Α7 經濟部智慧財產局員工消費合作钍印划代 ^ 44658δ _Β7___ 五、發明說明（1 ) 本發明是關於一受調控的微生物降解處理，可用以使 受六氯基苯（HCB)污染的土壤或沈澱物除污。 六氯基苯是製造氯化溶劑時的反應副產物，主要的氯 化溶劑是四氯化碳、四氯乙烯、三氯乙烯和二氯乙烯》 H C B也使用於播種處理劑的製造中，以及很多工業的應 用上。 有很多土地受到高毒性的H C Β污染數十年。這些地 方很多地區已不能使用，且要等到將這些地區的土壤大規 模除污之後方可利用。Α7 Marking of consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 44658δ _Β7 ___ V. Description of the invention (1) The present invention relates to a regulated microbial degradation treatment, which can be used to make soil contaminated with hexachlorobenzene (HCB) or The sediment is decontaminated. Hexachlorobenzene is a by-product of the reaction in the production of chlorinated solvents. The main chlorinated solvents are carbon tetrachloride, tetrachloroethylene, trichloroethylene and dichloroethylene. HCB is also used in the manufacture of seed treatment agents, and Many industrial applications. Many lands have been contaminated by highly toxic HCB for decades. Many of these areas are no longer available and will not be available until the soil in these areas has been extensively decontaminated.
Zeneca Corp. U.S. Patents Nos. 5，660，612 及 5 ，660，6 1 3中揭示受DDT污染之土壤的矯正， 經由存在未適應之土壤固有的厭氧反好氧微生物在特殊的 水含量、溫度及氧化還原電位狀態下經由無氧堆製處理後 有氧堆製處理，能使微生物將D D T轉形爲無害物質。 上述方法也嘗試用於去除含有D D T以外之不同污染 物之土壤的除污。雖然此方法已發現對有限的特定污染物 有效，但對很多污染物包括H C B則失敗。此方法沒有確 實的方法可預測那些化合物可被有效的分解，且在含有化 學性不同之H C Β的土壤中無法預期是否可成功除去 D D Τ。 許多硏究者企圖經由在不同少量修飾的無氧堆製處理 下在含泥漿的水溶液中藉由無氧堆製處理降解H C Β。參 閱 P.L. Van Hoof and C. T. Jafvert，1 996 , Environmental Toxicology and Chemistry, 15(11), 1914-24; J. Nowak, W. 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公芨） <IIIIIIJIII.IIl --I---- I — — — — — — 1» --^----- 11 ---I--I----I I ί I I (請先閱讀背面之注意事項再填寫本頁} -4- 經濟部智慧財產局員工消費合作社印製 446585 A/ B7 五、發明說明（2 )Zeneca Corp. US Patents Nos. 5,660,612 and 5,660,6 1 3 disclose the correction of DDT-contaminated soils through the special water content, Under the conditions of temperature and redox potential, the anaerobic stacking process after the anaerobic stacking process can enable microorganisms to transform DDT into harmless substances. The above methods have also been tried for decontamination of soils containing different pollutants other than D D T. Although this method has been found to be effective for a limited number of specific pollutants, it has failed for many pollutants, including H C B. This method does not have a solid method to predict those compounds that can be effectively decomposed, and it is impossible to predict whether D D TT can be successfully removed in soils containing different chemically H C B. Many investigators have attempted to degrade H C B by an anaerobic stacking process in a slurry-containing aqueous solution under differently modified anaerobic stacking processes. See PL Van Hoof and CT Jafvert, 1 996, Environmental Toxicology and Chemistry, 15 (11), 1914-24; J. Nowak, W. This paper size is applicable to China National Standard (CNS) A4 (2) 0 X 297 male芨) < IIIIIIJIII.IIl --I ---- I — — — — — — 1 »-^ ----- 11 --- I--I ---- II ί II (Please read first Note on the back, please fill out this page again} -4- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 446585 A / B7 V. Description of Invention (2)
Hegeman and H. Stan, 1996, 45, 700-709; S. Masunaga, S .Susarla and Y. Yonezawa, 1996, Wat. Sci. Tech., 33(6), 173-180;和 P. Rosenbrock, R. Martens, F. Buscot and JC. Munch, 1 997，Appl. Microbial Biotechnol, 48，115-12◦。然 而這些硏究者的技術沒有一項可成功適用於已知可接受的 商用標準。這些硏究者的泥漿處理不適合於大規模的土壤 處理。 通常在全部的嘗試中，無法完全將無氧堆製處理的 H C B脫氯及切開芳香環，通常會留下單一或多氯苯毒性 代謝物。在無氧降解中只顯示部分的氯原子移除，且從未 顯現過單一氯基苯。 發明槪述 本發·明提供一方法可將含有H C Β污染物的土壤和/ 或沈澱物除污，並將污染物轉換成無害的物質。此方法能 將土壤除污到所期望的程度，亦即可部分除污或完全矯正 〇 更特別的是本發明提供的土壤除去H C Β污染的方法 包括： C a )製備一接種物’製造一包含較少量污染物的受污染 土壤及闻度營養的異營性培養基的混合物，且該混合物貯 存在2 0 °C到3 0 °C至足夠時間，使微生物適應環境而產 生及製造可存活的厭氧及好氧微生物，可轉換存在於土壤 中的污染物爲無害物質’而在無氧和有氧的除污處理狀態 本紙張尺度適闬中圉囷家螵準（CNS)A4規格（210*297公爱） -------,1;---甘^-------訂---------線--》 (請先間讀背面之注意事項再填寫本頁) -5- 經濟部智慧財產局員工消費合作社印-*'|私 ^ 446585 Α7 _ Β7 五、發明說明（3 ) 下這些厭氧及好氧微生物可存活； (b )將該土壤與改良物質混合，並接種以形成一包含有 機養分物質和1〜2 0 %該接種物的固體堆製混合物， (c )初始堆製處理該土壤時將溫度維持在2 〇 一 6 5 °c ’以及該堆製混合物水含量約4 0〜1 0 0 %保水力： (d )初始堆製處理期間維持該堆製混合物的氧化還原電 位約低於負2 0 0 m V以下，直到該污染物有顯著量被降 解：以及 (e )之後氧化該堆製混合物以提高其氧化還原電位到正 1 0 OmV以上，且維持氧化還原電位約正1 〇 以 上至有顯著量的污染物被降解。 此方法包括製備一含有可存活之厭氧及好氧微生物族 群的接種物而能將污染物轉換爲無害物質，且透過此無氧 及有氧狀態之處理仍可存活。然後以這些微生物在固態堆 製處理這些土壤，如文中以下所述。 接種物的製備是經由將少量的污染物，最好的最後接 種混合物重量的1 0到1 0 〇爲佳，與習慣上常用的高養 分水溶液配方的異營性培養基混合。理想下加入一些土壤 到此混合物中仍是液態。然後將此液態混合物於2 〇 °C到 3 ◦ °C貯存6到1 0週。在此期間形成內生性可適應環境 的厭氧及好氧微生物，而可將特殊的污染物轉形成無害物 質，且透過此無氧及有氧狀態之處理仍可存活。 除污處理包括將受H C B污染之土壤與改良物質混合 形成一含有有機養分物質的固體堆製混合物，於2 〇到 本紙張尺度適用中固國家標準（CNS)A4規格（210* 297公3E ) (請先間讀背面之注意事項再填寫本頁) ---a±^-------訂---------線-〉--------------------^--- -6- 經濟部智慧財產局員工消費合作社印糾衣 446585 Α7 ____ Β7 五、發明說明（4 ) 6 5 °C範圍內加入1〜2 0%體積/體積的接種物到堆製 混合物內，且此堆製混合物的水含量約4 〇 %〜1 〇 〇 % 的保水力（W H C );在堆製處理期間維持此堆製混合物 的氧化還原電位低於負2 0 OmV以下，直到有顯著：量的 污染物被降解，大部分爲毒性H C B代謝產物；之後提高 此堆製混合物的氧化還原電位約正1 〇 〇 m ν以上，直到 有更進一步顯著量的污染物被降解。此負/正氧化還原電 位的連續階段，若必要可重覆進行至土壤或沈澱物有微量 之污染物。 定義 文中所使用的A堆製處理〃是意指經由利用生物活性 將土壤和/或沈澱物中的污染物降解轉形爲無害的物質， 此過程於存在有機養分物質的固體狀態下進行。 改良# ’〜改良物質"及"土壤改良物質"是意指 含有有機養分的物質，主要是加入土壤中給微生物除污時 利用。 a污染物〃是意指HCB及從HCB降解的毒性代謝 產物。 當使用 ''降解〃於H C B和及代謝產物時意指移除一 個或更多個氯原子和/或切開苯環。 "無害物質〃意指此物質存在於土壤或沈澱中的濃度 是無異議的。 w H C Β的毒性代謝產物#意指H C Β的降解產物， 本紙張尺度適用中0國家標準（CNS)A4规格（210 X 297公釐） — III — — —-— — 111 — ^ I ί i 11 I «Ι1ΙΙΙ1Ι — — — Υ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印袈 4 46 5 8 5 A7 ____B7 五、發明說明（5 ) 是從H C B分子移除一個或更多個氯原子，但η C B尙未 完全降解到無害物質。 ''除污作用〃是意指轉形污染物爲無害物質，包括生 物降解此污染物和/或結合此污染物到土壤或其它物暂。 Α矯正〃是意指將土壤/沈澱物中的污染物除污至無 異議的程度。 土壤 是意指土地’譬如：腐植土 ·砂和顆粒岩石 ，以及包來自水表面以上或以下的沈降物。 發明之詳述 在本發明之處理的降解步驟中，被除污的土壤必需包 含透過適當種類之可存活微生物的處理而能降解此污染物 。因此必需存在厭氧和好氧微生物，這些微生物必需可在 無氧和有氧狀態下存活，以使它們可存在於此處理過程。 再者’當堆製混合物進行無氧及有氧狀態處理時，此微生 物族群不能被殺死或不利之影響，以致於它們不會充分的 降解HCB。這些微生物通常是細菌、真菌、放線菌屬以 及少部分的原蟲類。如往後所述，本發明的第一步驟是要 從微生物製備一合適的接種物，初始將微生物存在於欲處 理的土壤內，使其能適應污染物而將之除污。從已除污土 壤可再循環利用額外的活性微生物。 在本發明的實行中，固態堆製混合物的製備是經由將 合適的土壤改良物質混合到土壤中而達除污作用，其中的 改良物質至少佔總量的1 〇 %，最多是達此混合物重量的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公;8 ) -------.---j---^)-------訂---------線--Y (請先閱讀背面之注意事項再填寫本頁) -8 - 4465 85 Α7 Β7 經濟部智慧財產局員工消費合作杜印製 五、發明說明（6 ) 9 5%，而較佳是約3 0%〜7 〇%重量的改良物質，有 些可能已存在於土壤內。土壤改良物質包含一在堆製處理 期間給微生物用的慣用之有機養分來源=較佳的改良養分 物質是農業廢料和都市下水道污泥，如馬、牛、綿羊、火 雞、雞或魚的糞肥或已活化之下水道污泥爲佳。紫花苜蓿 、乾草、鋸屑、泥媒、牧草和其它增大物質可能存在於堆 製混合物中，糞肥的起源或特別被加入。接種物以足夠量 加到堆製混合物內以顯著影響微生物的族群，至少1 %是 必需的，以及以1 - 2 %接種物體積/體積加到改良物質 爲佳。 在一些案例中可能需要包括一表面作用劑在土壤改良 中以使污染物更容易被生物性降解作用。合適的表面作用 劑包括聚山梨酸鹽、辛苯聚醇、陰離子烷基硫酸酯、陰離 子烷基芳香基硫酸酯和乙氧酸鹽。合適的表面作用劑範例 包括來自ICI Americas, Inc.的TWEEN ®非離子性表面作用 劑，來自Union Carbide的TRITON ®非離子性表面作用劑 商品’以及來自Procter & Gamble的DAWNTM淸潔劑商品。 改良物質也可以包含或補充液體或固體的有機或無機養分 ，含高量硝酸鹽和磷酸鹽的有機物質常被使用。 堆製混合物維持在一含濕度的固體狀態中。透過整個 處理其濕度維持在小於1 〇 〇 %的混合物保水力（w H C ) >以約4 0〜7 0 %的保水力爲佳。 混合之後，混合物內的有機物質的生物性降解作用才 開始，升高溫度及消耗氧氣使成無氧狀態。之後將此混合 本紙張尺度適用中國囷家標準（CNS>A4規格（210 X 297公笼> <請先閱讀背面之注意事項再填寫本頁)Hegeman and H. Stan, 1996, 45, 700-709; S. Masunaga, S. Susarla and Y. Yonezawa, 1996, Wat. Sci. Tech., 33 (6), 173-180; and P. Rosenbrock, R Martens, F. Buscot and JC. Munch, 1 997, Appl. Microbial Biotechnol, 48, 115-12. However, none of these investigators' technologies have been successfully applied to known commercially acceptable standards. These researchers' mud treatments are not suitable for large-scale soil treatment. Usually in all attempts, the anaerobic stacking of H C B cannot be completely dechlorinated and the aromatic ring is cleaved, which usually leaves a single or polychlorinated toxic metabolite. Only partial chlorine atom removal was shown during anaerobic degradation, and a single chlorobenzene was never shown. SUMMARY OF THE INVENTION The present invention provides a method for decontaminating soil and / or sediments containing H C B pollutants and converting the pollutants into harmless substances. This method can decontaminate the soil to a desired degree, that is, partially decontaminate or completely correct it. More specifically, the method for removing HC B pollution in the soil provided by the present invention includes: C a) Preparation of an inoculum 'manufacturing a A mixture of contaminated soil containing a small amount of pollutants and a nutrient-free heterotrophic culture medium, and the mixture is stored at 20 ° C to 30 ° C for a sufficient time to allow microorganisms to adapt to the environment to produce and produce viable Anaerobic and aerobic microorganisms, can convert pollutants present in the soil into harmless substances, and in the anaerobic and aerobic decontamination treatment state This paper is suitable for the standard (CNS) A4 ( 210 * 297 public love) -------, 1; --- Gan ^ ------- order --------- line-- (Please read the note on the back first Please fill in this page again for matters) -5- Seal of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy-* '| 私 ^ 446585 Α7 _ Β7 V. Description of the invention (3) These anaerobic and aerobic microorganisms can survive; (b) will The soil is mixed with a modified substance and inoculated to form a solid piled mixture containing organic nutrient substances and 1 to 20% of the inoculum, (c) The temperature of the soil during initial stacking is maintained at 065 ° C 'and the water content of the stacking mixture is about 40 ~ 100% water retention: (d) The soil is maintained during the initial stacking treatment. The oxidation-reduction potential of the stacking mixture is less than about minus 200 m V until the pollutant is degraded in a significant amount: and (e) the stacking mixture is oxidized to increase its oxidation-reduction potential to above 10 OmV. And maintain a redox potential of more than about 10 to a significant amount of pollutants are degraded. The method includes preparing an inoculum containing a viable anaerobic and aerobic microbial population to convert pollutants to harmless substances, and surviving through this anaerobic and aerobic treatment. These soils are then treated in a solid state with these microorganisms, as described below. The inoculum is prepared by mixing a small amount of contaminants, preferably 10 to 100 by weight of the final inoculation mixture, and mixing it with a heterotrophic medium formulated with a conventional high-nutrient aqueous solution. Ideally adding some soil to this mixture is still liquid. This liquid mixture is then stored at 20 ° C to 3 ° C for 6 to 10 weeks. During this period, endogenous anaerobic and aerobic microorganisms that can adapt to the environment are formed, and special pollutants can be transformed into harmless substances, and they can still survive through this anaerobic and aerobic treatment. Decontamination treatment includes mixing HCB-contaminated soil with improved materials to form a solid stacking mixture containing organic nutrient substances, and applying the National Solid State Standard (CNS) A4 specification (210 * 297mm 3E) from 20 to this paper size (Please read the precautions on the back before filling in this page) --- a ± ^ ------- order --------- line-> ---------- ---------- ^ --- -6- Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Cooperative Printing and Printing Co., Ltd. 446585 Α7 ____ Β7 V. Description of the Invention (4) 6 5 ° C 1 ~ 2 % Vol / vol of inoculum into the stacking mixture, and the water content of this stacking mixture is about 40% to 100% of the water retention capacity (WHC); the redox of this stacking mixture is maintained during the stacking process The potential is lower than minus 20 OmV until it is significant: the amount of pollutants is degraded, and most of them are toxic HCB metabolites; the redox potential of this stacked mixture is then increased by about positive more than 100 m ν until more Further significant amounts of pollutants are degraded. This continuous phase of negative / positive redox potential can be repeated if necessary until trace amounts of contaminants are present in the soil or sediment. Definition A heaping treatment 〃 used in the text refers to the conversion of pollutants in soil and / or sediment to harmless substances through the use of biological activity. This process is performed in the solid state in which organic nutrient substances are present. Modified # ‘~ Improved Substances’ and “Soil Modified Substances” mean substances containing organic nutrients, which are mainly used when added to the soil to decontaminate microorganisms. a Pollutant 〃 means HCB and toxic metabolites degraded from HCB. The use of '' degradation of H C B and metabolites when used '' means removal of one or more chlorine atoms and / or cleavage of the benzene ring. " Harmless substance means that the concentration of the substance in the soil or sediment is unquestionable. w HC Β 的 toxic metabolite # means the degradation product of HC Β, this paper size applies to the National Standard (CNS) A4 specification (210 X 297 mm) — III — — — — — — 111 — ^ I ί i 11 I «Ι1ΙΙΙΙ1Ι — — — Υ (Please read the notes on the back before filling out this page) Seal of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 46 5 8 5 A7 ____B7 V. The description of the invention (5) is transferred from the HCB molecule Except for one or more chlorine atoms, η CB 尙 is not completely degraded to harmless substances. '' Decontamination effect '' means that the transformed pollutant is a harmless substance, including biological degradation of the pollutant and / or binding of the pollutant to soil or other substances. Α Correction means decontamination of contaminants in soil / sediment to the point where it is not objectionable. Soil means land, for example: humus soil, sand and granular rocks, and sediments that come from above or below the water surface. DETAILED DESCRIPTION OF THE INVENTION In the degradation step of the treatment of the present invention, the soil to be decontaminated must contain a treatment capable of degrading the contaminant through the treatment of a suitable type of viable microorganisms. Therefore, anaerobic and aerobic microorganisms must be present, and these microorganisms must be able to survive in anaerobic and aerobic conditions so that they can exist in this process. Furthermore, when the stacked mixture is treated in an anaerobic and aerobic state, this microbiota cannot be killed or adversely affected so that they do not sufficiently degrade HCB. These microorganisms are usually bacteria, fungi, actinomycetes, and a small number of protozoa. As will be described later, the first step of the present invention is to prepare a suitable inoculum from microorganisms. The microorganisms are initially present in the soil to be treated so that they can adapt to contaminants and decontaminate them. Additional viable microorganisms can be recycled from decontaminated soil. In the practice of the present invention, the preparation of the solid heaping mixture is achieved by decontamination by mixing suitable soil improvement materials into the soil, wherein the improvement materials account for at least 10% of the total amount, up to the weight of the mixture. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 male; 8) -------.--- j --- ^) ------- Order ---- ----- Line--Y (Please read the precautions on the back before filling this page) -8-4465 85 Α7 Β7 Printed by the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Production Description (6) 9 5% , And preferably about 30% to 70% by weight of the improved substance, some may already exist in the soil. Soil improvement materials include a customary organic nutrient source for microorganisms during the composting process. = Better modification nutrients are agricultural waste and municipal sewage sludge, such as horse, cattle, sheep, turkey, chicken or fish manure. Or activated sewage sludge is preferred. Alfalfa, hay, sawdust, sludge, pasture, and other bulking materials may be present in the composting mixture, and the origin of the manure may be specifically added. Inoculum is added to the stacking mixture in sufficient amounts to significantly affect the population of microorganisms. At least 1% is required, and preferably 1-2% of inoculum volume / volume is added to the improved material. In some cases it may be necessary to include a surfactant in soil improvement to make pollutants more susceptible to biological degradation. Suitable surface-active agents include polysorbates, caprylic polyols, anionic alkyl sulfates, anionic alkyl aryl sulfates, and ethoxylates. Examples of suitable surfactants include TWEEN® nonionic surfactants from ICI Americas, Inc., TRITON® nonionic surfactant products from Union Carbide, and DAWNTM detergent products from Procter & Gamble. Improved substances can also contain or supplement liquid or solid organic or inorganic nutrients. Organic substances containing high levels of nitrate and phosphate are often used. The stacked mixture is maintained in a solid state containing moisture. Through the whole process, the water retention (w H C) of the mixture whose humidity is maintained at less than 1000% is preferably about 40 to 70%. After mixing, the biodegradation of organic substances in the mixture begins, increasing the temperature and consuming oxygen to make it anaerobic. This paper is then mixed. This paper size applies the Chinese standard (CNS > A4 size (210 X 297 male cage) < Please read the precautions on the back before filling this page)
- I 甘.^— 111 11 —訂·1 — — If — — ---W---I i 1111------I------I -9- 4465 A7 B7 五、發明說明（7 ) 物的溫度維持在2 0 - 6 5 °C的範圍內，可經由控制透過 堆製混合物的空氣移動（譬如透過導管）以及/或經由加 入營養物質來輕易完成。低於2 0°C時，生物降解作用進 行慢得不符合經濟效應，而高於6 5 °C時可能會發生過多 的微生物被殺死。較佳的溫度範圍是約2 0 — 5 0 °C。堆 製混合物內的厭氧微生物在接下去的有氧降解步驟中仍可 存活，以及此厭氧微生物在繼續之無氧降解步驟的任何需 要中仍可存活。因此，本發明之處理過程必需維持好氧和 厭氧降解微生物的存活。 無氧步驟期間，堆製混合物是維持低的氧化還原電位 ，至少約負200mV，而以負300mV到500mV 爲佳，此範圍已發現是無氧過程的最適合範圍。經由透過 堆製處理的濕空氣移動以及/或經由加入慣用的還原劑， 譬如亞硫酸鹽和醋酸鹽還原化合物來維持氧化還原電位在 此範圍內11 第一次無氧步驟和任何接下去的無氧步驟持續至一顯 著量的污染物被降解爲止，而此可藉由分析決定之。典型 情況是在第一次無氧步驟中降解3 0%到7 〇%的H C B 污染物初始含量。在第一次無氧階段內的土壤/糞肥混合 物中的污染物含量顯著減少之後，經由任何合適的方法氧 化此混合物，以經由給與空氣和/或與混合物混合至達到 有氧狀態爲佳。在有氧處理期間的氧化還原電位要適合於 足夠的氧化作用必需維持在正1 〇 〇 m ν以上°此有氧狀 態進一步活化降解作用來產生無害物質’此有氧降解步驟 本纸張又度通用中®國家櫟單（CNS)A4規格（210x 297公芨） (請先間讀背面之泫意事項再填寫本頁) 經濟部智慧財產局員工消費合作.钍印裂 -------^---------線—-----—------------------ -10- 經濟部智慧財產局8工消費合作社印髮 446 5 85 Α7 ___ Β7 五、發明說明（8 ) 持續到以有氧處理後之污染物的量顯著被降解。 在大部分案例中，在第一次無氧/有氧處理順序中無 法達到將污染物生物性降解作用至可接受的矯正程度。在 '極好的無氧/有氧處理順序過程中，爲使土壤除污至可接 受程度需持續重覆一次或更多次是必需的。經由此多次_ 順序較佳處理可達到持續性完全矯正、改良的作用。 此處理的所要特性是此降解用微生物在無氧/有氧處 理循環中需維持可活性，使重覆此處理循環前不需要再補 充微生物。然而，加入更多改良物質、糞肥或其它常用發 酵組成分是需要的，主要是補充此有機原料的補給，並也 導入更多的膨脹劑。 如前文所述，要有效率實行本發明處理，在無氧和有 氧步驟中的堆製混合物維持適當的氧化還原電位是必需的 。合適的氧化還原電位可經由加入慣用的營養物質和/或 亞硫酸鹽和/或醋酸鹽化合物等還原劑來維持。絕對無氧 和有氧狀態是必需的（雖然短暫局部偏離是可預期的）。 爲本發明之目的，氧化還原電位少於負2 0 OmV就視爲 無氧，且是無氧步驟所必需：以及氧化還原電位大於正 1 0 OmV就視爲有氧，且是有氧步驟所必需。無氧步驟 期間，氧化還原電位以負3 0 0到5 0 0 m V爲佳：以及 在有氧步驟期間，氧化還原電位以正2 0 0到3 0 0 m V 爲佳。氧化還原電位在負2 0 OmV到正1 0 OmV視爲 缺氧的。在本發明中，從無氧進行到有氧狀態時1以及反 觀時，缺氧狀態是存在於堆製混合物中。在此期間會發生 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇χ 297公;" -11 - ^ J---兮、^--------訂---------線--W------------------------ (請先閱讀背面之泫意事項再填寫本頁) 446585 經濟部智"时產局員工消費合作：ΐ!印設 Α7 Β7 五、發明說明（9 ) 一些污染物的降解作用，但速率很慢。因此，迅速從一狀 態轉移到另一狀態可加速完整之降解作用。 實行化合物時，可能可設計成在一部分的堆製混合物 '中是有無氧狀態，且同時在另一部分是有氧狀態，這是合 適的•因爲在堆製混合物的不同部分具有不同的初始污染 物濃度和/或降解速度。因此，爲達降解作用的一致，堆 製物的一些部分要維持較長的無氧或有氧狀態是必需的。 堆製處理期間會出現高微生物計數，以每公克最多 1 〇8有氧菌落形成單位（c i U )爲佳，可經由標準平板 計數技術測量之，而無氧最多以1 〇 6 c f U /克爲佳。這 些微生物計數當然包括降解污染物之外的微生物。 實行本處理是在一堆製處理容器內操作，通常是在一 容器小室或堆列成排內實行。欲處理的土壤可在實驗室內 分析及堆製，以決定最適合的改良組成分條件，以及無氧 /有氧處理時間和順序號碼。 如上所述，本發明過程包括在無氧堆製處理階段後再 一無氧堆製階段。然而，可在第一次無氧階段前將土壤初 始的無氧處理，以使先前已存在的不合適物質含量降低。 以下範例是例舉本發明的較佳實行例。 範例1 製備一使用於將含有H C B 土壤除污作用的接種物， 將2 5毫升稀釋異營性培養基*混合6 2 5微升的2毫克/ 毫升HC Β甲醇溶液和5 0%的未受污染土壤。然後將接 本紙張尺度適用中國國家標準（CNS) A4規格（2]0 * 297公釐） --------τ---#---'^^-------訂---------線 1，^------------------------- (請先閱讀背面之注意事項再填寫本頁) -12- 4 4 6 5 8 5 A7 B7 五、發明說明（10 ) 種物貯存在無氧狀態的無氧室中2 2 °C 6週。 然後將約含25ppm HCB的1公 )土壤與含有4 0 0 〇毫升牛糞肥的堆製混 毫升的稻草和上述的5 0毫升接種物混合。 覆做一次，並將此混合物在室內無氧堆製處 間的無氧堆製混合物的保水力、氧化還原電 分別約7 0 %，低於2 5 ◦ m V，及2 2 °C 的H C B降解作用。 之後，藉由氧化作用提升氧化還原電位 物成有氧狀態。在此期間的W H C、氧化還 平均分別約70%，高於200mV及34 著的進一步污染物降解作用於有氧階段期間。 這些連續無氧/有氧處理的8週階段重. 致上將更·多污染物降解。本實驗所得的降解 ，依照此技術在大規模除污作用中，可得到 矯正。 *稀釋之異營性培養基組成： 斤（6 〇毫升 合物，及5〇 相同的樣本重 理6週。此期 位及溫度平均 ，則發生顯著 使此堆製混合 原電位及溫度 °C，則發生顯 複一次，可大 作用程度指出 最想要的合適 ,---^----------訂---------線--》， (請先閱讀背面之沒意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 葡萄糖 0.1克/升 酵母菌萃取物_ 0.1克/升 蛋白脾 -0,05克/升 *** _ 〇.〇5克/升 Μσ30 · — 0.6 克/升-I Gan. ^ — 111 11 —Order · 1 — — If — — --- W --- I i 1111 ------ I ------ I -9- 4465 A7 B7 V. Invention Note (7) The temperature of the substance is maintained in the range of 20-65 ° C, which can be easily accomplished by controlling the air movement through the stacking mixture (such as through a duct) and / or by adding nutrients. Below 20 ° C, biodegradation is slow to comply with economic effects, while above 65 ° C, too many microorganisms may be killed. The preferred temperature range is about 20-50 ° C. The anaerobic microorganisms in the composting mixture will survive the subsequent aerobic degradation step, and the anaerobic microorganisms will survive any need for the continued anaerobic degradation step. Therefore, the treatment process of the present invention must maintain the survival of aerobic and anaerobic degradation microorganisms. During the anaerobic step, the stacking mixture maintains a low redox potential, at least about negative 200 mV, and preferably between negative 300 mV and 500 mV. This range has been found to be the most suitable range for anaerobic processes. The redox potential is maintained in this range by the movement of humid air through the stacking process and / or by addition of conventional reducing agents such as sulfites and acetate reducing compounds. 11 The first anaerobic step and any subsequent The oxygen step continues until a significant amount of pollutants are degraded, which can be determined by analysis. A typical situation is the degradation of 30% to 70% of the initial H C B pollutant content in the first anaerobic step. After a significant reduction in the content of contaminants in the soil / manure mixture during the first anaerobic phase, the mixture is oxidized by any suitable method, preferably by aerating the air and / or mixing with the mixture to achieve an aerobic state. The redox potential during aerobic treatment is suitable for sufficient oxidation. It must be maintained above 1000 m ν. This aerobic state further activates the degradation to produce harmless substances. This aerobic degradation step of this paper General China® National Oak List (CNS) A4 Specification (210x 297 cm) (Please read the intentions on the back before filling out this page) Consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs. -^ --------- 线 ——--------------------------- -10- Printed by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Fat 446 5 85 Α7 ___ B7 V. Description of the invention (8) Continue until the amount of pollutants treated with aerobic treatment is significantly degraded. In most cases, biodegradation of pollutants to an acceptable level of correction was not achieved during the first anaerobic / aerobic treatment sequence. During the 'excellent anaerobic / aerobic treatment sequence, continuous repetition of one or more times is necessary to decontaminate the soil to an acceptable level. After this many times, the sequential better treatment can achieve the effect of continuous complete correction and improvement. A desirable characteristic of this treatment is that the degradation microorganisms need to remain active during the anaerobic / aerobic treatment cycle, so that it is not necessary to replenish the microorganisms before repeating the treatment cycle. However, it is necessary to add more improved substances, manure or other commonly used fermentation components, mainly to supplement the supply of this organic raw material, and also to introduce more expansion agents. As mentioned earlier, in order to effectively carry out the process of the present invention, it is necessary to maintain the proper redox potential of the stacked mixture in the anaerobic and aerobic steps. A suitable redox potential can be maintained by adding conventional nutrients and / or reducing agents such as sulfite and / or acetate compounds. Absolute anaerobic and aerobic conditions are required (although transient local deviations are to be expected). For the purposes of the present invention, an oxidation-reduction potential of less than negative 20 OmV is considered anaerobic, and is necessary for the anaerobic step: and an oxidation-reduction potential greater than positive 10 OmV is considered aerobic, and it is the essential. During the anaerobic step, the redox potential is preferably from 300 to 500 m V: and during the aerobic step, the redox potential is preferably from 2000 to 300 m V. A redox potential between negative 20 OmV and positive 10 OmV is considered hypoxic. In the present invention, from the anaerobic state to the aerobic state1 and, in contrast, the anoxic state is present in the stacking mixture. During this period, it will happen that this paper size applies the Chinese National Standard (CNS) A4 specification (2) 0 297 297; " -11-^ J --- Xi, ^ -------- order --- ------ Line--W ------------------------ (Please read the notice on the back before filling this page) 446585 Economy Ministry of Intellectual Property   Consumer Affairs Cooperation of the Time Production Bureau: ΐ! 印 A7 Β7 V. Description of the Invention (9) The degradation of some pollutants, but the rate is very slow. Therefore, the rapid transition from one state to another can accelerate the completeness It may be possible to design the compound to have an anaerobic state in one part of the compounded mixture and an aerobic state in the other part when implementing the compound. This is suitable because different parts of the compounded mixture have different Initial pollutant concentration and / or degradation rate. Therefore, in order to achieve consistent degradation, it is necessary for some parts of the stack to maintain a long anaerobic or aerobic state. High microbial counts occur during the stacking process , Preferably a maximum of 108 aerobic colony forming units (ci U) per gram, which can be measured by standard plate counting techniques without A maximum of 106 cf U / g is preferred. These microbial counts, of course, include microorganisms other than degrading contaminants. This treatment is performed in a stack of processing vessels, usually in a container cell or in a row. The soil to be treated can be analyzed and piled in the laboratory to determine the most suitable improved composition conditions, as well as the time and sequence number of the anaerobic / aerobic treatment. As described above, the process of the present invention includes the anaerobic reactor. The anaerobic composting stage is followed by the processing stage. However, the initial anaerobic treatment of the soil can be performed before the first anaerobic stage to reduce the content of pre-existing unsuitable substances. The following examples illustrate the invention Example 1 Preparation of an inoculum for decontamination of soil containing HCB, 25 ml of diluted heterogeneous culture medium * mixed 6 2 5 microliters of 2 mg / ml HC Β methanol solution and 5 0% of uncontaminated soil. Then the paper size will be applied to the Chinese National Standard (CNS) A4 specification (2) 0 * 297 mm) -------- τ --- # --- '^ ^ ------- Order --------- line 1, ^ ------------------------- (Please read the precautions on the back before filling this page) -12- 4 4 6 5 8 5 A7 B7 V. Description of the invention (10) The species are stored in an anaerobic chamber at 2 ° C for 6 weeks. One milliliter of soil containing approximately 25 ppm of HCB was then mixed with a milled milliliter of straw containing 4000 milliliters of cow manure and the 50 milliliter inoculum described above. Cover it once, and store the mixture in the indoor anaerobic stacking site. The water retention capacity and redox capacity of the anaerobic stacking mixture are about 70%, less than 2 5 ◦ m V, and HCB at 2 2 ° C. Degradation. Thereafter, the oxidation-reduction potential is raised to an aerobic state by oxidation. During this period, W H C and oxidation also averaged about 70%, respectively, and further pollutant degradation above 200 mV and 34 during the aerobic phase. The 8-week phase of these continuous anaerobic / aerobic treatments is heavy. As a result, more pollutants are degraded. The degradation obtained in this experiment can be corrected in large-scale decontamination according to this technology. * Diluted heterogeneous culture medium composition: kg (60 ml of the compound, and 50 of the same sample were reprocessed for 6 weeks. At this stage and the temperature averaged, a significant increase in the stacking potential and temperature ° C occurred, It will happen again and again, and it can indicate the most suitable fit with a great degree of effect, --- ^ ---------- Order --------- line-- "(Please read first Please fill out this page on the back of the page.) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed glucose 0.1 g / L yeast extract _ 0.1 g / L protein spleen-0,05 g / L trinitrotoluene _. 〇5 g / L Μσ30 · — 0.6 g / L
CaCb , 2ΗΌ — 0.07 克/升 MOPS - 0.1 克/升 維生素(BME 100X)—】.〇毫升/升 Ho-Le's礦物質—丨.〇毫升/升 2莫耳濃度磷酸鹽水溶液—I·0毫升/升PH7.53 本纸張尺度適用中國國家標準（CNS>A4堤格（210x297公釐） -13 - 446585 經濟部智慧財產局員工消費合泎社扣裂 A7 B7 ^____ _________ 五、發明說明（11 ) 範例2 - 8 實驗程序依照範例1 ’但改良（堆製混合物）組成分 ’堆製處理時間和堆製條件如下表所指示。在每一個範例 中，接種物的製備是依照範例1的程序。CaCb, 2ΗΌ — 0.07 g / l MOPS-0.1 g / l vitamins (BME 100X) —] .0 ml / l Ho-Le's minerals — 丨 ml / l 2 molar aqueous phosphate solution — 1.0 ml / Liter PH7.53 This paper size applies the Chinese national standard (CNS > A4 Tiege (210x297 mm) -13-446585 Employee Consumption Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Spike A7 B7 ^ ____ _________ 5. Description of the invention ( 11) Examples 2-8 The experimental procedure is in accordance with Example 1 'but modified (compounded mixture) composition'. The processing time and conditions are indicated in the table below. In each example, the inoculum was prepared according to Example 1. program.
表I 實驗號碼 改良物質（體積/體積） 土壤內容物 無氧/有氧 階段時間 順序 2 馬糞肥-20% 6/4週 1 3 雞糞肥-35% 4/2週 3 4 下水道污泥-80% 6/3週 1 5 牛糞肥-60% 8/3週 2 6 3 0 %污泥，2 0 %牧草 3/3週 1 7 魚糞肥，80% 4/5週 2 8 馬糞肥，40% 4 / 4週 2 本發明在任何號碼的方法中因人爲技藝及全部可見之 相同情形而有所改變，但這些仍落在此說明書及申請專利 範圍內。本說明書可提供解釋說明申請專利的指引，但沒 必要限制其內容。 本纸張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公« ) . Ϊ---*--I -------^-----------W------------------------- (請先閲讀背面之注意事項再填寫本頁) -14-Table I Experiment number Improved substance (volume / volume) Anaerobic / aerobic phase time sequence of soil contents 2 Horse manure-20% 6/4 weeks 1 3 Chicken manure-35% 4/2 weeks 3 4 Sewer sludge-80 % 6/3 weeks 1 5 cattle manure-60% 8/3 weeks 2 6 3 0% sludge, 20% pasture 3/3 weeks 1 7 fish manure, 80% 4/5 weeks 2 8 horse manure, 40% 4/4 week 2 The method of the present invention has been changed in any number of methods due to man-made skills and all the same visible conditions, but these still fall within the scope of this description and patent application. This specification provides guidance to explain patent applications, but it is not necessary to limit its content. This paper size applies to China National Standard (CNS) A4 specification (2) 0 X 297 male «). Ϊ --- *-I ------- ^ ----------- W ------------------------- (Please read the notes on the back before filling out this page) -14-