아닐린의 산화적 카르보닐화에 의한 에틸페닐카바메이트 합성의 속도론적 고찰

박내정,박재근 ( Nae Joung Park,Jae Keun Park ) 한국공업화학회 1992 공업화학 Vol.3 No.4

에틸페닐카바메이트를 120℃, 79 atm에서 전이금속촉매와 할로겐화 알칼리금속을 조촉매로하여 아닐린의 산화적 카르보닐화반응에 의하여 합성하였다. 산화제로서 산소를 사용하였으며 반응속도를 조사하고 활성화에너지를 추정하였다. 5시간 반응후 전환율은 100%, 선택도는 95%이었고 촉매로서는 Pd촉매가 Rh촉매조다 약간 효과가 좋았으며 조촉매로서의 효율은 KI>KBr>KCl 순이었다. 75℃에서 120℃사이에서 온도의 증가에 따라 반응속도가 증가되었으며 반응은 겉보기 1차반응이었고 활성화 에너지는 5% Pd/C와 5% Rh/C에서 각각 5.647, 5,780 ㎉/㏖이었다. Ethylphenyl carbarmate(EPC) was synthesized by oxidative CO carbonylation of aniline in the presence of transition metal catalysts and alkali metal halide cocatalysts at 120℃ under the pressure of 79atm. Oxygen gas was used for oxidizing agent. Kinetics of the reaction was studied and activation energies with different catalysts were estimated. About 100% conversion to EPC and 95% selectivity was obtained in 5 hour reaction. 5% Pd/C was more effective than 5% Rh/C. Effectiveness of cocatalysts was in the order of KI>KBr>KCl. As the temperature increased from 75℃ to 120℃, the conversion rate increased. The reaction was apparent first order and the acitivation energies with 5% Pd/C and 5% Rh/C were 5.647 and 5.780 ㎉/㏖, respectively.

셀룰로오스질 유기고형폐물의 열분해에 관한 연구

박내정,Park Nae Joung 대한화학회 1977 대한화학회지 Vol.21 No.4

셀룰로오스질 유기고형폐물로서 목피 및 톱밥과 순수한 셀룰로오스로서 여지를 $300^{\circ}C$ 질소기류하 또는 질소와 공기의 혼합기류하에서 열분해하고 생성물은 공기냉각, 수냉각, 드라이아이스-아세톤 냉각에 의해서 응축되는 성분과 비응축성 가스 및 탄화찌끼의 양을 조사하였다. 또 이중 드라이아이스-아세톤 냉각에 이해서 포집된 휘발성 액체 성분을 기체크로마토그래프를 이용하여 분리하고 이들 성분의 머무는 시간과 시린지반응에 의해 동정하였다. 질소기류하에서 열분해할 경우에는 타아르성분이 13.4 ∼ 29.6${\%}$, 수용성액체가 0.01 ∼ 0.12${\%}$, 휘발성액체가 0.24 ∼ 1.43${\%}$, 비응축성가스가 9.84 ∼ 42.4${\%}$, 탄화찌끼가 44.0 ∼ 65.81${\%}$이었고 혼합기류하에서 열분해할 경우에는 다른 성분이나 응축성 액체의 양이 감소되고 비응축성가스가 증가되었다. 질소기류하에서 포집된 휘발성액체는 Porapak Q 칼럼에 의해서 분해물질에 상관없이 19가지의 똑같은 성분으로 분리되었고 다만 각 성분의 상대적 양만이 차이를 나타내었다. 혼합기류하에서 열분해할 경우에는 6개성분만이 생성되었고 주로 methanol, formaldehyde 등의 분자량이 적은 물질만이 생성되었다. 분리된 19성분을 머무는 시간과 시린지 반응에 의해 동정해 본 결과 methanol, formaldehyde, acetone, acetaldehyde, acetic acid와 3개의 hydroxyl기를 가진 것으로 추측되는 성분이 동정되었다. Cellulosic organic solid wastes such as bark and sawdust, and filter papers as a pure cellulose were pyrolyzed at $300^{\circ}C$ under nitrogen current and mixed current of nitrogen and air. Amounts of condensates collected in air, water, and dry ice-acetone cooling traps, noncondensable gases, and carbonized residues were surveyed. The components of volatile liquids condensed in dry ice-acetone trap were separated by means of gas chromatograph and identified by retention times and syringe reactions. Pyrolysis under nitrogen current produced 13.4∼29.6${\%}$ of tar, 0.01∼0.12${\%}$ of aqueous liquids, 0.24∼1.43${\%}$ of volatile liquids, 9.84∼42.41${\%}$ of noncondensable gases, and 44.0∼65.81${\%}$ of carbonized residues. Pyrolysis under mixed current decreased tar and condensable liquids, but increased noncondensable gases.Volatile liquids collected under nitrogen current separated into the same 19 components by Porapak Q column regardless of the materials and only difference among materials was relative amounts of components. Volatile liquids collected under mixed current separated into six components and mainly lower molecular weight compounds such as methanol and formaldehyde were produced. According to the retention times and syringe reactions, methanol, formaldehyde, acetone, acetaldehyde, acetic acid, and three other compounds presumably containing hydroxyl group in the molecular structure were identified out of 19 compounds.

Effect of Lime on Growth of Rice and Changes in pH, Eh, Fe²⁺ and Al in an Acid Sulfate Soil

박내정,박영선,김영섭,Park, Nae Joung,Park, Young Sun,Kim, Yung Sup 한국토양비료학회 1971 한국토양비료학회지 Vol.4 No.2

A pot experiment with an acid sulfate soil from Kimhae was carried out to find out the cause of toxicity in rice plant. The effect of liming on changes in pH, Eh, Al, and $Fe^{2+}$ in soil and leachate was examined at two-week interval during the growth of rice. Also, total $P_2O_5$, $SiO_2$, Fe and Al contents in plants at harvesting stage were determined. In the early stage, the rice plant in the check soil showed the same healthy growth as did in limed soil even at high Al in soil and leachate. Around panicle forming stage, reddish brown mottlings suddenly infested all over the plants when accompanied with strong reduction, and afterward growth was severely retarded, and finally caused the significant difference in yield. During the strong reduction, significant amount of sulfide was formed only in check soils, but no free $H_2S$ was detected. Appreciable Al was still present in soil and leachate, and $Fe^{2+}$ in check soil was lower than that in limed soil, but $Fe^{2+}$ in leachate was slightly higher. Limed soils were more reduced and produced more $Fe^{2+}$ due to increased microorganism activity in the neutral pH. In the leachate, the check showed slightly higher $Fe^{2+}$ concentration but considerably higher than limed one at later stage. Appreciable amount of Al was detected only in check soil and leachate from transplanting to panicle formation stage. Plant tissues at harvesting stage contained very low P regardless of liming. Uptake of Si was markedly increased by liming. Contents of Fe an Al was markedly higher in check than limed one, but difference in Fe content was more drastic possibly due to more Fe uptake in presence of markedly higher $Fe^{2+}$ in soil and leachate at later growing stage. In conclusion toxic symptom in this acid sulfate soil seems to be primarily due to Al when accompanied with low pH and strong reduction. But association with $Fe^{2+}$ toxicity is not completely excluded. In order to differentiate the effect of $Fe^{2+}$ from that of Al more detailed plant analysis at different stage is required. 김해특이 산성토양에서 벼생육을 저해하는 원인을 구명하고자 폿트에 벼를 재배하면서 생육기간동안 2주일 간격으로 토양 및 용출액 pH, Eh, $Fe^{2+}$, Al 등의 변화를 조사하였고 수확기 식물체에 대해 P, Si, Fe, Al 등을 분석한 결과를 요약하면 다음과 같다. 생육초기에는 무처리구나 석회처리구에서 모두 정상적인 생육을 하였으나 유수형성기 며칠 전에 무처리구에서 갑자기 적갈색반점이 나타나기 시작하여 2~3일 사이에 극심하게 전 부위에 퍼졌다. 이때에 생육이 극히 저해를 받아 그 이후의 생육은 상당히 억제되어 결국 수량에 있어서 큰 차이를 가져왔다. 이 시기에 토양은 급격한 환원이 일어났으며 FeS의 생성이 현저하였으나 유리 $H_2S$는 검출되지 않았다. 피해가 없었든 석회처리구에서는 Al이 검출되지 않았으나 무처리구에서만 토양이나 용출액 중에 Al이 상당량 존재해있었다. $Fe^{2+}$은 토양 중에서는 석회처리구에서 오히려 높았고 용출액 중에서는 석회구보다 무처리구에서 약간 높은 경향이었으나 그차는 크지 않았다. 그러나 용출액중의 $Fe^{2+}$의 함량은 무처리에서 후기 계속 높은 경향이었으나 석회구에서는 극히 낮은 농도로 떨어졌다. 토양에서도 후기에는 석회처리구를 훨씬 능가하여 높은 함량을 보였다. 식물체 분석결과 처리에 무관하게 P의 함량이 보통답에서 자란 벼보다 낮은 경향이었고 석회처리에 의해 Si의 흡수량이 현저히 증가하였다. Fe나 Al의 함량은 무처리구에서 모두 높았는데 Fe 함량 차이가 더 뚜렷하였다. 이는 생육후기에 무처리구에서 $Fe^{2+}$가 계속 높은 함량을 보였기 때문으로 보인다. 결론적으로 이 특이 산성토양에서의 피해는 pH가 낮고 Al 함량이 비교적 높은 상태에서 강한 환원에 의해 유발되는 것으로 생각되어 $Fe^{2+}$에 의한 피해 여부를 조사하기 위해서는 생육기간중 Fe 흡수상황을 식물체 분석을 통하여 더욱 검토하여야 할 것이다.

철 비료로서의 자연 Chelate

박내정 한국토양비료학회 1971 한국토양비료학회 학술발표회 Vol.1971 No.6

활성오니(活性汚泥) 및 녹개퇴비중 수용성 철 킬레이트의 분리와 특성에 관한 연구

박내정,월라드엘린지 한국농화학회 1975 Applied Biological Chemistry (Appl Biol Chem) Vol.18 No.4

This study was conducted to study the properties of the water-soluble natural chelating agents from garbage compost and activated sewage sludge responsible for Fe chelation, which is closely associated with the effectiveness in correcting iron chlorosis in plant. The water-soluble fraction of these materials was fractionated by menas of Sephadex gel filtration and the fractions of Fe chehates were traced by radioactive ^(59)Fe. The fractions were examined by ultraviolet and infrared. spectroscopy and stability constants for Fe. The water-soluble fraction from garbage compost was separated by Sephadex G-25 into approximately four fractions. Most of the added ^(59)Fe was associated with fraction I, which appeared at the void volume. Further fractionation by Sephadex G-50 indicated that the molecular weight of water-soluble chelating agents is in the approximate range of 5000 to 10,000. The water-soluble fraction from activated sewage sludge gave six fractions by Sephadex G-25. Most of the added ^(59)Fe was found in the fraction I,II, and III, The molecular weights of most chelating agents associated with ^(59)Fe appeared to be less than 5,000 and those of fraction I that appeared at the void volume was in the range of 5, OOf~ to 1,000. Discrepancy between radio activity count and UV absorption indicated the heterogeneity of the fractions obtained by Sephadex gel filtration. Ultraviolet absorption spectra of all fractions separated by Sephadex G-25 and containing chelating agents showed no differences. Fraction IV and V of sewage extract showed absorption maxima and shifting similar to nucleic acid components suggesting the presence of decomposition products of nucleic acid. Similarity fraction VI contained phenolic type amino acid groups. Fraction I of compost extract contained most of the added ^(59)Fe and showed weak but extra definite absorption in the 1230, and 1270㎝^(-1) region, suggesting that extra oxygen groups in polyphenolic structure were probably involved in Fe chelation. In sewage extract, fraction I,II, and III in which most of the ^(59)Fe was found, showed strong definite polypeptide absorption in the region of 1540㎝^(-1) due to NH deformation and C-N stretching of amide groups in the peptidebond. These extra functional groups in fraction I, II, and III appeared to be associated with Fe chelztion. The other fractions, not associated with ^(59)Fe, still have carboxyl and hydroxyl groups, suggesting that these functional groups in these water extracts may not independently form the Fe chelates. Precipitation of ferric hydroxide precluded measuring the stability constants for Fe-chelates. However, the formation constants for Zn chelates as log K values for compost extract and sewage extract at pH 4.0 from which the strength of chelation with Fe could be presumed, were 8.23, and 9.75, respectively, indicating strong complexation with metals. The chelating capacity of compost extract containing 6.5 g organic matter per liter was 0.82 mM, and that of sewage extract containing 5.3 g per liter was 0. 64 mM.

P-Aminoacetanilide의 제조에 관한 연구

박내정 弘益大學校 科學技術硏究所 1994 科學技術硏究論文集 Vol.4 No.-

Production processes p-aminoacetanihide from acetanilide were studied by nitration with nitric aced and mixed acids and redyction with iron and iron(Ⅲ) chloride and hydrogen in the presence of palladium catalyst. Best result of nitration was obtained when acetanilde dissoved in 70% nitric acid in perchloroethylene was added into 95% sulfuric acid. P-aminoacetanilide was easily purified bt heating to 85℃ for two hours in the mixed solution of water and perchloroethylene. Hundred percent conversion of p-nitroacetanilide to p-aminoaceta-ncetanilide was achieved by 30psi hydrogen in the presence of 5% pd/c catalyst at 60℃ in methanol solution. Recycled catalyst was as effective as fresh one. Small amount of acetic acid effectively prevented from production of p-phenylenediamine.

아닐린의 산화적 카르보닐화에 의한 에틸페닐카바메이트의 합성의 속도론적 고찰

박내정,박재근,Park, Nae-Joung,Park, Jae-Keun 한국공업화학회 1992 공업화학 Vol.3 No.4

에틸페닐카바메이트를 $120^{\circ}C$, 79 atm에서 전이금속촉매와 할로겐화 알칼리금속을 조촉매로하여 아닐린의 산화적 카르보닐화반응에 의하여 합성하였다. 산화제로서 산소를 사용하였으며 반응속도를 조사하고 활성화에너지를 추정하였다. 5시간 반응후 전환율은 100%, 선택도는 95%이었고 촉매로서는 Pd촉매가 Rh촉매보다 약간 효과가 좋았으며 조촉매로서의 효율은 KI>KBr>KCl 순이었다. $75^{\circ}C$에서 $120^{\circ}C$사이에서 온도의 증가에 따라 반응속도가 증가되었으며 반응은 겉보기 1차반응이었고 활성화 에너지는 5% Pd/C와 5% Rh/C에서 각각 5.647, 5,780 kcal/mol이었다. Ethylphenyl carbarmate(EPC) was synthesized by oxidative CO carbonylation of aniline in the presence of transition metal catalysts and alkali metal halide cocatalysts at $120^{\circ}C$ under the pressure of 79atm. Oxygen gas was used for oxidizing agent. Kinetics of the reaction was studied and activation energies with different catalysts were estimated. About 100% conversion to EPC and 95% selectivity was obtained in 5 hour reaction. 5% Pd/C was more effective than 5% Rh/C. Effectiveness of cocatalysts was in the order of KI>KBr>KCl. As the temperature increased from $75^{\circ}C$ to $120^{\circ}C$, the conversion rate increased. The reaction was apparent first order and the activation energies with 5% Pd/C and 5% Rh/C were 5.647 and 5.780 kcal/mol, respectively.

산업 고형유기폐물의 자원화에 관한 연구 (제1보) 산업 고형유기폐물의 비료와 Humus 원으로서의 물리적 및 화학적 특성에 관하여

박내정,김용인,Park Nae Joung,Kim, Yong In 대한화학회 1975 대한화학회지 Vol.19 No.4

유기폐물을 다량으로 배출하는 산업중에서 대표적인 제지·펄프공업, 식품공업을 선택하여 고형유기폐물과 폐수처리오니의 합리적인 자원화 방법으로서 이들물질의 비료적 가치 및 humus원으로서의 개발가치를 중심으로 이들 물질의 물리적 및 화학적 특성을 조사한 결과이다. 제지${\cdot}$펄프공업 유기고형폐물은 비료성분이 적고 lignin 함량이 높아 비료로서 보다는 humus화하여 토양개량제로서 개발하는 것이 합리적이다. 제혁공업 폐수처리오니는 비료로서 효과도 기대되어 산성토양 개량효과도 기대되나 다량으로 함유한 Cr 으로 인해 오염효과가 문제가 된다. 식품공업의 고형 유기폐물 또는 폐수처리오니는 비료로서 또는 미량요소 공급원으로서 가치가 인정되며 수용성 당류의 량이 높거나 C/N율이 20이하로 낮은 물질은 속성 humus화를 위한 첨가 재료로서의 가치도 인정된다. The physical and chemical characteristics of solid organic wastes from paper and pulp industries, tanneries, and food processing industries were studied with regard to fertilizer value as well as humus sources as a rational method of waste utilization. The pulp and paper mill wastes containing low mineral nutrients but high lignin may be utilized for soil amendments through humus preparation. Chemical treatment sludges of tannery wast water contained appreciable fertilizer nutrients andiliming materials, but utilization as fertilizers or soil amendments depends on the pollution effect of high chromium content, which has not been well understood. Food processing wastes may be utilized as organic fertilizers or micronutrient sources for plant. Some wastes containing high water-soluble sugars or lower C/N ratio than 20 may be utilized as additives for rapid humus preparation.

A Study on the Physico-Chemical Characteristics of Acid Sulfate Soil in Kimhae Plain

박내정,박영선,Park, N.J.,Park, Y.S. 한국토양비료학회 1969 한국토양비료학회지 Vol.2 No.1

김해평야(金海平野)에 분포(分布)된 특이산성토(特異酸性土)(답(畓))에서 저수확지토양(低收穫地土壤)과 고수확지토양(高收穫地土壤)의 표토(表土), 심토(心土), 28점(點)과 수(數) 10년전(年前) 및 10여년전(餘年前)에 개답(開畓)된 2개(個)의 대표적(代表的)인 층위별(層位別) 토양시료(土壤試料)의 이화학적(理化學的) 성질(性質)을 분석조사(分析調査)한 결과(結果)를 요약(要約)하면 다음과 같다. 1. 토성(土性)에 있어서는 저수확지(低收穫地), 고수확지(高收穫地) 토양간(土壤間)에 별차이(別差異)가 없고, 대부분(大部分)이 미사질(微砂質) 식토(埴土) 또는 미사질(微砂質) 식양토(埴壤土)이었다. 2. 토양(土壤)의 pH, 염기포화도(鹽基飽和度) 및 알미늄함량(含量)에 있어서는 그 차이(差異)가 커서 저수확지토양(低收穫地土壤)의 표토(表土) 및 심토(心土)에서는 pH가 낮고 염기포화도(鹽基飽和度)가 적을뿐아니라 알미늄함량(含量)이 많았다. 3. 저수확지토양(低收穫地土壤)의 염기치환용량(鹽基置換容量)은 비교적(比較的) 높았으며 고수확지(高收穫地) 토양(土壤)과는 큰 차이(差異)가 없었다. 고수확지토양(高收穫地土壤)에서는 치환성(置換性) 석회(石灰)나 고토(苦土)는 거의 같은 양(量)이었으나 저수확지토양(低收穫地土壤)에서는 석회(石灰)에 비(比)하여 고토함량(苦土含量)이 상당(相當)히 많았다. 4. 가용성(可溶性) 염류(鹽類)는 비교적(比較的) 높고 특(持)히 심토(心土)와 저수확지토양(低收穫地土壤)에서 더 높았다. 저수확지토양(低收穫地土壤)의 가용성(可溶性) $SO_4{^=}$는 $Cl^-$ 보다 더 많았다. 5. 유기물(有機物)은 보통답(普通畓)에 비(比)하여 약간 많았으나 질소(窒素)는 비교적(比較的) 적었다. C/N Ratio 는 12정도(程度)이었다. 6. 유황함량(硫黃含量)은 대단(大端)히 높았으며 반면(反面)에 가산화성유황(可酸化性硫黃)은 대단(大端)히 적었다. 전유황(全硫黃)은 대개 심토(心土)와 저수확지토양(低收穫地土壤)에서 높았다. 7. 활성철(活性鐵)과 유효규산은 보통답(普通畓)에 비(比)하여 약간 많았으며 토양간(土壤間)에는 별차이(別差異)가 없었다 역환원성(易還元性) 망간은 보통답(普通畓)에 비(比)하여 적은 편(便)이며 특(持)히 저수확지(低收穫地)에서 대단(大端)히 적었다. 8. 유효인산은 고저수확지토양(高低收穫地土壤) 다같이 대단(大端)히 적었다. 9. 2개(個)의 대표(代表)되는 층위별(層位別) 시료중(試料中) 오래전(前)에 개답(開畓)된 토양(土壤)에서는 유리산(遊離酸), 유황화합물(硫黃化合物), 알미늄, 가용성염류등(可溶性鹽類等)이 근래(近來)에 개답(開畓)된 토양(土壤)에서 보다 적었다. 10. 고수확지토양(高收穫地土壤)에서의 높은 수량(收量)은 보다 많은 토양(土壤)의 용탈(溶脫)과 석회질물질(石灰質物質) 시용(施用)으로 그 토양(土壤)의 산도(酸度)를 중화(中和)한데 기인(基因)된다. 따라서 이들 토양(土壤)의 생산력은 관개배수(灌漑排水)나 석회질물질(石灰質物質)을 시용(施用)함으로서 증가(增加)시킬수 있다. The study on physico-chemical characteristics of the acid sulfate soil present in Kimhae plain was carried out with 28 surface and subsoils from lower and higher produtive area and two representative profile samples from the areas reclaimed a few decades ago and around 10 years ago respectively. 1. There are no differences in soil texture between lower and higher productive soils being mostly silty clay loam and silty clay. 2. Very significant differences in pH, degree of base saturation and extractable aluminium content are observed; lower pH, lower degree of base saturation and higher aluminium in the lower productive soils and subsoils. The pH and degree of base saturation of these soils are extremely low whereas aluminium content is very high compared to ordinary paddy soil. 3. Cation exchange capacity of these soils are slightly higher than ordinary paddy soils. In higher productive soils, exchangeable calcium and magnesium are of same order, whereas in lower productive soils magnesium content is appreciably higher than calcium. 4. Though the soil is derived from marine and estuarine sediment, the soluble salt content is not high. There are only few lower productive surface soils and subsoils having Ec values of the saturation extracts higher than 4 mmhos but lower than 9 mmhos/cm. 5. Organic matter content of these soils is a bit higher compared to ordinary paddy soils, but, nitrogen content is comparatively low. C/N ratio of these soils is around 12. 6. Sulfur content is considerably higher but oxidizable sulfur is found to be very low. Total sulfur is generally high in subsoils and lower productive soils. 7. Active iron and available silica are slightly higher than ordinary paddy soils but easily reducible manganese is very low. Almost no differences are also observed between lower and higher productive soils. 8. Available phosphorus content is extremely low in particular, regardless of higher or lower productive soils. 9. The two representative profiles from the area of earlier reclamation and recent one show that samples from earlier reclaimed area contain less amount of free acids, sulfur compounds, toxic aluminium and soluble salts etc. than the other. This indicate greater leaching and possible addition of lime for a longer period of time. 10. From the results obtained, it can be concluded the higher productivity of group I soils is due to the greater leaching and neutralisation of acidity by liming materials, It can also be concluded that the productivity of both types can be increased by addition of liming materials and improvement of drainage facilities.

학술발표 요지 : 대맥의 NPK 응수에 미치는 기상 및 주요토양인자들의 영향에 관하여

박내정,이춘수,유인수,박천서 한국토양비료학회 1972 한국토양비료학회 학술발표회 Vol.1972 No.9