材種從某些工業程序之廢氣流製造產物、 氫、醇、盘有機給與如有機酸、單一細胞蛋白質rscp”）、 ，尤並關认一鹽寺物之方法、程序、微生物、與裝置 成此轉換之3於厭氣條件下使用連續氣體基質發酵以達 ^造有機酸、醇、氫與有機酸鹽之傳統步驟爲石油衍生 妄U(化學合成。石油快速上揚的成本使得利用更新或廢 ^乍爲儲料之發酵程序所製造的這些有價値商品已產 相當大的利潤。爲發酵所得副產物之單-細胞蛋白質可 用作動物飼料。 -、 ^ τ 經濟部中央標隼局員工消費合作社印製 、對於—傳統工業程，序所產生之大量空氣污染物與溫室氣體 π有著日盈急迫之關切。環境保護機構近來評估，工業界 f年排放超過六百萬公噸之一氧化碳與將近四百萬公噸之 風氣。一本質部分之此廢棄一氧化碳與氫氣爲碳黑製造與 煤焦生產之結果，大致上爲2.6百萬公噸之C0與〇.5百萬公 八之H2大曼的一氧化竣或氫氣亦可由氨工業（丨991年有 5,144 a哺之C 0 )、煉油（每一千桶8公嘴）、製鋼（每製得 么噸鋼有152磅）、與硫酸製漿（每噸木漿286镑）產生。在 1991年，己二酸工業產生40,773公噸之一氧化碳，其作爲 燃料價値燃燒掉或驟燃掉。在很多情形下，這些氣體被直 ，接排放至大氣中，對環境造成重大的污染負擔。 典型上’工業產物製造所帶來之廢氣於低壓與低溫下釋 放。現今之技術無法利用此種條件下之這些稀釋氣體。採 用現存之技術從這些廢物流中分離與回收氫氣或一氧化碳 _____—___ - 4 - 本纸浪尺Ϊ適用中國國家標準（CNS ) A4規格（2I0X297公慶) - -- 2542857 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 相當筇貴且不實際。 η Q所述對於利用上述廢氣並以石油衍生儲料之化學 合成外（万法製得產物、材料、中間產物、及如有機酸、 醇氫、與有機酸鹽等物方面，有其成本效益與實用方法 、微生物與設備上之需求。 發明概述 根據本發明，從工業程序之廢棄一氧化碳、氫及/或二氧 化碳製造產物、材料、中間產物、與如有機酸、醇、氫、 單一細胞蛋白質及/或有機酸鹽等物，藉以降低污染，同時 節省能源與化學儲料。 — ' 根據本發明之一舉例方法，將稀釋氣體中之所欲成分引 入含一或多種厭氣菌培養菌株之生物反應器中，該菌以一 直接心途徑利用該廢氣成分，而產生所欲之化合物。於分 離器中利用一適合所製得化合物之回收方法從水相中回收 孩化合物。回收方法之實例包括萃取、蒸餾、或其組合、 或其它有效的回收方法。將細菌由水相中移出並回流，以 避免毒性並維持高細胞濃度，因此使反應速率答最大。若 有必要’以離心、膜超濾、或其他技術達成細胞分離。 本發明之主要目的在於提供一種從一氧化礙、氫及/或二 氧化竣製造產物、中間產物、材料、與如有機酸、氫、單 =細胞蛋白質、醇及/或有機酸鹽等物之方法及/或微生物 本發明之另一目的在於提供從如煉油、後黑、煤焦、氨 、與甲醇製造等工業程序之廢氣流製造有機酸、醇、氫、 -5- 衣纸張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項寫本頁) 裝· .鼈 A7 B7 五、 發明説明 在本發明之發展中，已單離出新的厭氣菌菌株，其以高 ^率使此轉化作用。此外，對某㈣株發酵條件之修飾會 導致產生乙醇而非醋酸。從廢氣形成產物時必須列入考虞 之變數視所使用之特殊微生物而定，包括營養组成與濃度 、介質、壓力、溫度、氣體流率、液體流率、反應pH値、 攪動速率（若使用連續式攪拌槽反應器）、接種度、避免抑 制之最大基質（引入氣體）濃度、與避免抑制之最大產^濃 經濟部中央標準局員工消費合作社印製 根據本發明如圖式中圖丨所示之一示範實例，轉化程序中 之第一步驟爲厭氣菌營養基（10)之製備。營養基之内容物 根據所用厭氣菌型式與所欲產物而有所不同。將營養基穩 定進、’、σ至發酵槽反應器（12)，其包含一或多個容器及/或 塔 '其型式包括連續攪拌式（CSTR)、固定床式（ICR)、滴流 床式（TBR)、氣泡管式、氣提式發酵槽，或其它適合之發 酵反應器。在生物反應器（12)中置有該氣體轉化程序中所 用之厭氣菌之單純或混合培養物。就CSTR、TBR、氣泡管 式與氣提式發酵槽而言，這些細菌分散在整個反應器液相 中而生存，但就ICR而言，細菌黏著至内部之堆疊介質。 此堆®介質必須提供最大的表面積、高質傳速率、低壓滴 降、甚至氣體與液體分佈、且必須使栓塞、堵塞、結巢與 •牙出壁道之情形減至最小。此種介養材料之實例有陶磁伯 爾鞍（ceramic Bed saddle)、拉西環（Raschig ring)或其它高 效堆疊物。 將廢氣（14)連續引入生物反應器（12)中。該氣體被留置於 -9 - 私纸張尺度適用中國國家標準（CNS ) A4規格（210X297公慶） 542857 A7 B7 五、發明説明（7 ) 生物反應器（12)中一段使程序效率最大之時間。然後釋放 出含鈍性物與未反應基質氣體之排放氣體（16)。該液體流 出物（18)通過一離心、中空纖維膜或其它過濾裝置（2〇)，以 分離出夾帶之微生物。使這些微生物（22)回到生物反應器 (12)中，以維持高細胞濃度，而得致較快之反應速率（細胞 回收）。 本程序之下一步驟爲將所欲之生物法製得產物從滲透物 或離心物（24)中分離。在圖1所示之實施例中，使滲透物或 離心物（24)通至一萃取室（26)，於此處與一溶劑（28)接觸。 該溶劑（28)應具有所欲最終產物之高分佈係數、高回收因 子、對人類低毒性、對細菌低毒性、與水不互溶、適度之 高滞點’且不與生物反應器成分形成乳化物。溶劑與水相 間溶質之分佈將決定熱力學之可施行性與所需移出最終產 物之溶劑量。典型之溶劑包括適當溶劑中之二級與三級胺 、適‘共么劑中、之續酸三丁基g旨、乙酸乙酯、三辛基膦氧 化物與相關化合物、長鏈醇、己烷、環己烷、氯仿、與四 氣乙歸^。 經濟部中央標準局員工消費合作社印製 水相（30)中之營養與物質通回至生物反應器（12)中，而溶 劑/酸/水溶液（32)通至一蒸餾管柱（34)，於此處加熱至一足 以將溶劑（28)與酸和水（36)分離之溫度。該溶劑（28)由蒸餾 管柱（：> 4)經過一冷卻室（3 8)以使溫度—降至最適於萃取之溫度 ，然後回到萃取室（26)再使用。該酸和水溶液（36)通至一終 端蒸館管柱（40)，所欲之最終產物（42)於此處與水分離並移 出。水（44)則循環以爲營養製備所用。 __ -10- 本紙張尺度適用中國國家標準（CNS ) M規格（21〇χ 297公釐 五、發明説明（ % 圖- tf由廢氣（48)製造道路除冰醋酸鈣鎂（CMA)(46)之 程序：該程序與圖1透過溶劑萃取之醋酸程序相同。亦即 ’於連~發酵巾使用相同的有機體、營養與程序條件，包 括反應槽。類似地，在該程序中亦同樣使用中空纖維膜、 離心:或其它過濾、裝置。最後，進行萃取室中醋酸之萃取 ’接者無酸介質之回收。 萃取後，產生CMA之方法與圖丨中之醋酸製程大不相同 。在IXCMA程序中，含醋酸與少量水之溶劑（5〇)被送至反 應芬〇2)中以爲CMA生產所用。溶劑流中之水含量視用於 醋酸萃取中之落劑而定。適當共溶劑中之二級與三級胺、 適备共，谷劑中之磷酸三丁基酯、乙酸乙酯、三辛基膦氧化 物與相關化合物、長鏈醇、己烷、環己烷、氯仿、與四氯 乙烯等落劑再度可用，而效用不同。CMA之反應槽（52)最 適合者爲連續式攪拌槽反應器（CSTR)，雖然可用其它反應 器系統。於水中之白雲石灰（dolomitic lirne)與氧化鎂混合 物（54)被加至含醋酸與水之溶劑中。反應於水溶液中於飽 和程度或低於飽和程度下發生，以製得CMA。 經濟部中央標準局員工消費合作社印製 然後將CMA、水與溶劑（56)送至一靜置澄清裝置（58)， 以將水相與溶劑相分離。使溶劑相（60)回到萃取室以循環 。該CM A/水（62)被送去乾燥/顆粒化（64)以製得顆粒化之 CM A產物。 —： 〜可以苛性鉀鹼（或氧化鉀）代替.白雲:石灰而製得另種產物 醋酸鉀（KA)。因K A係以5 0個百分比之水溶液製得，不需 乾燥與顆粒化。 -11 - 本纸張尺度適用中國国家標準（CNS ) A4規格（210X297公釐） 542857 A7 B7 五、發明説明（9 ) 圖3顯示由廢氣製造乙醇之程序。如圖1中者，將廢氣（66) 與營養（68)進給至一包含微生物培養物之反應器（70)。該反 應器可爲前述圖1中所述各式中之任一者。用於乙醇生產 程序中之有機體必須可產生乙醇，而非乙酸/乙酸乙酯。一 般而言，需要4.0-5.5之低發酵pH値，並配合營養上之限制 。於降低pH下可運作之前述所列細菌可用於此乙醇之製造 程序中。 將廢氣連同所需營養進給至可製得乙醇之包含微生物培 養物之反應器中。以如圖1中之類似方式製得乙醇作爲產 物。細胞回流（72)可用以增加反應器中之細胞濃度，但此 操作對该程序之工作而s並非必要。來自細胞回流裝置之 介質中包含稀釋乙醇之滲透物（74)被送去蒸餾（76)，水（78) 與乙醇（80)於此處分離。9 5個百分比之乙醇離開蒸館管柱 之頂端，而水（用過的介質）離開管柱之底部。用過的介質 被送回反應器作爲水回流。該9 5個百分比之乙醇被送至一 分子篩系統（82)以製得無水乙醇（84)。 經濟部中央標準局員工消費合作社印製 因此根據本發明，現在可利用氣體基質發酵產生有價値 之有基酸、醇、或有機酸鹽，不但降低了有價値化學儲料 之消耗，又從很多工業之廢氣流中移除了有害之大氣污染 物。前述以生物方式衍生這些化學品之方法係根據糖的 發酵。 、， 、在前述方法中，較佳者爲於高於1夫氣壓下進行之方法。 較佳於至高達30大氣壓下進行，更佳至高達2〇大氣壓下而 最佳至.高達1 5大氣壓下進行。 _ -12- 本紙張尺度適用中國國家標準（CN’S ) A4規格（210x7^公釐) 一--—_____ 542857 A7 B7 10 五、發明説明（ 以下 < 特殊實例用以説明但非限制本發明。除非另有指 明，否則說明書中與申請專利範圍中之所有份數與百分比 均根據體積而言。 實例1 由碳黑廢氣產製醋酸 此實例係關於用以將與碳黑製造之火爐所排放者相符之 廢氣組成物轉化爲醋酸之方法。該廢氣之組成爲約13個百 分比之一氧化碳、14個百分比之氫與5個百分比之二氧化 碳，而剩餘之68個百分比大多爲氮和微量之氧與硫化合物 。孩等廢氣之得致係因氣體或油與不足之空氣部分氧化而 形成非晶碳之結果，每磅元素碳產生約12磅之一氧化碳。 這些廢氣形成一系列空氣污染問題，亦代表著目前無法回 收有價値之化學儲料資源。 二在本万法<發展上，研究兩種不同的由碳黑廢氣產製醋 酸I途徑。直接途徑爲使(：〇與112〇或H2*c〇2分別根據式 (1)與（2)直接轉化爲醋酸。非直接途徑涉及使c〇與h2〇利 用水氣偏移反應轉化爲Η,與C〇2，然後由h2與C〇2製得醋 酸。發現此非直接途徑之技術利用較不具效率。 經濟部中央標準局員工消費合作社印製 所測試之醋酸原摘錄於表i中。在這些直接由C 〇製得 醋酸細菌中，醋酸菌屬之A· kivui與該新單離之菌株梭狀芽 ，胞桿菌屬之C· ljungdahlii ERH顯示_出,極優的⑶與％利用率 。·進一步之實驗係利用此兩種厭氣菌:而進行。 同時利用一氧化碳和氫之細菌有明顯之優點。此會提供 最有效之廢氣利用，並移除最大量之大氣污染物。 -13 - 張尺度適用中國國家標準（CNS ) A4規格（训幻97公釐） 542857 A7 B7 五、發明説明（13 ) h3bo3 300毫克 CoC12*6H20 200毫克 CuC12*H20 10毫克 NiCl2*6H20 20毫克 NaMo04*2H20 30毫克 Na2Se03 10毫克 蒸館水 1000毫升 10.0毫升維生素B 鹽酸吡哆醛 1 〇毫克 核黃素 50毫克 硫胺素 50毫克 於驗酸 50毫克 Ca-D-泛酸鹽 50毫克 硫辛酸 60毫克 P-胺基苯甲酸 50毫克 葉酸 20毫克 生物素 20毫克 維生素b12 50毫克 蒸餾水 1000毫升 經濟部中央標準局員工消費合作社印製 6. 0.5克半胱胺酸HC1 7. 0.06克 CaCl2 · 2H20 … -8. 2.0克 NaHC03 * 9. 1.0毫升重氮樹脂驗（；^532111*丨11)(0.01%) 1 0. 920.0毫升蒸餾水 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 542857 A7 B7 五、發明説明（14 請 先 閲 背 之 注 意 事 項 雲I 彥裝 頁 使用醋酸菌屬之A. kivui時，將營養基溶液之pH調至6.6， 而使用新菌株梭狀芽胞桿菌屬之C. ljungdahlii ERI-2時，將 pH調至4.9。於較低pH下操作之能力爲醋酸回收中之一優 點。然後以20% CO2與80%N2氣氛噴灑該溶液20分鐘，然 後於厭氣下轉移並高溫滅菌1 5分鐘。 同時以連續攪拌式反應器（CSTR)與固定床式反應器（ICR) 進行數個實驗。所得結果例示於以下資料中。 使用醋酸菌屬之A. kivui與梭狀芽胞桿菌屬之C. ljungdahlii ERK菌之CSTR實驗 訂 t 以CSTR及梭狀芽胞桿菌屬之厭氣菌C. ljungdahlii EKJW 與醋酸菌屬之A. kivui所進行之工作檯規模操作包含紐布蘭 斯維克科學公司（New Brunswick Scientific)之BioFlo IIC發 酵槽、細胞回收用之中空纖維膜單元、及萃取與蒸餾管柱 。營養基混合物以每分鐘3.2立方公分之速率進給至該生物 反應器。該反應器之容量爲2.5升，於其内維持1.5升之固定 流體高度。在大約每分鐘500立方公分之氣體引入速率下， 以至高達每分鐘1000轉之可變攪拌速度攪動該流體。該氣 體進給因細菌吸入而變，其反過來爲細胞密度之函數。 經濟部中央標準局員工消費合作社印製 來自生物反應器之液體以每分鐘55至70毫升之速率通過 中空纖維膜。從該中空纖維膜中以每分鐘1.5毫升之速率收 集滲透物。此渗透物之分析指出此階段之醋酸/醋酸酯濃度 在超過每升20克之範圍。於4.9之pH下操作，利用梭狀芽 胞桿菌屬之C. ljungdahlii ERI2形成42個百分比之酸形式之 產物。就醋酸菌屬之A. kivui而言，酸產率僅1.4個百分比 -17- 本紙張尺度適用中國國家標準（CMS ) A4規格（210X 297公釐） 542857 A7 p----------- B7 五、發明説明（） 一 15 7 。兩細菌不同次實驗之結果，包括轉化率與產率，摘錄於 表2與3中。Materials are produced from the exhaust gas stream of certain industrial processes, hydrogen, alcohol, organic compounds such as organic acids, single-cell protein rscp "), especially methods, procedures, microorganisms, and devices that recognize a salt compound The third step in this conversion is to use continuous gas substrate fermentation under anaerobic conditions to produce organic acids, alcohols, hydrogen, and organic acid salts. The traditional steps are petroleum-derived processes (chemical synthesis. The rapidly rising cost of petroleum makes use of renewable or Waste ^ These valuable 値 products manufactured by fermentation process of storage materials have produced considerable profits. Single-cell protein, which is a by-product of fermentation, can be used as animal feed.-, ^ Τ Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer cooperative, there is an urgent concern about the massive surplus of air pollutants and greenhouse gases π produced by the traditional industrial process. Environmental protection agencies have recently assessed that the industrial sector emits more than six million metric tons of carbon oxide a year and nearly 4 million metric tons of wind. A substantial part of this waste carbon monoxide and hydrogen is the result of carbon black manufacturing and coal coke production, which is roughly 2.6 million metric tons. C0 and 0.5 million H2 Daman ’s oxidation or hydrogen can also be produced by the ammonia industry (5,144 a C0 in 991), oil refining (8 male mouths per thousand barrels), steel making (each It produced 152 pounds of tons of steel, and produced it with sulfuric acid pulp (286 pounds per ton of wood pulp). In 1991, the adipic acid industry produced 40,773 metric tons of carbon oxide, which burned or burst out as a fuel price. In many cases, these gases are directly discharged into the atmosphere, causing a significant pollution burden on the environment. Typically, the exhaust gas produced by the manufacture of industrial products is released at low pressure and low temperature. Today's technology cannot take advantage of such conditions These diluent gases. Separation and recovery of hydrogen or carbon monoxide from these waste streams using existing technologies _____—___-4-This paper is suitable for China National Standard (CNS) A4 specifications (2I0X297 public celebration)--2542857 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The description of the invention is quite expensive and impractical. Η Q describes the chemical synthesis (products, materials, Intermediate products, and materials such as organic acids, alcoholic hydrogen, and organic acid salts have their cost-effective and practical methods, microorganisms, and equipment requirements. SUMMARY OF THE INVENTION According to the present invention, waste carbon monoxide, hydrogen, and / Or carbon dioxide to make products, materials, intermediates, and things like organic acids, alcohols, hydrogen, single-cell proteins, and / or organic acid salts to reduce pollution while saving energy and chemical storage. — 'According to one of the inventions For example, a desired component in a diluent gas is introduced into a bioreactor containing one or more anaerobic bacteria culture strains, and the bacteria use the exhaust gas component in a straightforward way to produce a desired compound. In a separator The compound is recovered from the aqueous phase using a recovery method suitable for the compound prepared. Examples of the recovery method include extraction, distillation, or a combination thereof, or other effective recovery methods. Bacteria are removed from the aqueous phase and refluxed to avoid toxicity and maintain high cell concentrations, thus maximizing the response rate. If necessary 'achieve cell separation by centrifugation, membrane ultrafiltration, or other techniques. The main object of the present invention is to provide a product, an intermediate product, a material, and an organic acid, hydrogen, a single cell protein, an alcohol, and / or an organic acid salt, etc. Method and / or microorganism Another object of the present invention is to provide production of organic acids, alcohols, hydrogen, and waste paper from waste gas streams from industrial processes such as oil refining, after black, coal coke, ammonia, and methanol manufacturing. China National Standard (CNS) A4 specification (210 × 297 mm) (please read the precautions on the back to write this page).. 鳖 A7 B7 V. Description of the invention In the development of the present invention, a new annoyance has been isolated. Bacterial strains that effect this transformation at high rates. In addition, modifications to the fermentation conditions of a strain can result in ethanol rather than acetic acid. The variables that must be included in the formation of products from the exhaust gas depend on the particular microorganisms used, including nutritional composition and concentration, media, pressure, temperature, gas flow rate, liquid flow rate, reaction pH, agitation rate (if used Continuous stirred tank reactor), inoculation degree, maximum substrate concentration to avoid inhibition (introduced gas), and maximum concentration to avoid inhibition. Concentration printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. An exemplary example is shown. The first step in the transformation procedure is the preparation of the anaerobic nutrient base (10). Nutrient-based contents vary according to the type of anaerobic bacteria used and the desired product. The nutrient base is stably fed into the fermentation tank reactor (12), which includes one or more containers and / or towers, and its types include continuous stirring (CSTR), fixed bed (ICR), trickle bed Type (TBR), bubble tube type, stripping type fermentation tank, or other suitable fermentation reactor. A simple or mixed culture of anaerobic bacteria used in the gas conversion procedure is placed in the bioreactor (12). In the case of CSTR, TBR, bubble tube and stripping type fermentation tanks, these bacteria are dispersed throughout the reactor liquid phase to survive, but in the case of ICR, the bacteria adhere to the internal stacking medium. This stack of media must provide maximum surface area, high mass transfer rates, low pressure drops, and even gas and liquid distribution, and it must minimize emboli, blockages, nesting, and dental exits. Examples of such mediating materials are ceramic bed saddles, Raschig rings or other highly efficient stacks. The exhaust gas (14) is continuously introduced into the bioreactor (12). The gas is left at -9-the size of the private paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public holiday) 542857 A7 B7 V. Description of the invention (7) A period in the bioreactor (12) to maximize the program efficiency . An exhaust gas (16) containing a passive substance and unreacted matrix gas is then released. The liquid effluent (18) is passed through a centrifugal, hollow fiber membrane or other filtering device (20) to separate the entrained microorganisms. These microorganisms (22) are returned to the bioreactor (12) to maintain a high cell concentration, resulting in a faster response rate (cell recovery). The next step in this procedure is to separate the desired biologically produced product from the permeate or centrifuge (24). In the embodiment shown in Figure 1, the permeate or centrifuge (24) is passed to an extraction chamber (26) where it is contacted with a solvent (28). The solvent (28) should have a high distribution coefficient of the desired final product, a high recovery factor, low toxicity to humans, low toxicity to bacteria, immiscibility with water, moderate high stagnation point ', and no emulsification with bioreactor components Thing. The distribution of the solute between the solvent and the water phase will determine the thermodynamic feasibility and the amount of solvent required to remove the final product. Typical solvents include secondary and tertiary amines in appropriate solvents, tributyl glycol, ethyl acetate, trioctylphosphine oxide and related compounds, long chain alcohols, Alkane, cyclohexane, chloroform, and tetrakistrione. The nutrients and substances in the water phase (30) printed by the staff cooperative of the Central Standards Bureau of the Ministry of Economic Affairs are passed back to the bioreactor (12), and the solvent / acid / water solution (32) is passed through a distillation column (34). Here it is heated to a temperature sufficient to separate the solvent (28) from the acid and water (36). The solvent (28) passes through a distillation column (:> 4) through a cooling chamber (38) to reduce the temperature to the temperature most suitable for extraction, and then returns to the extraction chamber (26) for reuse. The acid and aqueous solution (36) are passed to a terminal steaming column (40) where the desired final product (42) is separated from the water and removed. Water (44) is recycled for nutritional preparation. __ -10- This paper size applies the Chinese National Standard (CNS) M specification (21〇χ 297 mm V. Description of the invention (% Figure-tf Calcium acetate acetate (CMA) for road deicing made from exhaust gas (48) (46) Procedure: This procedure is the same as the acetic acid procedure by solvent extraction in Figure 1. That is, 'Yulian ~ fermentation towels use the same organisms, nutrition and procedure conditions, including reaction tanks. Similarly, hollow fibers are also used in this procedure. Membrane, centrifugation: or other filtration, equipment. Finally, the extraction of acetic acid in the extraction chamber, followed by the recovery of acid-free media. After extraction, the method of generating CMA is very different from the acetic acid process shown in Figure 丨. In the IXCMA program The solvent (50) containing acetic acid and a small amount of water is sent to the reaction fen 02) for use in CMA production. The water content in the solvent stream depends on the agent used in the extraction of acetic acid. Two of the appropriate co-solvents Grades and tertiary amines, suitable co-producers, tributyl phosphate, ethyl acetate, trioctylphosphine oxide and related compounds, long chain alcohols, hexane, cyclohexane, chloroform, and tetrachloride in cereals Ethylene equivalents are available again, but their effectiveness is not The most suitable CMA reaction tank (52) is a continuous stirred tank reactor (CSTR), although other reactor systems can be used. A mixture of dolomic lirne and magnesium oxide (54) in water is added to the acetic acid In a solvent with water. The reaction occurs in an aqueous solution at or below saturation level to produce CMA. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and then send the CMA, water and solvent (56) to a static A clarification device (58) was set to separate the water phase from the solvent phase. The solvent phase (60) was returned to the extraction chamber for circulation. The CM A / water (62) was sent to drying / granulation (64) to obtain Granulated CM A product. —: ~ Can be replaced by caustic potash (or potassium oxide). Baiyun: lime to obtain another product of potassium acetate (KA). Because KA is prepared by 50% aqueous solution, not Requires drying and granulation. -11-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 542857 A7 B7 V. Description of the invention (9) Figure 3 shows the procedure for producing ethanol from exhaust gas. Figure 1 The middle one feeds exhaust gas (66) and nutrition (68) to A reactor (70) containing a microbial culture. The reactor can be any of the formulae described in Figure 1 above. The organism used in the ethanol production process must be capable of producing ethanol, not acetic acid / ethyl acetate Ester. Generally speaking, a low fermentation pH of 4.0-5.5 is required, combined with nutritional restrictions. The bacteria listed above that can be operated at a lower pH can be used in this ethanol manufacturing process. The exhaust gas is added into the required nutrients into It is fed to a reactor containing a microbial culture where ethanol can be produced. Ethanol is produced as a product in a similar manner as in Figure 1. Cell reflux (72) can be used to increase the concentration of cells in the reactor, but this operation has Program work is not necessary. The permeate (74) containing diluted ethanol in the medium from the cell reflux device is sent to distillation (76), where water (78) and ethanol (80) are separated. 9 5 percent of ethanol leaves the top of the column in the steaming hall, and water (used media) leaves the bottom of the column. The used medium is returned to the reactor as water reflux. The 95 percent ethanol is sent to a molecular sieve system (82) to produce anhydrous ethanol (84). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. According to the present invention, it is now possible to produce valuable tritium base acids, alcohols, or organic acid salts using gas-based fermentation, which not only reduces the consumption of valuable tritium chemical storage materials, but also Harmful atmospheric pollutants are removed from the industrial exhaust stream. The aforementioned method of biologically deriving these chemicals is based on the fermentation of sugars. Among the aforementioned methods, the method is preferably performed at a pressure higher than 1 husband. It is preferably carried out up to 30 atmospheres, more preferably up to 20 atmospheres and most preferably up to 15 atmospheres. _ -12- This paper size applies to the Chinese National Standard (CN'S) A4 (210x7 ^ mm) I ---_____ 542857 A7 B7 10 V. Description of the invention (Special examples below are used to illustrate, but not limit the invention. Unless otherwise specified, all parts and percentages in the description and the scope of the patent application are based on volume. Example 1 Production of acetic acid from carbon black exhaust gas This example relates to those emitted from a furnace made with carbon black. A method for converting a corresponding exhaust gas composition into acetic acid. The composition of the exhaust gas is about 13 percent of carbon oxide, 14 percent of hydrogen, and 5 percent of carbon dioxide, and the remaining 68 percent are mostly nitrogen and trace amounts of oxygen and sulfur. Compounds. Children's waste gas is caused by the partial oxidation of gas or oil and insufficient air to form amorphous carbon, which produces about 12 pounds of carbon oxide per pound of elemental carbon. These exhaust gases form a series of air pollution problems and also represent At present, valuable chemical storage resources cannot be recovered. 2. In the development of the Benwan Method, two different ways to produce acetic acid I from carbon black exhaust gas are studied. The direct route is to convert (: 0 and 1120 or H2 * c02 to acetic acid directly according to formulas (1) and (2), respectively. The indirect route involves converting c0 and h20 to Η using a water vapor shift reaction. Acetic acid was produced with Co2, and then with H2 and Co2. It was found that the use of this indirect approach was less efficient. The original acetic acid tested by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs was printed in Table i. Among these acetic acid bacteria prepared directly from C0, A · kivui of the acetic acid genus and the newly isolated strain of fusiform buds, C. ljungdahlii ERH of the genus Bacillus showed excellent ⑶ and% utilization · Further experiments are performed using these two types of anaerobic bacteria: while. Bacterial use of carbon monoxide and hydrogen has obvious advantages. This will provide the most efficient use of exhaust gas and remove the largest amount of atmospheric pollutants. -13 -Zhang scale is applicable to China National Standard (CNS) A4 specification (97mm training magic) 542857 A7 B7 V. Description of invention (13) h3bo3 300 mg CoC12 * 6H20 200 mg CuC12 * H20 10 mg NiCl2 * 6H20 20 mg NaMo04 * 2H20 30 mg Na2Se03 10 mg steamed water 1000 10.0 ml vitamin B pyridoxal hydrochloride 10 mg riboflavin 50 mg thiamine 50 mg test acid 50 mg Ca-D-pantothenate 50 mg lipoic acid 60 mg P-aminobenzoic acid 50 mg folic acid 20 Mg biotin 20 mg vitamin b12 50 mg distilled water 1000 ml printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 6. 0.5 g of cysteine HC1 7. 0.06 g of CaCl2 · 2H20… -8. 2.0 g of NaHC03 * 9. 1.0 ml Diazo resin test (; 532532 * 11) (0.01%) 1 0. 920.0 milliliters of distilled water -16- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 542857 A7 B7 V. Description of the invention (14 Please read the note on the back of the page. When using I. kivui of Acetic acid bacterium, adjust the pH of the nutrient-based solution to 6.6, and use the new strain C. ljungdahlii ERI-2 of Clostridium sp. At that time, the pH was adjusted to 4.9. The ability to operate at lower pH is one of the advantages of acetic acid recovery. The solution was then sprayed with an atmosphere of 20% CO2 and 80% N2 for 20 minutes, then transferred under anaerobic conditions and autoclaved for 15 minutes. Several experiments were performed simultaneously with a continuous stirred reactor (CSTR) and a fixed bed reactor (ICR). The results obtained are exemplified in the following data. The CSTR experiment of A. kivui of Acetobacillus and C. ljungdahlii ERK of Clostridium was used to test the CSTR and C. ljungdahlii of anaerobic bacteria of Clostridium and A. kivui of Acetobacter The bench scale operation performed included a New Brunswick Scientific BioFlo IIC fermentation tank, a hollow fiber membrane unit for cell recovery, and an extraction and distillation column. The nutrient-based mixture was fed to the bioreactor at a rate of 3.2 cubic centimeters per minute. The reactor had a capacity of 2.5 liters and maintained a fixed fluid height of 1.5 liters therein. The fluid is agitated at a variable agitation rate of up to 1000 revolutions per minute at a gas introduction rate of approximately 500 cubic centimeters per minute. This gas feed is changed by the inhalation of bacteria, which in turn is a function of cell density. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The liquid from the bioreactor passes through the hollow fiber membrane at a rate of 55 to 70 ml per minute. Permeate was collected from the hollow fiber membrane at a rate of 1.5 ml per minute. Analysis of this permeate indicated that the acetic acid / acetate concentration at this stage was in the range of more than 20 grams per liter. Operating at pH 4.9, C. ljungdahlii ERI2 of Clostridium was used to form 42% of the product in acid form. As far as A. kivui of the acetic acid genus is concerned, the acid yield is only 1.4% -17- This paper size applies the Chinese National Standard (CMS) A4 specification (210X 297 mm) 542857 A7 p -------- --- B7 V. Description of the Invention (1) 15 7. The results of different experiments of the two bacteria, including conversion and yield, are summarized in Tables 2 and 3.
使用細菌菌株梭狀芽胞桿菌屬之c ljungdahlii Erj;_2之ICR 實驗 於醋酸製程中亦測試固定床式反應器（ICR)，其包含塡充 有纖維以支撑細胞之外徑2付、高2 4付玻璃管，以及作爲 固足介質之Enkamat 7020。以梭狀芽胞桿菌屬之c Ijungdahlii ERI-2作爲醋酸原厭氣菌，於2 〇分鐘之氣體滯留 時間下有100個百分比之一氧化碳與7 9個百分比之氫被轉 化。在移出液體中之醋酸濃度大約每升6·〇克。UCR研究之 結果摘錄於表4中。 ICR在工業規模上有其某種親和力，其操作反應器之能 源消耗大幅降低。填充材料、溶液相與壓力之適度選擇可 得致接近CSTR之產製結果。 酸回收 經濟部中央標準局員工消費合作社印製 測試各種用以由滲透物中回收醋酸之溶劑，結果摘錄於 表5中。三丁基磷酸酯已知爲具有高分佈係數與高沸點者 。來自細胞分離器之溶劑與滲透物於一兩階段萃取程序中 混合。另外，亦可使用萃取管柱。將滲透物引入3升角錐 瓶中，於此與進入之溶劑混合。1份溶劑對1份滲透物之比 ，例功效良好，並得到高回收率。使—合併之流體通過混合器 在一 4升之沉淨室，溶劑/醋酸混·合物·於此處與水及營養基 分離成爲一較低密度相。在沉淨槽中使用約1 5分鐘之滯留 時間。萃取該較低金度相’並進給至一蒸餘瓶。將該殘餘 ---- —_____ _ 18 -The ICR experiment using the bacterial strain Clostridium spp. C ljungdahlii Erj; _2 was also tested in the acetic acid process. The fixed bed reactor (ICR) contains 塡 filled with fibers to support the outer diameter of the cells 2 pairs, high 2 4 Enkamat 7020 is a glass tube, as well as a solid medium. Using Clostridium genus c Ijungdahlii ERI-2 as an anaerobic acetogen, 100% of carbon dioxide and 79% of hydrogen were converted at a gas retention time of 20 minutes. The acetic acid concentration in the removed liquid was approximately 6.0 g per liter. The results of the UCR study are summarized in Table 4. ICR has some affinity on an industrial scale, and its energy consumption for operating the reactor is greatly reduced. Appropriate selection of filling material, solution phase and pressure can achieve production results close to CSTR. Acid Recovery Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The various solvents used to recover acetic acid from the permeate were tested. The results are summarized in Table 5. Tributyl phosphate is known to have a high distribution coefficient and a high boiling point. The solvent and permeate from the cell separator are mixed in a one- or two-stage extraction procedure. Alternatively, an extraction column can be used. The permeate was introduced into a 3-liter Erlenmeyer flask, where it was mixed with the incoming solvent. The ratio of 1 part of solvent to 1 part of permeate, for example, has good efficacy and high recovery. The combined fluid was passed through a mixer in a 4 liter settling chamber where the solvent / acetic acid mixture · separated from water and nutrients into a lower density phase. Use a retention time of approximately 15 minutes in the sink. The lower gold phase is extracted 'and fed to a steam bottle. Put the residue ---- —_____ _ 18-
---—J 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇>< 297公慶） ^2857 A7 —___ B7 _ 五、發明説明（16) 物由第一沉淨器通至第二混合器，其於此處與溶劑再度接 觸，然後被移至第二沉淨室。此可得更完全之醋酸萃取； 利用三丁基磷酸酯之酸回收由82個百分比增加至大於96個 百分比。使來自此沉淨器之溶劑/醋酸混合物回到該第一混 合器，而使水殘餘物與有機物通回至該生物反應器。 該蒸餾單元爲具沸騰泡沫之5升瓶。一般帶有迴流之蒸餾 管柱可用於完全之酸回收。因三丁基磷酸酯之高沸點，幾 乎以一步驟達成完全之回收。將該溶劑/醋酸混合加熱至 120X：，於冷凝管圈中上方收集醋酸。在此單一階段系統中 ’達到7 0個百分比之蒸餘係數。 同時測試溶劑混合物，而混合溶劑之分佈係數摘錄於表6 中。 實例2 由後黑廢氣產製醋酸於較高壓力下 經濟部中央標準局員工消費合作社印製 細胞反應中之質傳可藉由於增壓下操作系統而進一步改 進。進行簡單的批式實驗以測試此系統之動力狀態。發現 反應速率對壓力以線性比例増加，而在有效滯留時間上相 對減少。另一於增壓下操作之優點爲反應器體積可以線係 方式降低’亦即在10個大氣壓力下之操作需要之反應器體 積爲在1個大氣壓力下操作之反應器之十分之一。圖5與6 分別顯示隨壓力之增加下細胞密度矣醋酸濃度之增加。此 醋酸濃度遠超過大氣壓力下典型批式·反應器之分批濃度。 實例3 用界面活性劑由碳黑廢氣產製醋酸 _____________-19 _ 本纸張·又度適用中备國冬標準（CNS ) A4規格（21 〇 X]97公慶） '----—-- 542857 A7 B7 五、發明説明（17 ) 藉由界面活性劑之使用亦可增加質傳。表7表示出於梭狀 芽胞桿菌屬之C. ljungdahlii ERI-2上、不同市售界面活性劑 存在下所進行之一氧化碳吸收（uptake)測試。在每一種情沉 下，100(個百分比）之控制値代表於批式發酵中之C 0吸收 ，而該相同値代表界面活性劑存在下批式發酵之控制百分 比0 表1 醋酸原菌之C0、112與(：02轉化測試 細菌途徑同時消耗(：0與112 直接途徑 消化鏈球菌屬之P. productus 否 眞菌屬之E. limosum 否 醋酸菌屬之A. noterae 否 梭狀芽胞桿菌屬之C. aceticum 否 梭狀芽胞桿菌屬之C. thermoaceticum 否 S. sphaeroides 否 醋酸菌屬之A. woodii 是 經濟部中央標準局員工消費合作杜印製 醋酸菌屬之A. kivui 是 \ 梭狀芽胞桿菌屬之C. ljungdahlii ERI-2 是 間接途徑 -- 紅假單胞菌屬之R. gelatinosa 否 紫螺旋菌屬之R. rubrum 否 -20- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 542857 A7 B7 五、發明説明（18 ) 表2 .具細胞回流CSTR中之ERI2實驗摘錄 經濟部中央標準局員工消費合作社印製 氣體滯 留時間 液體 稀釋率 攪拌 速率 氣體轉化 百分比 乾細胞 重量濃度 產物濃度 HAC ETOH 比生產力 請 先 閲 讀 背 (min) (hr'1) (rpm) CO M2 (9/L) (g/L) (g/L) (g/L hr) (g / g hr) 面 9.30 0.056 750 80.75 74.5 2.3 9.7 0.07 0.43 0.18 i 事 9.28 0.055 750 82.1 72.0 3.32 9.56 0.094 0.52 0.16 項 6.14 0.061 750 73.6 46.5 4.11 12.78 0.125 0.78 0.19 寫 本 6.4 0.08 750 74.8 49.6 5.02 12.98 0.125 1.05 0.19 頁 4.74 0.087 750 68.5 37.2 4.79 12.38 0.125 1.08 0.23 4.91 0.10 750 68.8 50.2 4.53 10.73 0.05 1.08 0.24 4.05 0.102 750 65.5 58.1 5.27 11.49 0.076 1.17 0.22 3.98 0.103 900 74.3 67.9 6.17 12.73 0.1 1.31 0.21 2.89 0.117 900 66.1 33.9 5.91 11.69 0.04 1.38 0.23 3.28 0.105 1000 74.6 51.3 7.30 12.83 0.13 1.35 0.18 3.22 0.125 1000 73.1 54.0 10.25 13.57 0.08 1.71 0.17 2.65 0.13 1000 68.9 44.0 11.0 14.63 0.12 1.90 0.17 2.3 0.134 1000 66.0 38.7 11.1 20.59 0.113 2.77 0.25 2.7 0.11 1000 72.7 67.7 8.37 25.62 0.27 2.88 0.34 2.4 0.11 1000 68.6 63.3 9.88 25.82 0.36 2.95 0.30 ^2.55 0.122 1000 72.1 67.4 9.82 - *25.62 0.72 3.12 0.32 3.0 0.13 1000 76.6 73.3 12.4 22.33 0.52 2.90 0.23 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -21 - 542857 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（19 ) 表3 .具細胞回流CSTR中之A. kivui實驗摘錄 氣體滯 液體 攪拌 氣體轉化 乾燥細胞 產物 留時間 稀釋率 速率 百分比 重量濃度 濃度 比生產力 (min) (hr'1) (rpm) CO % (g/L) (g/L) (g /L hr) (g/ ghr) 5.0 0.058 750 67.8 44.2 4.00 16.15 0.96 0.24 4.4 0.958 750 65.7 38.5 4.8 16.63 0.94 0.19 4.3 0.058 900 71.3 40.7 4.5 17.03 0.99 0.21 3.72 0.058 900 69.0 37.3 5.14 19.16 1.13 0.22 3.72 0.076 900 70.3 41.1 5.28 16.17 1.21 0.23 3.2 0.076 900 66.4 41.4 5.71 16.85 1.23 0.23 2.8 0.076 900 61.5 29.1 5.00 16.16 1.22 0.23 2.8 0.076 1000 69.5 36.3 5.8 18.58 1.62 0.29 2.8 0.11 1000 70.2 41.6 5.9 18.4 1.84 0.36 2.2 0.11 1000 64.0 28.0 7.2 16.5 2.1 0.3 -22- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 542857 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（ 20 ) 1 1 I 表4.具ERI2之纖維ICR效能 1 1 J 產物濃度 N. I 請、 先1 閲 | 液體稀釋率氣體滯留時間 H2轉化 CD轉化 細胞濃度 HAC ETOHk 讀-背1 面 | (hr) (min) (%) (%) (g /L) (q/L) (q/L) 之- 塋1 0.23 4.83 38.62 54.66 .125 3.221 .778 意 I 事1 f 1 7.41 49.15 70.87 .120 2.690 .620 11.66 51.31 80.61 .067 舄 裝 本十 頁1 13.61 56.87 83.93 .064 2.099 .201 1 1 0.17 6.39 48.15 73.27 .161 3.382 1.365 1 1 11.21 68.96 92.82 .143 3.189 .495 1 訂 55.44 83.13 98.27 .112 .813 .058 1 1 I 0.12 6.26 43.89 70.76 .094 3.864 1.689 1 1 1 瓠 0.09 7.87 42.40 79.72 .095 4.423 2.733 1 Γ 19.82 59.63 92.92 .102 1 0.03 22.14 55.01 94.21 .071 4.878 2.631 1 1 _ · 29.00 78.60 100 ~ .018 5.604 2.748 I 60.48 83.33 100 * 1 1 -23- 1 1 1 1 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 542857 Μ Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（21) 表5 .醋酸分佈係數研究 平衡水溶液 溶劑 醋酸濃度，g/L 醋酸分佈係數 己烷 6.559 0.0 癸烷 5.968 0.08 氣仿 5.128 0.09 煤油 4.648 0.11 十六烷 5.866 0.13 十二烷 4.654 0.13 醋酸十二烷酯 5.787 0.15 磷酸二丁酯 4.615 0.18 油醇 5.114 0.28 三辛基胺 3.785 0.31 十一烷醇 4.528 0.40 乙酸乙酯· 4.550 0.41 丁酸乙酯 4.665 0.42 己醇 3.890 0.42 辛醇 4.358 0.45 壬醇 3.470 0.55 2 乙基-1 -己醇 3.308 -， 0.77 3:甲基環己醇 2.110 1.26 環己酮 2.702 1.66 磷酸三丁基酯 1.657 2.38 -24- 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 請 先 閱 讀 背 面 意 事 項 再 填 寫 本 頁 542857 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（22 ) 表6 .混合溶劑分佈係數 混合溶劑 分佈係數 增加百: 油醇 (10cc) 0.17 油醇 (10cc)+Cyc(lcc) 0.31 72 油醇 (10cc)+TBP(lcc) 0.29 61 油醇 (10cc)+Cyc(2cc) 0.45 150 油醇 (10cc)+TBP(2cc) 0.42 133 油醇 (10cc)+Cyc(3cc) 0.36 100 油醇 (10cc)+TBP(3cc) 0.42 133 油醇 (10cc)+Cyc(4cc) 0.35 94 油醇 (10cc)+TBP(4cc) 0.40 122 油醇 (10cc)+Gyc(6cc) 0.52 188 油醇 (10cc)+TBP(6cc) 0.63 261 油醇 (10cc)+Cyc(7cc) 0.69 283 油醇 (10cc)+TBP(7cc) 0.74 311 -25-本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 542857---— J This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297 public holiday) ^ 2857 A7 —___ B7 _ V. Description of the invention (16) The object is passed through the first sink Go to the second mixer, where it comes into contact with the solvent again, and is then moved to the second settling chamber. This results in a more complete acetic acid extraction; acid recovery using tributyl phosphate was increased from 82 percent to greater than 96 percent. The solvent / acetic acid mixture from the decanter is returned to the first mixer, and water residues and organics are passed back to the bioreactor. The distillation unit is a 5-liter bottle with boiling foam. Distillation columns with reflux can be used for complete acid recovery. Due to the high boiling point of tributyl phosphate, almost complete recovery is achieved in one step. The solvent / acetic acid mixture was heated to 120X: and the acetic acid was collected above the condensing tube ring. In this single-stage system ′ reaches a 70% distillate coefficient. The solvent mixture was tested simultaneously, and the distribution coefficients of the mixed solvents are summarized in Table 6. Example 2 Production of acetic acid from post-black waste gas at higher pressures Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Mass transfer in cell reactions can be further improved by operating the system under pressure. Perform a simple batch experiment to test the dynamic state of the system. It was found that the reaction rate increased linearly with the pressure, while the effective retention time decreased relatively. Another advantage of operating under pressure is that the reactor volume can be reduced in a linear manner, that is, the reactor volume required for operation at 10 atmospheric pressure is one tenth of that of a reactor operating at 1 atmospheric pressure. . Figures 5 and 6 show the increase in cell density and acetic acid concentration with increasing pressure, respectively. The concentration of acetic acid far exceeds the batch concentration of a typical batch reactor under atmospheric pressure. Example 3 Production of acetic acid from a carbon black exhaust gas with a surfactant _____________- 19 _ This paper is again suitable for the China National Standard for Winter (CNS) A4 (21 〇] 97 public celebration) '----— -542857 A7 B7 V. Description of the invention (17) Mass transfer can also be increased through the use of surfactants. Table 7 shows a carbon oxide uptake test performed on C. ljungdahlii ERI-2 of the genus Clostridium in the presence of different commercially available surfactants. In each case, 100 (percentage) control 値 represents the C 0 absorption in batch fermentation, and the same 値 represents the control percentage of batch fermentation in the presence of surfactant 0 Table 1 C0 of acetate bacteria , 112 and (: 02 transformation test bacterial pathways are consumed simultaneously (: 0 and 112 directly digest P. productus of Streptococcus, E. limosum, A. noterae, A. noterae, Clostridium C. aceticum No. Clostridium genus C. thermoaceticum No. S. sphaeroides No. Acetobacter A. woodii is the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs Du printed A. kivui Yes \ Clostridium C. ljungdahlii ERI-2 is an indirect route-R. gelatinosa of Pseudomonas spp. R. rubrum No. -20 of Pseudomonas spp. -20- This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) 542857 A7 B7 V. Description of the invention (18) Table 2. Excerpt from ERI2 experiment in CSTR with cell recirculation Printed by the Central Standards Bureau of the Ministry of Economic Affairs Employee Cooperatives Printed gas Retention time Liquid dilution rate Stir rate Gas Percentage of dry cell weight concentration product concentration HAC ETOH specific productivity please read back (min) (hr'1) (rpm) CO M2 (9 / L) (g / L) (g / L) (g / L hr) ( g / g hr) noodle 9.30 0.056 750 80.75 74.5 2.3 9.7 0.07 0.43 0.18 i event 9.28 0.055 750 82.1 72.0 3.32 9.56 0.094 0.52 0.16 item 6.14 0.061 750 73.6 46.5 4.11 12.78 0.125 0.78 0.19 writing 6.4 0.08 750 74.8 49.6 5.02 12.98 0.125 1.05 0.19 Page 4.74 0.087 750 68.5 37.2 4.79 12.38 0.125 1.08 0.23 4.91 0.10 750 68.8 50.2 4.53 10.73 0.05 1.08 0.24 4.05 0.102 750 65.5 58.1 5.27 11.49 0.076 1.17 0.22 3.98 0.103 900 74.3 67.9 6.17 12.73 0.1 1.31 0.21 2.89 0.117 900 66.1 33.9 5.91 11.69 0.04 1.38 0.23 3.28 0.105 1000 74.6 51.3 7.30 12.83 0.13 1.35 0.18 3.22 0.125 1000 73.1 54.0 10.25 13.57 0.08 1.71 0.17 2.65 0.13 1000 68.9 44.0 11.0 14.63 0.12 1.90 0.17 2.3 0.134 1000 66.0 38.7 11.1 20.59 0.113 2.77 0.25 2.7 0.11 1000 72.7 67.7 8.37 25.62 0.27 2.88 0.34 2.4 0.11 1000 68.6 63.3 9.88 25.82 0.36 2.95 0.30 ^ 2.55 0.122 1000 72.1 67. 4 9.82-* 25.62 0.72 3.12 0.32 3.0 0.13 1000 76.6 73.3 12.4 22.33 0.52 2.90 0.23 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -21-542857 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (19) Table 3. Extract of A. kivui experiment in CSTR with cell reflux. Gas stagnation liquid stirring gas conversion dry cell product retention time rate of dilution rate percentage weight concentration concentration specific productivity (min) (hr'1 ) (rpm) CO% (g / L) (g / L) (g / L hr) (g / ghr) 5.0 0.058 750 67.8 44.2 4.00 16.15 0.96 0.24 4.4 0.958 750 65.7 38.5 4.8 16.63 0.94 0.19 4.3 0.058 900 71.3 40.7 4.5 17.03 0.99 0.21 3.72 0.058 900 69.0 37.3 5.14 19.16 1.13 0.22 3.72 0.076 900 70.3 41.1 5.28 16.17 1.21 0.23 3.2 0.076 900 66.4 41.4 5.71 16.85 1.23 0.23 2.8 0.076 900 61.5 29.1 5.00 16.16 1.22 0.23 2.8 0.076 1000 69.5 36.3 5.8 18.58 1.62 0.29 2.8 2.8 0.11 1000 70.2 41.6 5.9 18.4 1.84 0.36 2.2 0.11 1000 64.0 28.0 7.2 16.5 2.1 0.3 -22- This paper size applies to Chinese national standards (CNS ) A4 specification (210X 297 mm) 542857 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (20) 1 1 I Table 4. ICR performance of fiber with ERI2 1 1 J Product concentration N. I Please First, read first | liquid dilution rate gas retention time H2 conversion CD conversion cell concentration HAC ETOHk read-back 1 side | (hr) (min) (%) (%) (g / L) (q / L) (q / L) of-tomb 1 0.23 4.83 38.62 54.66 .125 3.221 .778 meaning I matter 1 f 1 7.41 49.15 70.87 .120 2.690 .620 11.66 51.31 80.61 .067 outfit ten pages 1 13.61 56.87 83.93 .064 2.099 .201 1 1 0.17 6.39 48.15 73.27 .161 3.382 1.365 1 1 11.21 68.96 92.82 .143 3.189 .495 1 Order 55.44 83.13 98.27 .112 .813 .058 1 1 I 0.12 6.26 43.89 70.76 .094 3.864 1.689 1 1 1 瓠 0.09 7.87 42.40 79.72 .095 4.423 2.733 1 Γ 19.82 59.63 92.92 .102 1 0.03 22.14 55.01 94.21 .071 4.878 2.631 1 1 _ · 29.00 78.60 100 to .018 5.604 2.748 I 60.48 83.33 100 * 1 1 -23- 1 1 1 1 1 1 China National Standard (CNS) A4 specification (210X 297 mm) 54285 7 Μ Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) Table 5. Research on the distribution coefficient of acetic acid The equilibrium solution concentration of acetic acid in aqueous solution, g / L Distribution coefficient of acetic acid hexane 6.559 0.0 decane 5.968 0.08 Gas imitation 5.128 0.09 kerosene 4.648 0.11 cetane 5.866 0.13 dodecane 4.654 0.13 dodecyl acetate 5.787 0.15 dibutyl phosphate 4.615 0.18 oleyl alcohol 5.114 0.28 trioctylamine 3.785 0.31 undecanol 4.528 0.40 ethyl acetate 4.550 0.41 butane Ethyl acetate 4.665 0.42 hexanol 3.890 0.42 octanol 4.358 0.45 nonanol 3.470 0.55 2 ethyl-1 -hexanol 3.308-, 0.77 3: methylcyclohexanol 2.110 1.26 cyclohexanone 2.702 1.66 tributyl phosphate 1.657 2.38 -24- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) Please read the notice on the back before filling out this page 542857 Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 22) Table 6. Mixed solvent distribution coefficient 100% increase in mixed solvent distribution coefficient: oleyl alcohol (10cc) 0.17 oleyl alcohol (10cc) + Cyc (lcc) 0.31 72 oleyl alcohol (10cc) + TBP (lcc) 0.29 61 oleyl alcohol (10cc) + Cyc (2cc) 0.45 150 oleyl alcohol (10cc) + TBP (2cc) 0.42 133 oleyl alcohol (10cc) + Cyc (3cc ) 0.36 100 oleyl alcohol (10cc) + TBP (3cc) 0.42 133 oleyl alcohol (10cc) + Cyc (4cc) 0.35 94 oleyl alcohol (10cc) + TBP (4cc) 0.40 122 oleyl alcohol (10cc) + Gyc (6cc) 0.52 188 oleyl alcohol (10cc) + TBP (6cc) 0.63 261 oleyl alcohol (10cc) + Cyc (7cc) 0.69 283 oleyl alcohol (10cc) + TBP (7cc) 0.74 311 -25-This paper size applies Chinese National Standard (CNS) A4 size (210X 297 mm) 542857
7 B 經濟部中央標準局員工消費合作社印製 五、發明説明（23 ) 表7 .界面活性劑存在下ERI2之C Ο消耗 控制組* 具界面活性劑 DNAP (0.1%, v/v) 100 0 Nondiet P-40 (0.1%, v/v) 100 0 Tergitol NP-10 (0.1%, v/v) 100 0 Tergitol Min Foam IX (0.1%, v/v) 100 0 Tergitol TMN-10 (0.1%, v/v) 100 0 Triton X-15 (0.1%, v/v) 100 0 Triton X-100 (0.1%, v/v) 100 0 Triton X-114 (0.1%, v/v) 100 0 Triton N-101 (0.1%, v/v) - 100 5.83 Triton X-405 (0.1%, v/v) 100 7.82 Tergitol 8 (0.1%, v/v) 100 12.15 Triton N-42 (0.1%, v/v) 100 42.90 Witconol NS-500K (0.01%, w/v) 100 79.08 Tween 85 (0.1%, v/v) 100 82.16 Witconol H-33 (0.1%，v/v) 100 90.12 Witconol 6903 (0.1%, v/v) 100 92.39 Tween 80 (0.1%，v/v) 100 97.15 Arlacel 83 (0.1%，v/v) 100 97.43 Span 80 (0.1 %, v/v) 100 99.12 Tyloxapol (0.1%, v/v) 100 104.86 Witconol 5906 (0.1%, v/v) 100 108.42 Span 85 (0.1 %, v/v) 100 124.85 W-l (0.001，w/v) 第一次 100 105.89 第二次除氣 100 0 Brij 96 (0.004%，w/v)第一次 :100 107.98 * 第二次除氣 100 0 (請先閲讀背面之注意事項再填寫本頁) 1Ί -26- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 542857 A7 Β7 笔濟部中央標準局員工消費合作社印製 i、發明説明（24 ) 實例4由碳黑廢氣產製CMA含約14個百分比之c〇、17個百分比之七與斗個百分比 <C〇24碳黑廢氣於N2中作爲主成分，其被噴灑入16〇升 炙維持於6 atm、37°C下且包含梭狀芽胞桿菌屬之 Clostmdium ljungdahlii單離 ERI2 ATCC寄存 5538〇之連續攪 拌式反應器中。該等廢氣之得致係因碳氫化合物與不足之 空氣部分氧化而形成非晶碳之結果，每磅元素碳產生約12 磅足一氧化碳。這些廢氣形成一系列空氣污染問題，亦代 表著目前無法回收有價値之化學儲料資源。其氣體滞留時 間（定義爲標準狀況下反應器體積對氣體流率之比率）維持 於〇·52分鐘。使含水、驗性鹽、維生打、氮源與硫化物源 之水溶性液體介質以05 hri之液體稀釋速率（定義爲液體 流率對反應器體積之比率）進給至該反應器。此反應器中之 擾摔速率爲322 i*pm’溫度爲37。(：，而操作ρΙί爲5〇3。在 這些條件下，CO之轉化爲83個百分比，而Η〗之轉化爲“ 個百分比。使用一中空纖維膜細胞回收單元以維持反應器 内ΐ〇·5克/升之細胞濃度。來自包含13 2克/升醋酸/醋酸酯 I反應器之稀釋醋酸/醋酸酯產物流被送至三階段逆流萃取 裝置，於此處以溶劑萃取。溶劑對進料之比例爲丨比4。醋 酸/、醋酸酷產物流中之醋酸爲3.7克/亦。離開萃取器之溶^中之醋酸濃度爲16.7克/升。萃取-而来之水（介質）被送 酵器作爲回流。將白雲石灰/MgO直接加入溶劑相之醋酸中以形成 本纸張尺度it财CNS )域格（ (請先閱讀背面之注意事項再填寫本頁) _ 裝· 訂 I--------.l· l· 4 -27 542857 A7 〜____— B7 _ 五、發明説明（25 ) 。反應後，將飽和之CMA溶液送去乾燥與顆粒化，每磅醋 酸形成1· 15 lb含3/7之Ca2+/Mg2+莫耳比之CM A。] 實例5 由碳黑廢氣產製醋酸 將於N2中含約14個百分比之c〇、17個百分比之h2與4 個百分比之C 0 2之後黑廢氣噴灑入144升之於1.58 atm、37 °c下操作且包含梭狀芽胞桿菌屬之clostridiuin Tjungdahlii單 離ERI2ATCC寄存55380之滴流床式反應器中。滴流床式反 應器係以如拉西環或伯爾鞍之市售填充物填充之管柱，其 中液體與氣體因流經管柱而互相接觸'。在此實例中，液體 與氣體均以共流之方式由管柱頂部進入，雖然逆流亦爲可 行（氣體由底邵進入’液體由頂部進入）。氣體滯留時間維 持在0.46分鐘，而液體介質稀釋速率爲ο.〗7/小時。該液體 介質包含與實例1中相同之組成分。以液體循環利用60 gpm之循環速率提供反應器中之攪拌。反應器中之操作pH 値爲5·05。在這些條件下，CO之轉化爲57個百分比，而 H2之轉化爲5 8個百分比。使用一中空纖維單元以維持反應 器内13 · 6克/升之細胞濃度。 經濟部中央標準局員工消費合作社印製 將包含6.4克/升組合醋酸/醋酸g旨之稀釋醋酸/醋酸g旨產物 流與2克/升醋酸送至三階段逆流萃取管柱。溶劑對進料之 比例爲1 : 4。離開萃取器之溶劑中之醋酸爲丨〇克/升。來 自萃取單元之水（介質）被送回反應器祚爲回流。 將含醋酸之溶劑送去蒸餾以回收酸與溶劑。分離時使用 一眞空溶劑蒸餾管柱與一醋酸蒸餾管柱。製得之最終產物 _ -28- 本紙張尺度適财關家鮮（CNS 210X297公釐) 一 542857 A7 B7 五、發明説明（ 27 經濟部中央檩準局員工消費合作社印製 C0 2與H2 90個百分比轉化率之出口氣體流包含32個百 分比之⑶、64_4個百分比之Η〗、28 8個百分比之叫與36 個百分比（CH4。藉由溶劑萃取將c〇、c〇#CH4自氣體 流中移除。實例9 由竣黑廢氣產製其它化學品 將於N2中含約14個百分比之c〇、17個百分比之1^與4 個百分比1CH4之碳黑廢氣噴灑入i升之於3 7。〇與數吋水 壓下操作（CSTR中。反應器中之介質爲包含水、維生素B 、鹽與礦物質之基礎鹽混合物。反應器中之單一或混合培 養物製得曱醇、丙醇、丁醇、丙酸、丁酸或其它所欲產物 心硬相產物。該系統之建立基本上同於實例6。在稀釋產 物形成後，於包括萃取、蒸餾或其它已知產物回收技術之 適當產物回收系統回收產物。若製得多種產物，可使用階 段性產物回收系統。 因此可得知，本發明提供一種將廢氣轉化爲酸，包括如 醋酸寺有機酸、醇、氫、SCP或有機酸鹽之高效改良方法 ’藉此冗全符合主要與其它目的。熟習此技藝之人士所可 思及並認知者爲，從前述説明與所附圖式中，可於所舉實 Ή中C行修飾及/或改變而不脱離本發明。因此，明顯表示 -幻述説明與所附圖式僅係舉出之較—佳實施例，而不限制， 1本發明之實際精神與範圍係由如附:申請專利範圍所決 者。 本紙張尺 -30- (210X297公釐） (請先閲讀背面之注意事項再^寫本頁) _裝· 寫太 訂 47 B Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) Table 7. ERI2 C 0 consumption control group in the presence of surfactant * DNAP (0.1%, v / v) with surfactant 0 0 Nondiet P-40 (0.1%, v / v) 100 0 Tergitol NP-10 (0.1%, v / v) 100 0 Tergitol Min Foam IX (0.1%, v / v) 100 0 Tergitol TMN-10 (0.1%, v / v) 100 0 Triton X-15 (0.1%, v / v) 100 0 Triton X-100 (0.1%, v / v) 100 0 Triton X-114 (0.1%, v / v) 100 0 Triton N -101 (0.1%, v / v)-100 5.83 Triton X-405 (0.1%, v / v) 100 7.82 Tergitol 8 (0.1%, v / v) 100 12.15 Triton N-42 (0.1%, v / v ) 100 42.90 Witconol NS-500K (0.01%, w / v) 100 79.08 Tween 85 (0.1%, v / v) 100 82.16 Witconol H-33 (0.1%, v / v) 100 90.12 Witconol 6903 (0.1%, v / v) 100 92.39 Tween 80 (0.1%, v / v) 100 97.15 Arlacel 83 (0.1%, v / v) 100 97.43 Span 80 (0.1%, v / v) 100 99.12 Tyloxapol (0.1%, v / v) 100 104.86 Witconol 5906 (0.1%, v / v) 100 108.42 Span 85 (0.1%, v / v) 100 124.85 Wl (0.001, w / v) First 100 105.89 Second degassing 100 0 Brij 96 (0.004 %, W / v) First time: 100 107.98 * Second degassing 100 0 (Please read the precautions on the back before filling this page) 1Ί -26- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 542857 A7 Β7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs i. Invention Description (24) Example 4 CMA produced from carbon black exhaust gas contains approximately 14% of C0, 17% of 7%, and %% 〇24 carbon black exhaust gas is the main component in N2, which is sprayed into 160 liters, which is maintained at 6 atm, 37 ° C and contains Clostumdium ljungdahlii of Clostridium singular ERI2 ATCC storage 5538〇 continuous stirring type Reactor. These waste gases are obtained as a result of the partial oxidation of hydrocarbons and insufficient air to form amorphous carbon, producing approximately 12 pounds of full carbon monoxide per pound of elemental carbon. These exhaust gases create a series of air pollution problems, which also means that currently there is no way to recover valuable chemical storage resources. Its gas retention time (defined as the ratio of reactor volume to gas flow rate under standard conditions) was maintained at 0.52 minutes. A water-soluble liquid medium containing water, test salts, vitamins, nitrogen sources, and sulfide sources was fed to the reactor at a liquid dilution rate of 05 hri (defined as the ratio of liquid flow rate to reactor volume). The baffling rate in this reactor was 322 i * pm 'and the temperature was 37. (:, And the operation ρΙί is 503. Under these conditions, the conversion of CO is 83%, and the conversion of Η〗 is "%". A hollow fiber membrane cell recovery unit is used to maintain the inside of the reactor. Cell concentration of 5 g / l. The dilute acetic acid / acetate product stream from a reactor containing 132 g / l acetic acid / acetate I was sent to a three-stage countercurrent extraction device where it was extracted with a solvent. The ratio is 丨 ratio 4. The acetic acid in the acetic acid / acetic acid product stream is 3.7 g / y. The concentration of acetic acid in the solution leaving the extractor is 16.7 g / l. The extracted water (medium) is sent to fermentation The device acts as a reflux device. Dolomite / MgO is directly added to the acetic acid in the solvent phase to form the paper scale CNS) grid ((Please read the precautions on the back before filling out this page) _ Assembly · Order I --- -----. l · l · 4 -27 542857 A7 ~ ____ — B7 _ 5. Description of the invention (25). After the reaction, send the saturated CMA solution to dryness and granulation, forming 1.15 per pound of acetic acid. lb CM A with Ca2 + / Mg2 + Molar ratio of 3/7.] Example 5 Acetic acid produced from carbon black exhaust gas will be included in N2 After 14% of C0, 17% of H2 and 4% of C02, black waste gas was sprayed into 144 liters of clostridiuin Tjungdahlii isolated at 1.58 atm, 37 ° C and containing Clostridium spp. ERI2ATCC In a trickle bed reactor that holds 55380. The trickle bed reactor is a column filled with a commercially available packing such as Lacy Ring or Burr Saddle, in which liquid and gas come into contact with each other as they flow through the string. In this example, both liquid and gas enter from the top of the string in a co-current manner, although countercurrent is also possible (gas enters from the bottom to 'liquid enters from the top). The residence time of the gas is maintained at 0.46 minutes, and the liquid medium is diluted The rate is ο. 7 / hour. The liquid medium contains the same composition as in Example 1. The stirring rate in the reactor is provided at a circulation rate of 60 gpm of liquid recycling. The operating pH in the reactor is · 0.05. Under these conditions, the conversion of CO was 57 percent, and the conversion of H2 was 58 percent. A hollow fiber unit was used to maintain a cell concentration of 13.6 g / l in the reactor. Member of the Central Standards Bureau, Ministry of Economic Affairs The Consumer Cooperative printed the acetic acid / acetic acid dilute product stream containing 6.4 g / L combined acetic acid / acetic acid and 2 g / L acetic acid to a three-stage countercurrent extraction column. The solvent to feed ratio was 1: 4 The acetic acid in the solvent leaving the extractor is 10 g / l. The water (medium) from the extraction unit is sent back to the reactor for reflux. The solvent containing acetic acid is sent to distillation to recover the acid and solvent. Use in separation An empty solvent distillation column and an acetic acid distillation column. The final product obtained _ -28- This paper size is suitable for wealth and family (CNS 210X297 mm) 542857 A7 B7 V. Description of the invention (27 Central Ministry of Economic Affairs) The output of the 90% conversion rate of CO2 and H2 for the staff of the quasi-station employee cooperatives is 32% of the export gas flow, 64% of the 4% percentage, 28% of the 28% percentage, and 36% of the percentage (CH4. Co and co # CH4 were removed from the gas stream by solvent extraction. Example 9 Production of Other Chemicals from Black Waste Gas A carbon black waste gas containing about 14% of C0, 1% of 17%, and 4% of 1CH4 in N2 was sprayed into 3 to 7 liters. 〇 Operate under a few inches of water pressure (in CSTR. The medium in the reactor is a basic salt mixture containing water, vitamin B, salt and minerals. Single or mixed cultures in the reactor make methanol, propanol, Butanol, propanoic acid, butyric acid, or other desired product, a hard phase product. The system was set up essentially the same as in Example 6. After the dilute product was formed, the appropriate product including extraction, distillation, or other known product recovery techniques was used. The product is recovered by the recovery system. If multiple products are obtained, a staged product recovery system can be used. Therefore, it can be known that the present invention provides a method for converting exhaust gas into an acid, including organic acids such as acetate, alcohol, hydrogen, SCP or organic acid salts. The efficient improvement method 'is fully consistent with the main and other purposes. Those who are familiar with this technique can understand and recognize that from the foregoing description and the attached drawings, the C line can be modified and And / or changes without departing from the invention. Therefore, it is obvious that the description of the illusion and the attached drawings are only preferred embodiments without limitation, and the actual spirit and scope of the invention are as attached :Application Lee scope of those decision. This paper ruler -30- (210X297 mm) (Please read the Notes on the back page and then write ^) _ loaded, writing, too booked 4