Abstract
Larch ($\underline{Larix}$ $\underline{leptolepis}$ GORDON), one of the major afforestation species in Korea in view of its growing stock and rate of growth, is not favored as a raw material for pulp due to its low yield of pulp and difficulties with bleaching arising from the high content of extractives in wood, and the high heartwood ratio and the active phenolics, respectively. The purpose of this study is to investigate the characteristics of firstly pulping with various additives of cellulose protector for the yield of pulp, and secondly bleaching with oxygen for chlotination-alkali extraction of five stage-sequence to reduce chlorine compounds in bleaching effluents. The kraft cooking liquor for five age groups of larchwood was 18 percent active alkali with 25 percent sulfidity and 5 : 1 liquor-to-wood ratio, and each soda liquor for sap-and heart-wood of the 15-year-old larchwood was 18 percent alkali having one of the following cellulose protectors as the additive; magnesium sulfate ($MgSO_4$, 2.5%), zinc sulfate ($ZnSO_4$, 2.5%), aluminium sulfate ($Al_2(SO_4)_3$, 2.5%), potasium iodide (KI, 2.5%), hydroquinone (HQ, 2.5%), anthraquinone (AQ, 0.1%) and ethylene diamine (EDA, 2.5%). Then each anthraquinone-soda liquor for the determination of suitable cooking condition was the active alkali level of 15, 17 and 19 percent with 1.0, 0.5 and 0.1 percent anthraquinone, respectively. The cooking procedure for the pulps was scheduled to heat to 170$^{\circ}C$ in 90 minutes and to cook 90 minutes at the maximum temperature. The anthraquinone-soda pulps from both heartwood and sapwood of 15-year-old larchwood prepared with 0.5 percent anthraquinone and 18 percent active alkali were bleached in a four-stage sequency of OCED. (O: oxygen bleaching, D: chlorine dioxide bleaching and E: alkali extraction). In the first stage oxygen in atmospheric pressure was applied to a 30 percent consistency of pulp with 0.1 percent magnesium oxide (MgO) and 3, 6, and 9 percent sodium hydroxide on oven dry base, and the bleached results were compared pulps bleached under the conventional CEDED (C: chlorination). The results in the study were summarized as follows: 1. The screened yield of larch kraft pulp did not differ from particular ages to age group, but heartwood ratio, basic density, fiber length and water-extractives contents of wood and the tear factor of the pulp increased with increasing the tree age. The total yield of the pulp decreased. 2. The yield of soda pulp with various chemicals for cellulose protection of the 15-year-old larchwood increased slightly more than that of pure soda pulp and was slightly lower than that of kraft pulp. The influence of cellulose protectors was similar to the yield of pulps from both sapwood and heartwood. The effective protectors among seven additives were KI, $MgSO_4$ and AQ, for which the yields of screened pulp was as high as that of kraft pulp. Considering the additive level of protector, the AQ was the most effective in improving the yield and the quality of pulp. 3. When the amount of AQ increased in soda cooking, the yield and the quality of the pulp increased but rejects in total yield increased with decreasing the amount of active alkali from 19 to 15 percent. The best proportion of the AQ seemed to be 0.5 percent at 17 percent active alkali in anthraquinone-soda pulping. 4. On the bleaching of the AQ-soda pulp at 30 percent consistency with oxygen of atomospheric pressure in the first stage of the ODED sequence, the more caustic soda added, the brighter bleached pulp was obtained, but more lignin-selective bleaching reagent in proportion to the oxygen was necessary to maintain the increased yield with the addition of anthraquinone. 5. In conclusion, the suitable pulping condition for larchwood to improve the yield and quality of the chemical pulp to the level for kraft pulp from conventional process seemed to be. A) the selection of young larchwood to prevent decreasing in yield and quality due to the accumulation extractives in old wood, B) the application of 0.5 percent anthraquinone to the conventional soda cooking of 18 percent active alkali, and followed, C) the bleaching of oxygen in atmospheric pressure on high consistency (30%) with 0.1 percent magnesium oxide in the first stage of the ODED sequence to reduce the content of chlorine compounds in effluent.
우리나라에서는 일본잎갈나무가 대량(大量) 조림(造林)되어 축적(蓄積)과 생장량(生長量)으로 보아 주요(主要)한 조림(造林) 수종(樹種)이나 각종(各種) 추출물(抽出物)과 활성(活性) phenol 성분(成分)이 많고 심재율(心材率)이 높아 펄프화(化)에서 수율저하(收率低下)와 표백곤란(漂白困難)이 초래(招來)되어 펄프원료(原料)로서의 이용(利用)이 기피(忌避)되고 있다. 따라서 일본잎갈나무의 화학(化學)펄프 원료화(原料化)의 제고(提高)로서 펄프수율(收率) 향상(向上)과 표백성(漂白性) 개선(改善)을 위하여 셀룰로오스보호제를 첨가(添加)한 소다펄프화(化) 특성(特性)을 구명(究明)하였다. 증해(蒸解)는 최고온도(最高溫度) 170$^{\circ}C$까지 90분간(分間) 가열(加熱)하고 90분간(分間) 유지(維持)하는 일정조건(一定條件)으로 황화도(黃化度) 25%, 활성(活性)알칼리 18%의 크라프트법(法)으로 일본잎갈나무의 수령별(樹齡別) 펄프화(化) 특성(特性)을 구명(究明)하고, 18%활성(活性) 알칼리의 소다증해(蒸解)에 첨가제로 2.5% $MgSO_4$, 2.5% $ZnSO_4$, 2.5% $Al_2(SO_4)_3$, 2.5% KI, 2.5% hydroquinone, 2.5% ethylene diamine 또는 0.1~1.0% anthraquinone를 가(加)하여 15년생(年生) 일본잎갈나무의 변재(邊材)와 심재별(心材別) 소다펄프화(化) 특성(特性)을 구명(究明)한 후(後), 0.5% anthraquinone과 18% 활성(活性)알칼리로 증해(蒸解)된 펄프를 3%, 6%, 9% NaOH를 투입(投入)한 30%의 고농도(高農度)펄프를 상압(常壓) 산소표백(酸素漂白)하고, 이산화염소(二酸化鹽素)의 DED로 계속표백(繼續漂白)한 결과(結果) 다음과 같은 결론(結論)을 얻었다. 1. 일본잎갈나무의 수령별(樹齡別) 크라프트펄프는 수령간(樹齡間)에 펄프의 정선수율(精選收率)은 차(差)가 없으나, 수령(樹齡)이 증가함에 따라 펄프의 총수율(總收率)은 감소(減少)하고 비인열도(比引裂度)는 증가하였으며, 목재(木材)의 심재율(心材率), 용적밀도(容積密度) 수(數), 섬유장(纖維長) 및 온수추출물(溫水抽出物)도 증가하는 경향(傾向)을 나타냈다. 2. 일본잎갈나무의 변재(邊材)와 심재별(心材別) 소다증해(蒸解)에 셀룰로오스 보호제로 첨가(添加)된 7종(種)의 첨가제들은 변재(邊材)와 심재(心材)펄프화(化)에 대한 영향(影響)이 대체로 소다법(法)보다 증가되었으나 크라프트법(法)에 미치지 못하고, 크라프트펄프법(法)에 가까운 첨가제는 펄프수율(收率)에서 KI $MgSO_4$, anthraquinone이며, 특(特)히 다른 첨가제의 25분(分) 1이 첨가(添加)된 anthraquinone은 펄프의 정선수율(精選收率)과 KappaNo. 및 비파열도(比破裂度)에서 다른 첨가제보다 효과적이었다. 3. anthraquinone첨가량(添加量)에 따른 변재(邊材)와 심재별(心材別) 소다펄프의 품질(品質)은 변재(邊材)와 심재(心材) 모두 첨가량(添加量)이 많을수록 탈(脫)리그닌도(度)와 펄프수율(收率)이 높으나 활성(活性)알칼리가 낮으면 정선수율(精選收率)도 낮았으며 활성(活性)알칼리 17%의 소다 증해액(蒸解液)에 0.5% anthraquinone을 첨가(添加)한 조건(條件)에서는 크라프트펄프보다 비교적(比較的) 양호(良好)한 펄프가 얻어졌다. 4. 일반화(一般化)된 CEDED표백중(漂白中) 염소화(鹽素化)와 알칼리 추출단계(抽出段階) 대신(代身)에 30%의 고농도(高濃度)펄프에 상압(常壓) 산소표백(酸素漂白)한 ODED표백(漂白)은 산소단계(酸素段階)에서 변재(邊材)와 심재(心材)펄프 모두 NaOH투입량(投入量)이 증가될수록 백색도(白色度)와 비인열도(比引裂度)가 향상(向上)되나 펄프수율(收率)과 Kapa No.는 감소(減少)되었으며, NaOH 투입량(投入量)이 높을수록 펄프품질(品質)은 CEDED 표백(漂白)과 유사(類似)하나 펄프수율(收率)이 떨어졌다. 5. 따라서 본(本) 실험(實驗)에서는 펄프수율(收率) 향상(向上)을 위해서는 원료(原料)에서 심재율(心材率)이 낮은 수령(樹齡)의 경우가 펄프재(材)로 적당(適當)하고, 0.5% anthraquinone을 첨가(添加)한 활성(活性)알카리 18%의 소다증해(蒸解)하는 것이 적당(適當)하며 폐수중(廢水中)의 염소화합물(鹽素化合物)을 감소(減少)시키기 위하여서는 펄프농도(濃度) 30%이상(以上)의 고농도(高濃度)에서 상압(常壓) 산소(酸素)로 표백후(漂白後) 이산화(二酸化) 염소(鹽素)로 DED 표백(漂白)하면 일본잎갈나무의 크라프트법(法)보다 비교적(比較的) 우수(優秀)한 펄프를 얻을 수 있다.