used for olefin/paraffin separation commercially. but the process has been extremely high energy-consuming; about 20% of the energy of petrochemical industry have been consumed. Facilitated transport membranes (FTMs) could be a promising alternative for olefin/paraffin separation, We have prepared dense and composite FTMs using polymeric ion complex containing AgNO3. Excellent olfein/paraffin selectivity and olefin flux with the FTMs were obtained through pure gas permeation test. A simulation program based on the obtqined results was developed , which could predict the FTMs could provide high-purity olefin at high recovery from olefin/paraffin mixtrue at one-stage process.