421 6 b b A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（，） 本發明傜有關一種多孔性球狀粒子及其製法。更詳言 之，傜有關尤其適合做為流動床型徹生物載體所使用的 以聚乙烯基縮薛糸樹脂為架構之多孔性球狀粒子、及適 合製诰該多孔性球狀粒子之多孔性球狀粒子製法。 以往，在反應器内填充撤生物或酵素，且藉由該撤生 物之酵素反製得生産物的方法，偽稱為生物反應器， 在食品、醫111品、化學品之製造範圍或下水道、排水、 排氣等之處理範圍中廣受工業上予以活用而且，近年 來為使處理能力較為效率化，故研究使該擻生物觸媒在 反應槽内予以高密度填充的方法。 其中最具代表性者俗為使微生物載負於粒狀載體上， 詳言之，分為使榭生物載負於載塍表面上，利用生物膜 之生物膜法與在載體内部使撤生物固定之包括固定化撤 生物法兩種。此外，該載體之原料有高分子物質及無機 条物質，載體的使用形態，例如有使載體固定於反應槽 内部所使用的固定床型、或使載體流動的流動床型。 其中，流動床型所使用的載體，由於其流動性能及比 重極重要，故高分子条粒狀載體較無機糸載醴，較為一 般所採用。該粒狀載體之原料例如有聚乙烯醇凝膠（PVA 凝膠），丙烯醯胺凝膠、聚乙烯醇凝膠等之凝驩狀粒狀 物，或聚乙烯、聚氛基甲酸乙酯、聚氛化亞乙基、甲基 級雒等多孔質粒狀物。 以往，此等之粒狀物傜如下述之方法予以製造。換言 之.使在溶解有原料之水溶液中混練有氣孔形成劑，交 (請籴閏讀背面之注意事項再填寫本頁) 裝. 訂 ir421 6 b b A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (,) The present invention relates to a porous spherical particle and a method for producing the same. In more detail, it is related to porous spherical particles based on a polyvinyl polyether resin which is particularly suitable for use as a fluidized bed type biological carrier, and the porosity suitable for making the porous spherical particles. Method for making spherical particles. In the past, a method of filling a reactor with an organism or an enzyme, and using the enzyme of the organism to produce a product, was pseudo-called a bioreactor, which was used in the manufacture of food, medicine 111, chemicals, or sewage, In the treatment range of drainage and exhaust gas, it is widely used industrially. In addition, in order to make the processing capacity more efficient in recent years, a method of filling the dysprosium biocatalyst in the reaction tank with high density has been studied. The most representative custom is to carry microorganisms on a granular carrier. In detail, it is divided into carrying organisms on the surface of the carrier, using the biofilm method of biofilm and fixing the organisms inside the carrier. They include two methods of immobilized biological removal. In addition, the raw materials of the carrier include a polymer substance and an inorganic strip substance, and the use forms of the carrier include, for example, a fixed-bed type in which the carrier is fixed inside the reaction tank, or a fluid-bed type in which the carrier flows. Among them, the carrier used in the fluidized bed type is more commonly used than the inorganic carrier because of its extremely important fluidity and specific gravity. The raw materials of the granular carrier are, for example, polyvinyl alcohol gel (PVA gel), acrylamide gel, polyvinyl alcohol gel and the like, or polyethylene, polyurethane, Porous particles such as ethylene and methyl fluorene. Conventionally, such granules are produced as follows. In other words, the pore forming agent is mixed in the aqueous solution in which the raw materials are dissolved, and it is handed in (please read the precautions on the back before filling this page). Order ir
本紙張尺度適用,中國國家梂準（CNS )人4此格（210 X Μ:公簷J 663五、發明説明（ 聯劑，觸 或空氣浴 氣孔形成 大型嵌段 Η狀，且 或紐狀高 撤米角之 多孔質物 狀物經拉 撤生物 外，流動 媒等之 予以反 劑以製 狀高分 使該Η 分子多 立方形 藉由切 拔機以 載體所 性能、 添加物 應且不 得嵌段 子多孔 狀物切 孔質物 粒子。 Μ成數 數橄米 企求的 比重、 Α7 Β7 者流人 溶化。 狀高分 質物籍 成數撤 各切成 另外， 微米之 單位拉 性質， 射摩損 大型的 此外， 子多孔 由切Η 米單位 数橄米 使上述 厚度而 拔製得 例如除 性、耐 反應槽中 藉由水洗 質物β然 成數撤米 而成紐狀 的長度， 大型嵌段 成片狀. 粒狀多孔 與徹生物 候（光）性 ,以湯浴 萃取除去 後，使該 厚度而成 ,最後使 以裂造數 狀高分子 再使該片 質物e 之親和性 ,耐撖生 請 先. 閱 之 注 意 事 項 再 填、I装 頁 經濟部中央標準局貝工消費合作社印裝 同 載被酯物考型粒粒 製成 不 於易乙生於床一性 以以 所和，時酸受，動均孔 予予 有親佳擦甲易外流的多。法段 亦之不摩基身此為球的者裂階 質物箸壁氛本。做 _知份之個 性生顯内聚素短高近習充述 3 之撤質槽、維命提接惟夠上箱 等與性應烯纗赛及得，不以仍 此醸擦反乙，，，裂要鲇於後 ，.載摩與聚高壊性能重該由應 同狀附或-不崩擦可為為物反 不隈是擦且質於摩儘掻故狀 ， 類凝其摩而性易耐，像，粒時 種，尤的 *候睦高時物子性小 體中-生短 E 載提性狀粒孔數 載類低産命，時、動球形多箱 視種度間毐物用充流性方之少 ,雔強體體狀使焴之孔立知至 等喊械載載粒期之體多為習時 性各機時使質長器載之於，應 解述惟動，孔，容物徑由外反 分上異流損多解對生直物另 ， 物。猓體磨等分應撤子狀 造. 訂^. 本紙伕尺度適用中國國家搮準（CNS ) A4规格（2丨Ο X 297公釐） . · *. · - .- 42彳 658 A7 B7 五、發明説明（；） 形，目必須至少2天以上之製造天數以形成數撤米，均 一的粒狀物。而且若為以拉拔型予以拉拔時，數徹米之 粒子容易阻塞於拉拔型、必須予以取出除去此等之後處 理。此外，使嵌段狀多孔質物藉由後加工予以切片、切 斷或拉拔時，為投資收益低者。 該點、大幅地縮短後加工之時間、提髙投資收益之方 法，例如有使嵌段狀高分子物不要切片，直接以粉碎器 等予以粉碎的方法。該方法確實可能大幅地縮短加工時 間，惟不易製得均一粒子直徑之多孔性球狀粒子。 另外，上述之任一方法為了進行各形狀之反應時，必 須按生産景之增加比例，反應槽之空間亦應擴大，於所 限定的設備中其生産量受到限制，且生産性不佳。 本發明之課題係為提供一種機械強度及耐摩擦性高、 且具有與撤生物之親和性、適合做為撤生物載體，尤其 是流動床型撤生物載體之多孔性球狀粒子。而且，本發 明之課題亦提供一種可以簡單，且高生産性製造儘可能 接近均一粒子直徑的多孔性球吠粒子之製法。 經濟部中央標準局員工消費合作社印裝 (請先閱讀背®之注意事項再填寫本頁) 本發明人等為了解決上述課題，再三深入研究的結果 ,發現使用以聚乙烯基縮醛糸樹脂為架構的多孔性球狀 粒子，尤其是以聚乙烯基縮e糸樹脂為架構之海綿狀多 孔性球狀粒子（其中，以聚乙烯基甲縮醛樹脂為架構之 多孔性球狀粒子）時，可得優異的耐摩擦性，耐候（光） 性、耐撤生物分解性，流動性及徹生物親和性之原料。 本發明偽為以聚乙烯基縮κ条樹脂為架構的多孔性球 本紙張尺度適用t國躅家#準（CNS.) A4it格（210X297公釐） 421658 A7 B7 五、發明説明（4 ) 狀粒子。此外，為由具有做為氣孔之連通孔的海綿狀聚 乙烯基縮醛集樹0旨所成的多孔性球狀粒子。因此，徹生 物之載體若使用聚乙烯基縮醛糸多孔性球狀粒子，尤其 是聚乙烯基甲縮醛（PVF)之多孔性球狀粒子時，為具優 異的耐摩擦性、耐候（光）性、附撤生物分解性、流動性 及徹生物親和性之撤生物載體。 經濟部中央梯準局員工消費合作社印製 叫裝-- (請‘閱讀背_面之注意事項再填寫本頁) 該多孔性球狀粒子由於不為含水凝膠構造.而為具聚 乙烯基縮醛之架構構造的海綿狀多孔質物，較凝膠狀物 具優異的耐摩檫性及機械強度，除可做為撤生物載體外 ，並滴用於農作物之水耕栽培中溶液保持材或植物支持 材、動植物細胞之培地、人工水笞、土壤改良材、配管 洗淨部材、過濾材、吸水材等。另外特殊使用例亦可利 用為水中流動型洗淨部材或水中流動型按摩部材。此處 ，水中流動洗淨部材係為使細致的蔬菜或凹凸多的蔬菜 等之表面洗淨，故在水中加入蔬菜的同時自水槽的底部 産生泡之，藉由吹泡攪伴全饈，與蔬菜等接觴，稱為洗 淨蔬菜表面之洗淨部材。另外，水中流動型按摩部材係 指對人體而言可得按摩效果者，在浴槽等之水槽中使該 粒子流動旦藉由接陆人體、陚予皮慮剌激而得按摩效果 之部材。 待別是檝生物載體時，具有與撤生物之親和性，且具 闱異的流動性，故最適用於流動床型之用途。尤其為以 聚乙烯基縮醛条樹脂為架構、接近圓球之均一粒子直徑 的多孔性球狀粒子時，具有更優異的機械強度及耐摩擦 本紙伕尺度通用中囷國家榇準（CNS ) A4規格（210X297公釐) 42彳 658 A7 B7 經濟部中央標準局貝工消費合作社印裝 五、發明説明 ( f ) 1 性 ， 可 更 上 — 層 提 高 容 器 之 11 充 性 或 做 為 撤 生 物 載 體 1 1 之 流 動 性 〇 1 1 此 外 本 發 明 人 等 發 現 製 造 此 等 之 多 孔 性 球 狀 粒 子 之 請 1 先 1 方 法 1 傜 在 酸 性 溶 液 中 滴 入 具 凝 膠 化 性 質 之 水 溶 性 髙 分 閱 讀 1 子 與 含 聚 乙 烯 醇 及 類 之 溶 液 9 且 使 該 溶 液 凝 膠 化 的 同 S f 之 1 時 薙 由 使 該 液 滴 中 聚 乙 烯 醇 與 m 類 反 應 可 製 得 以 聚 乙 烯 i 1 I 縮 m % 樹 脂 為 架 構 之 多 孔 性 球 狀 粒 子 〇 承 項 1 I 再 1 二 1 m 由 本 製 造 方 法 » 由 於 形 成 粒 子 之 原 液 液 滴 與 反 應 液， 填’ 寫 本 裝 接 觸 直 接 形 成 粒 子 r 故 可 同 時 進 行 縮 化 處 理 與 球 狀 粒 頁 1 1 子 之 成 形 過 程 0 而 且 1 與 為 縮 m 化 之 觸 媒 的 酸 類 接 觸 時 1 1 1 由 於 含 有 凝 膠 化 水 溶 性 高 分 子 故 不 會 使 液 滴 的 形 狀 崩 1 j 鹿 〇 因 此 * 不 需 如 習 知 的 多 値 X 程 * 且 可 簡 BB 早 ， 又 髙 生 1 訂 産 地 來 製 迪 接 近 圓 球 之 均 —· 粒 子 直 徑 的 多 孔 性 球 狀 粒 子。 1 本 發 明 為 以 聚 乙 烯 縮 甲 链 % 樹 脂 為 架 構 之 多 孔 性 球 1 1 狀 粒 子 〇 而 且 > 為 種 由 具 做 為 氣 孔 之 連 通 孔 的 海 綿 狀 1 I % 乙 烯 基 縮 醛 % 樹 脂 所 成 的 多 孔 性 球 狀 粒 子 0 1 本 發 明 所 得 的 聚 乙 烯 基 縮 糸 多 孔 性 球 狀 粒 子 俗 使 聚 〆線 1 乙 二 酵 與 m 類 反 應 而 得 者 〇 對 於 原 料 之 聚 乙 烯 醇 没 有 待 1 1 别 的 限 制 * 惟 以 平 均 聚 合 度 為 500 , -3800之聚乙烯醇為 1 宜 而 且 以 兀 金 m 化 > 或 混 合 部 份 鹼 化 物 及 低 聚 合 度 物 嘗· 1 者 為 宜 〇 若 平 均 聚 合 度 小 於 500 時. 不易製得具高氣孔率 I 1 者 而 若 平 均 聚 合 度 大 於 3800 時 f 由 於 溶 Λ71 m 於 水 時 其 粘 1 1 度 太 高 f 故 於 混 練 等 工 程 中 不 易 處 理 〇 而 且 亦 可 使 用 1 I 混 合 聚 合 度 不 同 的 聚 乙 7 烯 酵 原 料 t 並 亦 可 使 用 混 合 不 在 1 1 ! 1 1 t 1 本紙張尺度適用中國國家樣準（.CNS) A4規格.（210X297公釐） 421658 A7 B7 經濟部中央標準局舅工消費合作社印笨 五、- 發明説明 〔占 ) 1 1 上 述 範 圍 者 (如聚合度] 5ί 10或聚合度： 10〔 1者 ) 1 $不會有 1 1 問 題 産 生 〇 尤 其 為 得 彈 性 、 柔 軟 性 、 質 感 、 氣 孔 率 之 調 1 1 整 N. 吸 水 性 提 高 等 » 亦 可 使 用 低 聚 合 度 之 聚 乙 烯 醇 樹 脂 0 請 1 先 1 該 聚 乙 烯 基 縮 m 糸 多 孔 性 球 狀 粒 子 的 氣 孔 率 » 視 其 所 閱· 讀 1 使 用 的 用 途 而 設 定 1 沒 有 待 別 的 限 制 9 惟 以 5 C 〜 9ί % 較 背 面- 1 I 之 1 佳 d 苕 上 述 氣 孔 率 小 於 5C % 時 各 氣 孔 間 不 易 互 相 郯 接 注 意 1 事 1 故 會 有 獨 泡 存 在 的 情 形 因 此 會 顯 著 阻 害 透 水 性 〇 此 外 項 [ 再 \ t 氣 孔 率 大 於 98 % 時 > 由 於 耐 摩 擦 性 等 之 機 械 強 度 降 低 填 寫 本 裝 » 視 其 用 途 而 使 用 上 受 到 限 制 而 産 生 問 題 頁 •s_^· 1 I 有 關 聚 乙 烯 基 縮 醛 多 質 物 之 縮 m 化 度 » 没 有 待 別 的 J 1 限 制 i 惟 縮 醛 化 度 以 3 0 〜 85 莫 耳 % 為 宜 * 較 佳 者 為 4 5 〜 1 1 7 0 奠 耳 % 〇 其 中 * 甲 縮 m 化 度 為 30 85 冥 耳 % (較佳者 1 訂 為 4 5 7 0 莫 耳 % )之聚乙烯基甲缩醛為佳。 1 m 由 使 縮 m 化 度 調 整 於 該 範 圍 内 9 可 得 柔 軟 且 具 耐 摩 1 1 擦 性 之 撤 生 物 載 體 〇 而 且 若 縮 化 度 小 於 30 莫 耳 % 時 ί | * 分 子 交 聪 度 低 9 強 度 不 佳 ». 摩 擦 堅 牢 度 低 〇 因 此 % 待 [ 1 別 做 為 流 動 床 型 粒 子 多 孔 質 物 時 9 於 載 體 流 動 時 會 因 産 ，‘泉 1 生 載 體 間 之 摩 擦 或 與 反 mac m 槽 内 之 摩 擦 而 易 於 摩 損 9 致 使 1 | 載 體 壽 命 降 低 0 另 外 J 就 耐 撤 生 物 侵 蝕 性 降 低 而 -J=~ 係 不 Γ 為 企 求 〇 而 且 有 於 製 造 工 程 上 不 易 處 理 的 問 題 0 另 外 * 1 \ 若 縮 化 度 大 於 85 其 耳 % 時 氣 孔 率 降 低 且 假 比 重 增 加 1 1 1 含 水 率 降 低 ’ 尤 其 是 做 為 流 動 床 型 粒 狀 多 孔 質 物 時 » 1 1 易 沈 降 而 不 易 浮 游 I 故 曰 降 低 處 理 槽 内 之 流 動 性 能 0 此 外 1 ί 9 持 別 是 在 殘 存 羥 基 量 減 少 時 伴 随 親 水 性 降 低 不 為 企 求 \ \ 〇 另 外，就 濕 潤 時 反 JVO W 性 8 降 低 1 趿 水 性 及 耐 久 性 而 S 偽 不 為 1 J i 1 本紙張尺/liiM 家梂羋（CNS ) Λ4規格（210X297公釐〉 42165 8 A7 B7 經濟部中央標準局員工消費合作社印裝 五、發明説明 ( 7 ) 1 -| 企 求 〇 待 別 θ 疋 施 予 乾 燥 壓 縮 加 工 而 成 壓 縮 壓 製 時 卽 使 1 1 在 處 理 槽 中 等 使 其 濕 m » 不 易 恢 復 原 來 的 形 狀 或 無 法 復 I 1 原 » 勿 受 永 久 斜 而 無 法 做 為 壓 製 加 工 品 〇 基 於 該 點 t---- 詩 1 先 1 若 將 縮 化 度 30 8£ 莫 耳 % (較佳者45_ 一 70莫耳％ ) 之 聚 閱 1 乙 烯 基 縮 % 多 孔 質 物 » 尤 其 曰 疋 甲 縮 m 化 度 30〜 8E 莫 耳％ 背 面 1 之 1 (較佳者為4 5〜？ 0莫耳％ ) 之 聚 乙 烯 基 甲 縮 m 時 ， 就 耐 撤 ί 1 | 生 物 侵 蝕 性 而 言 為 佳 1 且 其 強 度 優 異 » 摩 擦 堅 牢 度 大 〇 孝 項 1 I 再ί 1 1 所 以 » 尤 其 是 使 用 於 流 動 床 型 粒 狀 多 孔 質 物 時 可 提 4 寫 本 1 高 載 BM 腊 m 命 〇 而 且 * 使 用 為 流 動 床 型 粒 狀 多 孔 質 物 時 * 頁 1 I 可 保 有 使 處 理 槽 内 易 於 浮 沈 流 動 之 氣 孔 率 » 及 含 水 狀 態 1 ί 之 假 bb 重 4 且 由 於 如 親 水 性 良 好 t 故 可 發 揮 歷 異 的 流 動 性 1 j 能 〇 此 外 » 濕 m 時 之 反 彈 性 變 高 1 且 施 予 乾 燥 壓 縮 加 工 1 訂 » 即 使 做 為 壓 縮 壓 製 品 仍 不 易 受 到 永 久 歪 斜 » 使 其 在 處 1 理 槽 中 等 濕 潤 仍 可 回 復 至 原 來 的 形 狀 0 因 此 > 本 發 明 之 ί 1 多 孔 性 球 狀 粒 子 可 做 為 壓 製 加 工 品 且 做 為 壓 縮 多 孔 性 ! I 球 狀 粒 子 可 使 粒 狀 多 孔 質 物 之 搬 蓮 性 飛 躍 地 提 高 » 且 1 1 使 其 在 處 理 槽 中 等 m 潤 時 ， 處 理 液 被 溶 化 > 吸 水 而 回 線 i 復 至 m 來 的 形 狀 且 可 在 處 理 槽 中 垂 直 地 浮 沈 流 動 \ 不 需 保 持 至 成 含 水 粒 子 ♦ 可 顯 箸 地 縮 短 處 理 時 間 〇 而 且 J i ， 壓 縮 多 孔 性 球 狀 粒 子 偽 指 使 本 發 明 之 多 孔 性 球 狀 粒 子 1 I 以 任 何 形 狀 予 以 壓 縮 (壓製） 的 it丄 粒 子 0 1 ί 另 外 > 決 定 該 多 孔 性 球 狀 粒 子 之 性 質 的 重 要 原 因 之 一 1 1 為 粒 子 之 tfc 種 〇 粒 子 之 比 重 可 以 上 述 之 氣 孔 率 來 控 制 » 1 I 惟 視 其 用 途 粒 子 之 tb 重 9 可 更 小 m 更 輕 層 0 持 別 是 為 1 1 1 1 1 1 本紙張尺度適用中國國家橾準（CNS ) A4規.(2丨OX 297公釐） 658 Β7 經濟、邓中央標隼局貝工消費合作社印製 五、發明説明 ( 8 ) 1 1 流 動 床 等 使 用 的 m 生 物 載 體 時 ， 由 於 流 動 性 為 重 要 的 因 1 1 素 * 對 於 控 制 比 重 之 廣 範 圍 極 為 重 要 此 處 耐 摩 擦 性 及 1 1 機 械 強 度 優 異 的 以 聚 乙 烯 基 缩 % 樹 脂 為 架 構 之 多 孔 性球 請 1 先 1 狀 粒 子 内 部 為 中 空 狀 粒 子 時 * 視 其 中 空 程 度 而 定 1 合 乎 閲· I 1 多 孔 構 造 可 使 粒 子 之 比 重 控 制 為 廣 範 圍 〇 而 且 9 本 發 明 背 1 | 之 1 之 中 空 粒 子 藉 由 下 述 之 方 法 可 簡 «3d 早 地 製 造 〇 注 意 1 I 本 發 明 之 徹 生 物 載 體 的 含 水 狀 態 之 假 fcb 重 以 調 整 為 1 . 0 事 項 真 1 1 1 . 2較佳。 若 含 水 狀 態 之 假 fcb 重 小 於 1 . 〇時， 投入處 填 寫 本 裝 1 理 槽 中 只 會 浮 起 來 > 致 使 處 理 不 易 > 而 若 大 於 1 2時， 頁 S- 1 I 容 易 沈 降 而 欠 缺 流 動 性 〇 因 此 聚 乙 烯 基 縮 m % 多 孔 質 1 1 物 之 含 水 狀 態 的 假 比 重 為 1 . 0 - -1 .2 之 本 發 明 撤 生 物 載 體 1 1 t 尤 其 是 做 為 流 動 床 型 粒 狀 多 孔 質 物 時 ， 可 發 揮 適 當 1 訂 良 好 的 流 動 性 « 1 而 且 i 本 發 明 之 微 生 物 載 體 被 處 理 液 充 谋 於 多 孔 質 物 I 1 之 氣 孔 内 時 的 bt 重 俗 以 較 接 近 被 處 理 液 本 身 之 比 重 者 1 1 較 佳 〇 若 使 被 處 理 液 以 水 換 算 時 1 含 水 狀 態 之 假 fcb 重 為 1 1 1 . 〇以上， 且以接近1 .0 者 最 佳 〇 惟 做 為 聚 乙 烯 基 縮 m 糸 ，旅 ) 多 孔 質 物 之 實 用 上 含 水 狀 態 的 假 比 重 如 上 述 為 1 - 〇 - ^ 1 .2 1 1 ， 較 佳 者 為 1 . 0 1 1 . 1 0 原和 士本身之真Η s重為1 .2 4〜1 .28 [ 1 較 佳 者 為 1 * 2 5 1 . 2 6 0 以 具 此 等 範 圍 之 比 重 的 聚 乙 烯 1 1 | 基 縮 m 糸 多 孔 質 物 做 為 m 生 物 載 體 時 ) 尤 其 是 做 為 流 動 I 1 床 型 粒 狀 多 孔 質 物 可 發 揮 良 好 的 流 動 性 〇 1 I 本 發 明 之 微 生 物 載 體 * 含 水 狀 態 之 大 小 為 1 m 1D〜 2 0 m m 1 1 之 粒 狀 物 為 宜 〇 藉 此 可 提 高 流 動 性 能 * 發 揮 橄 生 物 處 理 1 1 10 I 1 1 本紙張尺度適用中國國家標绛（CNS、Λ4見烙（210X297公釐） 421658 A7 B7 五、發明説明（9 ) ---------^ — 請先閱讀背面之注意事項寫本頁 能力，且可使用於設置有粒狀撤生物載體之回收過濾器 的污水處琿装置等，通過該回收過逋器並不會自裝置之 處理排液的排出口流出，且可使榭生物嬝度保持於高濃 度。 經濟部中央標準局員工消費合作社印裝 若粒子大小大於20π»β時，使用本發明之多孔性球狀粒 子做為撤生物載體時不利。換言之，不僅會降低粒子之 流動性能，且由於欠缺載負撤生物之有效表面積，故不 易維持撤生物為高滠度，且會降低撤生物處理能力。此 處，粒子直徑小者其流動性佳，在流動床型反應器中為 使載體流動之能源小，可提高處理性能，惟若過小時， 具髖而言若粒子之大小小於lam時，使用於設置有粒狀 撤生物載醴之回收過濾器的污水處理裝置等時，通過該 回收過油：器，會有自裝置之處理排液的排出口流出之問 題，且榭生物之濃度不易保持於高濃度。此處，回收過 濾器亦可以考廉為設置於處理液流出口、開口為1.5mro 楔形銷絲篩網之狹縫更小者。然而.排水中之徹粒子、 撤生物之拈性生産物等會附著於該狹縫上，而導致閉塞 情形，故過濾器之開口大小於本身會有限制，由粒狀徹 生物載體之回收過濾器的關像，來決定聚乙烯基縮K糸 多孔性球狀粒子之最適當的大小。 本發明多孔性球狀粒子之大小如下所述，可藉由滴下 之液滴大小予以簡單地控制。具體而言，藉由任意調整 液滴之吐出量與滴下所需的噴嘴口徑，可製得任意粒徑 之粒子。 _ 1 1 - (CNS)A4規格（2!0X297公釐） · · · - . + 經濟部中央標準局員工消费合作社印裝 42 1 b5 8 ' A7 B7 五、發明説明（) 本發明之多孔性球狀粒子，平均氣孔徑傜多數具備可 使2fl〜300/Zb之水或空氣自由來去的尺寸之孔，與單純 具有以分子水平之網目構造的凝膠不同。撤生物載體使 用於$動槽内時，水中之有機物質、磷或氮糸化合物等 ，於該尺寸之孔可自由來去、易於進出。而且，具備多 數的20〜30Qjuin氣孔經之孔的撖生物載體，妣生物易形 成膜且載體表面上所形成的撖生物膜不易剝離，故適合 使用β此外，有關氣孔徑之控制傜藉由使用如下述之製 法，可適當的控制。 本發明由多孔性球狀粒子所成的海綿，同樣地多數具 備有可使水或空氣自由來去的尺寸之孔，且以水膨脹為 水份率為50%狀態之50%壓縮應力，具2〜200Χ 103Ν/η2 之適度彈性。该適度彈性可達載體流動時之良好的耐摩 擦效果。 此外，提高該多孔性球狀粒子之射摩擦性及機械強度 ,係具有在粒子表面上具細孔之皮膜，且使粒子内部為 多孔質構造傺為企求。下述之本發明製法作成的球狀粒 子係在表面上附有皮膜，為機械強度優異者。 本發明之多孔性球狀粒子，不僅投入流動床型處理 槽中，且藉由做為含水多丑質物曝氣於處理槽内等，良 好地浮沈、流動、且材質上與微生物之親和性良好、徹 生物附著、可優異地進行生物處理。而且，由於具良好 的耐摩擦性、故即使因載體流動時所産生的載體間之摩 擦或與反應槽内壁之摩擦，仍不易被摩損。3外，具高 本紙張尺度適用中國國家棵準（CMS ) A4#見格（2in_.<?97公9 ) (請先'閲讀背.之注意事項再填寫本頁)This paper is applicable to China National Standards of Standards (CNS) person 4 this grid (210 X Μ: public eaves J 663 V. Description of the invention) After the porous material of the rice corner is pulled out of the organism, the mobile medium is reversed to make a high score to make the puppet molecule multi-cubic by the cutting machine with the performance of the carrier. The additives should not be blocked. The porous material cuts the pore material particles. The specific gravity required by the megacells is reduced, and the A7 and B7 are melted away. The high-quality materials are cut and cut into separate, micron-scale tensile properties, the abrasion is large, and the sub-porous Granular porous and with Complete biochemical (light) properties, after extraction and removal in a soup bath, the thickness is formed, and finally a number of macromolecules are cracked, and then the affinity of the sheet material e is made, and the breeding resistance is first. Please read the precautions Again 、 I Loading pages The Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed the same loaded esters, and made them into granules that are not easy to be born in the bed. Jia Jia is more likely to leak. The method is also not good. The body is a ball player who splits the texture of the wall. This is a _ Zhifen personality that shows cohesive short height. And the life-saving mention is only enough to get into the box and the sexual response should not be defeated, but not to wipe the anti-B, and the cracks should be later. The performance of the bearing and the polymer should be the same. Attached or-not collapsing rubbing can be the object is not rubbing and rubbing, and the quality is as good as rubbing, so it is easy to tolerate, such as, when the seeds are seeded, especially when the nature is high. In the body, the short-lived E-loading traits, the number of pores, and the low-yielding type, the time and the moving spherical multi-boxes, depending on the fluidity of the species between the species, are sparse, and the stubborn body shape makes the pores of the spores known and so on. Most of the bodies in the mechanical load-carrying stage are loaded by the long-time device with habitual time and time. It should be explained that the movement, holes, and material path are divided from the external anti-flow loss, and the multiple fluid solutions are straight and straight. Corpus callosum Order ^. The paper size is applicable to China National Standard (CNS) A4 (2 丨 〇 X 297 mm). · *. ·-.- 42 彳 658 A7 B7 V. Description of the invention (;) The mesh must be manufactured for at least 2 days to form several grains of rice, and uniform grains. And if it is drawn with a drawing type, the particles of several meters are easily blocked in the drawing type, and must be removed to remove it. Wait for subsequent processing. In addition, when the block-shaped porous material is sliced, cut, or drawn by post-processing, it is the one with the lowest return on investment. At this point, the time for post-processing is greatly shortened, and the method of improving investment returns, For example, there is a method in which the block-like polymer is directly pulverized with a pulverizer or the like without slicing. This method does make it possible to significantly shorten the processing time, but it is not easy to produce porous spherical particles with uniform particle diameters. In addition, in order to carry out the reactions of various shapes in any of the above methods, the proportion of the production scene must be increased, the space of the reaction tank should also be enlarged, the production capacity of the limited equipment is limited, and the productivity is not good. The object of the present invention is to provide a porous spherical particle having high mechanical strength and friction resistance, and having affinity with a living organism, and is suitable as a living organism carrier, especially a fluidized bed type biological carrier. In addition, the subject of the present invention also provides a method for producing porous ball-bark particles that can be made as simple and highly productive as possible with a uniform particle diameter. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back and fill in this page). The inventors and other researchers have intensively studied the results of the above-mentioned problems and found that the use of polyvinyl acetal resin Structured porous spherical particles, especially sponge-like porous spherical particles based on polyvinyl efluorene resin (including porous spherical particles based on polyvinyl methylal resin), Raw materials with excellent abrasion resistance, weather resistance (light) resistance, biodegradation resistance, fluidity, and biocompatibility can be obtained. The present invention is a porous sphere based on a polycondensation κ strip resin as a framework. The paper size is applicable to the national standard #CNS. A4it grid (210X297 mm) 421658 A7 B7 V. Description of the invention (4) particle. In addition, it is a porous spherical particle made of a sponge-like polyvinyl acetal tree having a communication hole as a pore. Therefore, if the polyvinyl acetal and porous spherical particles are used as the carrier of the organism, especially the porous spherical particles of polyvinyl formal (PVF), it has excellent friction resistance and weather resistance (light ), Biodegradability, fluidity, and biocompatibility. Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China-(please 'read the notes on the back side and fill out this page) The porous spherical particles are polyethylene-based because they do not have a hydrogel structure. The sponge-like porous material of the acetal structure has superior friction resistance and mechanical strength than the gel. It can be used as a biological carrier, and is used as a solution retention material or plant in hydroponic cultivation of crops. Support materials, cultivation of animal and plant cells, artificial leech, soil improvement materials, piping cleaning materials, filter materials, water-absorbing materials, etc. In addition, for special use cases, it is possible to use a water-flow-type washing member or a water-flow-type massage member. Here, the water-washing parts are used to wash the surface of delicate vegetables or vegetables with many unevenness. Therefore, when vegetables are added to the water, bubbles are generated from the bottom of the water tank, and the whole is stirred by blowing, and Vegetables, etc., are called washing parts that clean the surface of vegetables. In addition, the underwater flow-type massage member refers to a member that can obtain a massage effect for the human body, and the particles can be caused to flow in a water tank such as a bath, and the massage effect can be obtained by contacting the human body and irritating skin. When it is different from the tritium biological carrier, it has affinity with the organism and has different fluidity, so it is most suitable for the use of fluidized bed. Especially for porous spherical particles with a uniform particle diameter close to a sphere based on a polyvinyl acetal strip resin, it has more excellent mechanical strength and friction resistance. This paper is widely used in China (CNS) A4. Specifications (210X297 mm) 42 彳 658 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (f) 1 can be improved-the level of the container can be increased to 11 or the bio-removal 1 The fluidity of 1 1 In addition, the present inventors have found that to make these porous spherical particles, please 1 first 1 method 1 滴 drip into a water-soluble water-soluble gelation properties with an acidic solution 阅读 Read 1 When the solution containing polyvinyl alcohol and the like is 9 and the solution is gelatinized as in S f, the polyethylene i 1 I can be prepared by reacting the polyvinyl alcohol in the droplet with the m-type resin. Porous sphere Particles 0 Item 1 I 1 2 1 m by this manufacturing method »Since the original liquid droplets forming the particles and the reaction liquid are filled in, the writing device contacts directly to form particles r, so the shrinking treatment and the spherical particles can be performed at the same time. The forming process is 0 and 1 when it is in contact with an acid that is a shrinking catalyst. 1 1 1 Because it contains a gelled water-soluble polymer, it does not collapse the shape of the droplet. The multi-step X process *, and can be simplified BB early, but also produced 1 order origin to make close to the average sphere-the porous spherical particles of particle diameter. 1 The present invention is a porous sphere 1 1 shaped particles with polyethylene methylated chain% resin as the framework. Also, it is a sponge-like 1 I% vinyl acetal% resin with communicating holes as pores. Porous spherical particles 0 1 The polyvinyl polycondensation porous spherical particles obtained in the present invention are obtained by reacting polyfluorene 1 with ethylene glycol and m. There is no waiting for the polyvinyl alcohol of the raw material 1 1 Restrictions * Only polyvinyl alcohol with an average degree of polymerization of 500, -3800 is 1 and it is better to use gold> or mixed with some alkali compounds and low degree of polymerization; 1 is better if the average degree of polymerization When it is less than 500, it is not easy to produce a high porosity I 1 and if the average degree of polymerization is greater than 3800, f is difficult to handle in mixing and other projects because the viscosity is 11 degrees too high f when dissolved in 71 m in water. Use 1 I mixed poly (ethylene 7) enzymes with different degrees of polymerization Raw materials t can also be mixed. 1 1! 1 1 t 1 This paper size is applicable to Chinese National Standard (.CNS) A4. (210X297 mm) 421658 A7 B7 Central Standards Bureau, Ministry of Economic Affairs, Masonry Consumer Cooperative, India Ben Wu 、 Explanation of the invention [occupation] 1 1 Those in the above range (such as the degree of polymerization) 5ί 10 or the degree of polymerization: 10 [one of them] 1 $ will not have 1 1 problems 〇 especially for flexibility, softness, texture, porosity 1 1 N. Improved water absorption, etc. »Polyvinyl alcohol resin with low degree of polymerization can also be used. 0 Please 1 first 1 The porosity of the porous spheroids of this polyvinyl shrinkable m.» As you read and read 1 Set for use 1 No other restrictions 9 Only 5 C ~ 9ί% is lower than the back-1 I of 1 d d When the porosity is less than 5C%, it is difficult for each stomata to communicate with each other. Attention 1 Matter 1 When there is a bubble As a result, water permeability is significantly impeded. In addition to this [when \ t porosity is greater than 98% > Fill in this package due to reduced mechanical strength such as friction resistance, etc. »Problems due to restrictions on use due to its use • s_ ^ · 1 I About the degree of polycondensation of polyvinyl acetal polysaccharides »No other J 1 limit i, except that the degree of acetalization is preferably 30 to 85 mol% * The most preferred is 4 5 to 1 1 7 0 Molar% 〇 Among them * Polyvinyl methylal with a degree of methylation of 30 85 mol% (preferably 1 is 4 570 mole%) is preferred. 1 m by adjusting the shrinkage degree within this range 9 to obtain a soft and abrasion-resistant bioremovable carrier 1 1 and if the shrinkage degree is less than 30 mol% | * low molecular cross-talk degree 9 intensity Poor ». Low friction fastness 〇 So% wait [1 Do not use as a fluidized bed type porous material 9 When the carrier flows, it will be produced due to friction between the carrier and the anti-mac m tank And it is easy to wear 9 and cause 1 | carrier life is reduced by 0. In addition, J has reduced resistance to bioerosion and -J = ~ is not Γ. It is a demand and there are problems that are difficult to handle in the manufacturing process. 0 In addition * 1 \ If the degree of shrinkage When the ratio is greater than 85, the porosity decreases and the false specific gravity increases. 1 1 1 The water content decreases, especially when used as a fluidized bed type granular porous material. »1 1 It is easy to settle but not easy to float. Therefore, it reduces the flow performance in the treatment tank. 0 In addition 1 ί 9 It is not desirable to reduce hydrophilicity when the amount of remaining hydroxyl groups is reduced. \ \ 〇 In addition, the anti-JVO W property 8 when wet is reduced by 1 趿 water resistance and durability, and S pseudo is not 1 J i 1 paper rule / liiM home CN (CNS) Λ4 specification (210X297mm) 42165 8 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) 1-| When pressing, make 1 1 wet in the processing tank, etc. »It is difficult to restore the original shape or cannot be restored to the original I 1 original» Do not suffer from permanent obliqueness and cannot be used as a pressed processed product. Based on this point t verse 1 first 1 If the degree of shrinkage is 30 8 £ mol% (preferably 45_-70 mol%), please read 1 Vinyl contraction porous material »In particular, the degree of reduction of methane 30 to 8E mol% Back 1 1 (preferably 4 5 ~? 0 mole%) of polyvinyl formaldehyde m, it is 1 in terms of resistance to biodegradability 1 and good in terms of bioerosion resistance and excellent in strength »friction fastness is high 0 Xiao Xiang 1 I again 1 1 so» especially » When used in a fluidized bed type granular porous material, you can write 4 copies of a book 1 High-load BM wax, and * When used in a fluidized bed type porous material * Page 1 I can maintain the porosity that makes the processing tank easy to sink and flow »And water-containing state 1 ί fake bb weight 4 and excellent fluidity due to good hydrophilicity 1 j energy 〇 In addition» the resilience when wet m is higher 1 and dry compression processing 1 order » Even if it is used as a compressed product, it is not easy to be permanently distorted »It can be restored to its original shape after being moistened in a processing tank. Therefore, the porous spherical particles of the present invention can be used as a pressing process. It is a compact porous material! I Spherical particles can greatly improve the transferability of granular porous materials »And 1 1 When the medium is wet in the treatment tank, the treatment solution is dissolved > Absorb water and return to the line i Shapes up to m and can float and flow vertically in the treatment tank \ It does not need to be kept to form water-containing particles ♦ It can significantly shorten the treatment time. Moreover, J i, the compression of porous spherical particles pseudoly refers to the porous spheres of the present invention. Shaped particles 1 I It 丄 particles that are compressed (pressed) in any shape 0 1 ί In addition, one of the important reasons for determining the properties of the porous spherical particles 1 1 is the tfc species of the particles. The specific gravity of the particles can be as described above. The porosity is controlled »1 I, but the tb weight of the particles depending on its use 9 can be smaller m lighter layer 0 0 is 1 1 1 1 1 1 This paper size applies the Chinese National Standard (CNS) A4 regulations. (2丨 OX 297 mm) 658 Β7 Economy, printed by Deng Central Bureau of Standardization, Shellfish Consumer Cooperative, V. Description of invention (8) 1 1 In the case of m biocarriers used in fluidized beds, etc., fluidity is important because of the 1 1 factor *, which is extremely useful for controlling a wide range of proportions. IMPORTANT Here is a porous sphere based on a polyethylene-based shrinkage resin with excellent mechanical strength. 1 1 If the inside of a 1-shaped particle is hollow, it depends on the degree of hollowness. 1 The porous structure allows the specific gravity of the particles to be controlled in a wide range. 9 Furthermore, the hollow particles of the present invention 1 | 1 can be produced early 3d by the following method. Note 1 I The water content of the biological carrier of the present invention The state of fcb is adjusted to 1.0. Matter 1 1 1.2 is better. If the weight of the fake fcb in the water state is less than 1.0, filling in the filling tank at the input will only float up > making handling difficult > and if it is greater than 12, the page S-1 will easily settle and lack flow. Therefore, the polyvinyl chloride shrinks m% of porous 1 1 in the water state with a false specific gravity of 1.0-1.2. The biological carrier 1 1 t of the present invention is especially used as a fluidized bed granular porous material. It can be used appropriately. Order good fluidity «1 Moreover, when the microbial carrier solution of the present invention is conspired in the pores of the porous material I 1, the bt weight is closer to the specific gravity of the liquid itself 1 1 It is better if the false fcb in a water-containing state when the liquid to be treated is converted to water is 1 1 1. 0 or more, and it is best to be close to 1.0. However, it is a polyethylene-based shrinkable porous material. Practically watery The false specific gravity is 1-〇- ^ 1.2 .2 1 1 as described above, preferably 1. 0 1 1. 1 0 The true meaning of the original Japanese person s is 1. 2 4 ~ 1.28 [1 comparative The best is 1 * 2 5 1.. 2 6 0 Polyethylene with a specific gravity in this range 1 1 | Basic shrinking m 糸 Porous material as m biological carrier) Especially as flowing I 1 bed granular porous The substance can exhibit good fluidity. 1 I The microbial carrier of the present invention * A granular material with a size of 1 m 1D ~ 2 0 mm 1 in an aqueous state is preferable. This can improve the flowability. * The olive biological treatment 1 1 10 I 1 1 This paper size applies to Chinese national standard (CNS, Λ4 see brand (210X297 mm) 421658 A7 B7 V. Description of the invention (9) --------- ^ — Please read the note on the back first The ability to write on this page, and can be used for sewage treatment equipment with a recovery filter equipped with a granular biological carrier. , And can keep the biological density at a high concentration. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs If the particle size is greater than 20π »β, it is disadvantageous to use the porous spherical particles of the present invention as a biological carrier. In other words, not only will the flow performance of the particles be reduced, but because of the lack of effective surface area of the load-removing organism, it is difficult to maintain the repellency to a high degree, and it will reduce the ability to retreat. Here, the smaller the particle diameter is, the better the fluidity is. In the fluidized bed reactor, in order to make the carrier flow less energy, the processing performance can be improved, but if it is too small, if the particle size is smaller than lam, it is used. In the case of a sewage treatment device or the like provided with a recovery filter for granular biological removal, there is a problem that the oil recovery device will flow out from the discharge outlet of the device's treatment and discharge liquid, and the concentration of biological organisms is not easy to maintain. At high concentrations. Here, the recovery filter can also be set to a smaller slit with a 1.5mro wedge-shaped wire mesh screen installed at the outlet of the treatment liquid. However, the particles in the drainage and the products of the inanimate organisms will adhere to the slit, which will cause occlusion. Therefore, the size of the filter opening will be limited by itself. The close image of the device determines the most appropriate size of the porous polyethylene particles. The size of the porous spherical particles of the present invention is as described below, and can be easily controlled by the size of the dropped liquid droplets. Specifically, by arbitrarily adjusting the discharge amount of the liquid droplets and the nozzle diameter required for dropping, particles with arbitrary particle diameters can be produced. _ 1 1-(CNS) A4 specification (2! 0X297 mm) · · ·-. + Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 42 1 b5 8 'A7 B7 V. Description of the invention () Porosity of the invention Spherical particles have many pores with an average pore size of fl, which have a size that allows water or air from 2fl to 300 / Zb to flow freely. This is different from a gel having a mesh structure with a molecular level. When the biological carrier is removed and used in the tank, organic matter, phosphorus or nitrogen compounds in the water can be freely moved in and out of the holes of this size. In addition, 撖 biocarriers with a large number of 20 ~ 30Qjuin pores can easily form membranes, and the 撖 biofilm formed on the surface of the carrier is not easy to peel off. Therefore, β is suitable for controlling the pore size. It can be controlled appropriately by the following manufacturing method. Similarly, the sponge made of porous spherical particles of the present invention similarly has pores of a size that allows water or air to move freely, and swells with water to 50% compressive stress at a water content of 50%. Moderate elasticity of ~ 200 × 103N / η2. This moderate elasticity can achieve good abrasion resistance when the carrier flows. In addition, in order to improve the shooting friction and mechanical strength of the porous spherical particles, it is desirable to have a film having pores on the surface of the particles and to make the inside of the particles a porous structure. The spherical particles prepared by the method of the present invention described below have a film on the surface and are excellent in mechanical strength. The porous spherical particles of the present invention are not only put into a fluidized bed type treatment tank, but also aerated and treated as a water-containing substance in the treatment tank, which floats and flows well, and has a good affinity with microorganisms on the material. It can be used for biological treatment with excellent biological attachment. In addition, since it has good abrasion resistance, it is not easy to be abraded even if the friction between the carriers or the inner wall of the reaction tank is caused by the carrier flowing. 3, with high This paper size is applicable to China National Standards (CMS) A4 # see grid (2in _. ≪? 97 公 9) (please read the precautions before filling in this page)
421658 A7 B7 五、發明説明（ 光 命粒 壽狀 體球 載性 且孔 , 多 性之 解構 分架 物為 生脂 撤樹 耐糸 、 0Itt縮 I 基 烯 候 乙 耐 聚 , 以 度 明 強 發 槭。本 機畏 載 ， 的化 fu 7" 細粒 之為 物使 質即 孔且 多而 含 ， ο 就合 者述適 異所極 優上言 體如而 載體物 物載生 生物撤 撤生著 為榭附 做之上 為«!而 傜上表 子 體 ，可 而且 然 ， 。度 途濃 用 髙 之持 型保 床物 動生 流徹 於使 用可 適1) 最 ， .法 性物 動生 流撤 的化 異定 fg固 具括 仍包 理為求 處用企 可適為 ，可像 ft * t 定量法 固生物 物産生 生泥撤 撤污化 使低定 由降固 藉3)括 2).包 ，物及 τπ·1 理機 、 處有 速收 高 回 之或 水質 排物 行定述 進待上 法 膜 物 生 撤 之 (請先閱讀背面之注意事項再填寫本頁) :裝 ° 棰 發積 開物 ，生 處撤 此使 化 定 固 物 生 徹 由0 内 ίϋ ? 細 之 物 質 孔 多 在 體 載 物 生 撤 的 定 固 地 光 分濃 物高 生持 撤保 耐物 、生 性徹 —使 可 候並 耐， ，性 性和 擦親 摩物 耐生 的撤 異及 優性 具動 可流 此， 藉性 解 物量 生生 撤産 的的 定泥 待污 定低 固降 由 ， 藉物 , 價 理收 處回 速或 高質 之物 水的 排定 行待 »C5 . ss S 可處 ，可 度而 訂 經濟部中央標準局舅工消費合作社印製 點點 優缺 之的 法者 物兩 生法 撤物 定生 固撤 括定 包固 與括 法包 膜與 物法 生膜 撤物 生生 産檝 可服 ，克 之可 ^llr-7且 換 - 制酸 限藻 的以 別若 持 0 有佳 没較 、劑 類定 種固 各物 用生 採撤. 可之 劑份 定成 固主 。物為 體生納 載撤酸 物-藻 生處以 撤此惟 之 - 容 可子 具粒 ，狀 時球 份性 成孔 主多 為糸 納薛 定 固 充 填 地 好 良 易 縮 基 烯 乙 聚 孔 多0 甲 基 烯 乙 聚 是 其 尤 狀 球 太*1«-认尺<_消坰中00家梯準（〇奶>八4規格（21〇父297公*> 經濟部中央標準局員工消費合作杜印製 421658 A7 B7五、發明説明（* ) 子之相性。而且，尤其就耐摩擦性而言良好。 使用撤生物固定劑來包括固定徹生物，例如可使多孔 性球狀粒子與含徹生物之撤生物固定劑的混合溶液予以 含浸，使上述撤生物固定劑不溶化於上述多孔質物之細 孔内，予以達成。 本發明之撤生物載體，可適用於不論是上述之包括固 定型（包括固定法）及上述之非包括固定型（微生物膜法） ，或習知之流動性，固定床之載體，另可適用於含污水 處理裝置，各種生物反應器之用途。 待別是本發明之撤生物載體，在處理槽内可適用為使 本發明之粒狀撤生物載體浮沈，對流處理的流動床型污 水處理裝置。 流動床型生物反應器，例如可適用於使上述之載體與 被處理液接觸，進行生物處理，化學處理者。具體而言 ，於適用有機物質等之分解外，亦適用於進行硝化脱氮 等之氣化還原，或加成、取代、變換、脫離等化學反應 之裝置。 本發明之多孔性球狀粒子，其特擞如上所述做為壓縮 壓製成型品傜為所企求。恃別是水份率為1 0 %以下之海 綿粒狀物，投人水中體積急速膨脹至2倍至1 0倍，且含 水狀態之大小為lmra〜20mm,以聚乙烯基縮K集多孔性 球狀粒子為宜。 使本發明之以聚乙烯基縮醛樹脂為架構的多孔性球狀 粒子懕縮壓製之壓縮多孔性球狀粒子（以下簡稱為壓縮 -14- ------------^------ΐτ------^ '· (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用t國國家標準（CNS ) Α4規格（2ΙΟΧ 297公釐） 421658 A7 B7 經濟部中央標準局負工消費合作社印氣 五、發明説明（ ) I 粒 子 ) 可藉由壓縮工程與乾燥工程予以製造< >該壓縮 1 I 粒 子 做 為 m 生 物 載 體投 入 處 理 槽 時 * 急 速 地 吸 水 回 復 I 1 成 原 有 的 形 狀 與 大 小 ,同 時 受 處 理 液 濕 潤 、 浸 染 、 可 浮 V 請 1 先 1 沈 流 勤 ύ 對 此 而 言 ,不 經 壓 縮 壓 製 的 多 孔 性 球 狀 粒 閲 讀 1 » 不 易 使 其 中 的 空 氣 分離 λ 浮 於 水 面 上 » 且 直 至 可 流 背 面 1 I 之 1 動 需 費 時 〇 另 外 t 藉 由壓 縮 壓 製 1 多 孔 質 物 之 體 積 m 意 1 I 小 4 如 上 所 述 亦 可 以 降低 搬 送 成 本 ύ 事 項 再 1 ] 此 外 ♦ 此 處 之 壓 縮 壓製 工 程 Μ 以 於 乾 燥 工 程 後 進 行 為 填 寫 本 1 宜 〇 ΙΠ 使 在 m m 狀 態 下予 以 壓 縮 壓 製 9 不 久 即 回 愎 原 狀 頁 1 I ， Μ 滴 當 的 條 件 所 製 造的 聚 乙 烯 基 縮 醛 多 孔 性 球 狀 粒 子 1 1 t 偽 Μ 由 在 其 水 份 率 為10%以下經乾燥的狀態下 予 以 壓 1 1 .縮 m 製 9 可 在 經 壓 縮 後的 狀 態 下 長 期 保 存 ， 且 投 入 水 中 1 訂 會 急 速 地 膨 脹 ， 回 復 成原 有 的 形 狀 與 大 小 〇 1 m 縮 率 愈 高 愈 好 * 以1/2〜1/10較佳。 壓縮為1/2 1/10 1 1 之 壓 縮 粒 子 » 投 入 水 中會 急 速 地 膨 脹 至 2 倍 10倍 * 回 1 1 復 成 原 有 的 形 狀 與 大 小。 多 孔 性 球 狀 粒 子 之 含 水 狀 態 的 1 1 大 小 1 使 用 為 徹 生 物 載體 時 > 基 於 刖 述 之 理 由 以 1， -2 0 e m 線 I 較 佳 〇 | 而 且 * 投 入 處 理 槽 後馬 上 予 以 使 用 時 r 企 求 含 水 狀 態 Ί 之 聚 乙 烯 基 縮 m % 多 孔性 球 狀 粒 子 〇 1 該 多 孔 性 球 狀 粒 子 ,除 做 為 如 上 所 述 之 徼 生 物 載 體 外 1 | 1 亦 可 使 用 於 酵 素 固 定載 體 1 曲 作 物 水 耕 栽 培 之 溶 液 保 1 1 持 材 或 植 物 支 持 物 、 動棺 物 細 胞 之 培 地 人 工 水 笞 土 1 | 壤 良 材 等 0 此 外 * 持殊 的 使 用 例 如 可 利 用 為 水 中 流 動 1 15- 1 1 1 本紙張尺度通川中^戌家疗t- ( CNS ) Λ4規格（2丨OX297公釐） 421 bb β A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 (»4 ) 1 1 型 洗 淨 部 材 或 水 中 流 動 型 按 摩 部 材 〇 1 1 I 使 多 孔 性 球 狀 粒 子 做 為 包 括 固 定 撤 生 物 載 體 時 使 1 1 多 孔 性 球 狀 粒 子 投 人 分 散 有 活 性 Β 泥 的 液 體 中 使 撤 生 請 ! 先 1 物 附 m 於 上 述 多 孔 性 球 狀 粒 子 表 面 及 / 或 細 孔 内 予 以 閲， 讀 1 背 1 固 定 r> 另 外 > 例 如 * 在 撤 生 物 之 固 定 使 用 微 生 物 固 定 劑 面- 之 1 時 亦 可 在 活 性 污 泥 中 分 散 固 定 劑 » 將 多 孔 性 球 狀 粒 子 注 意 1 事 1 投 入 其 中 赘 予 以 固 定 0 此 時 » 使 用 m 縮 粒 子 時 由 於 污 泥 項 再 1 快 速 地 浸 透 至 粒 子 的 内 部 故 較 佳 0 填 寫 本 裝 I 尤 其 使 用 m 酸 鈉 做 為 固 定 劑 時 t 在 上 述 之 多 孔 性 球 頁 1 1 狀 粒 子 之 撤 生 物 載 體 上 含 浸 含 撤 生 物 之 藻 酸 鈉 的 混 合 溶 1 1 液 t 再 在 含 浸 該 藻 酸 鈉 之 混 合 溶 液 所 得 的 撤 生 物 載 體 上 1 1 添 加 氣 化 鈣 水 溶 液 等 之 多 價 金 靥 鹽 水 溶 液 t 使 上 述 藻 酸 1 訂 1 1 鈉 不 溶 於 上 述 多 孔 質 物 之 表 面 及 / 或 細 孔 内 9 可 得 上 述 包 括 固 定 有 撤 生 物 之 粒 子 狀 多 孔 質 撤 生 物 載 體 0 而 且 1 1 ! 使 撤 生 物 固 定 劑 流 入 微 生 物 載 體 之 細 孔 内 9 % 在 減 壓 下 1 I 進 行 較 佳 〇 1 1 ..泉 1 本 發 明 多 孔 性 粒 子 之 撤 生 物 載 體 * 對 應 於 任 — 習 知 之 撤 生 物 處 理 裝 置 9 可 利 用 填 充 於 DB 早 槽 型 或 多 槽 型 撤 生 物 1 1 處 理 槽 中 對 厭 氣 性 處 理 * 好 氣 性 處 理 皆 具 效 果 性 作 用 1 Ο 而 且 * 本 發 明 之 撤 生 物 載 體 可 使 用 於 流 動 床 或 使 載 1 r 髖 固 定 於 反 應 槽 内 部 之 所 謂 的 固 定 體 型 載 體 〇 1 I 上 述 之 多 孔 性 球 狀 少丄 粒 子 9 可 Μ 由 下 述 之 製 法 9 予 以 簡 1 1 CltT 里 且 高 生 産 性 製 得 0 1 i 其 — 的 製 法 例 如 多 孔 性 球 狀 粒 子 之 製 法 j 其 恃 m 為 使 1 16 I 1 1 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 42 165 8 A7 B7 經濟部中央標隼局員工消費合作杜印製 五、發明説明 ( ) 1 存 醉 性 溶 液 中 具 凝 膠 化 性 質 之 水 溶 性 高 分 子 與 聚 乙 烯 醇 1 1 1 與 m 類 E 合 而 成 的 水 溶 液 滴 入 酸 性 溶 液 中 使 該 液 滴 凝 1 ! m 化 1 同 時 使 該 液 滴 中 之 聚 乙 烯 醇 與 m 類 反 應 * 製得 ^—v 請 1 先 1 以 聚 乙 烯 基 縮 m % 樹 脂 為 架 構 之 多 孔 性 球 狀 粒 子 〇 讀 1 I m 由 本 製 法 由 於 可 同 時 進 行 縮 m 化 處 理 球 狀 粒 子 之 背 面 1 I 之 1 成 形 過 程 » 故 不 需 習 知 之 多 段 式 工 程 * 可 簡 単 地 且 以 高 注 意 古 1 1 生 産 性 製 造 接 近 圓 球 之 均 一 粒 子 直 徑 的 多 孔 性 球 狀 粒 子 事 項 再 1 I 〇 此 外 j 粒 子 的 表 面 附 有 皮 膜 * 旦 具 有 優 異 的 機 械 強 度。 填 寫 本 1 裝 I 本 製 法 之 待 1 傜 使 含 聚 乙 烯 醇 之 溶 液 與 酸 性 溶 液 反 寅 1 1 應 * 由 形 成 液滴形狀的同時經做為觸媒之酸性溶液 1 1 作 用 * 使 該 液 滴 中 所 含 的 聚 乙 烯 醇 與 醛 類 之 縮 m 化 同 時 1 1 開 始 作 用 〇 換 -Λ，. 之 * 溶 液 中 之 聚 乙 烯 醇 與 m 類 > % 與 做 1 訂 為 觴 媒 之 酸 性 溶 液 不 接 觸 時 不 起 任 何 反 應 保· 持 溶 液 的 1 狀 熊 » 而 在 與 酸 性 溶 液 接 觸 的 同 時 開 始 縮 m 化 反 應 > 開 1 1 始 固 化 〇 此 外 ， 溶 液 所 含 的 酸 性 溶 液 中 具 凝 膠 化 性 質 之 1 | 水 溶 性 高 分 子 r 例 如 藉 由 離 子 交 換 反 應 具 凝 膠 化 性 質 之 1 1 線 1 水 m 性 高 分 子 藉 由 酸 的 作 用 1 馬 上 進 行 離 子 交 換 等 而 成 凝 m 狀 物 質 • 具 粘 性 故 可 防 止 直 至 聚 乙 烯 醇 與 m 類 反 I 應 终 了 之 間 球 狀 形 態 之 變 形 而 且 1 本 發 明 之 製 法 中 * 1 Ί 亦 可 U 由 使 徹 生 物 練 於 由 聚 乙 稀 醇 與 水 溶 性 高 分 子 與 1 m 類 所 成 的 水 溶 液 中 而 製 成 包 括 固 定 載 體 等 > 視 其 使 ! I 用 巨 的 亦 可 做 配 比 m 整 等 之 必 要 處 理 0 1 ! Iff 由 該 方 法 所 得 的 粒 子 成 為 多 孔 性 9 乃 是 Μ 由 使 該 球 1 | 狀 粒 子 乾 燥 » 存 在 於 聚 乙 烯 基 縮 醛 % 架 構 粒 子 中 » 例 如 1 17 1 1 1 1 本紙張尺度適用中國國家標準（CNS ) Λ4叱輅i :m_y 公ft ) 421658 ' A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 (<y ) ί* 由 m 酸 鈣 等 之 凝 嘐 乾 燥 r 收 縮 會 形 成 空 隙 〇 而 且 t 在 粒 子 表 而 上 形 成 皮 膜 之 理 由 % 由ΐ 在其表面上不 存 在 有 做 為 氣 孔 形 成 劑 功 能 之 物 質 (水溶性高分子凝膠 、 澱 粉 等 之 氣 孔 形 成 劑 兩 者 )、 而無法製得， 與富含有 氣 孔 形 成 劑 之 粒 子 内 部 與 薛 類 反 時 形 成 柑 同 的 架 構 之 工 程 〇 結 果 1 以 球 狀 粒 子 之 形 態 進 行 縮 醛 化 反 應 之 本 發 明 粒 子 表 面 t 係 多 孔 性 球 狀 粒 子 而 表 面 上 具 有 細 孔 之 薄 膜 設 於 粒 子 表 面 之 粒 子 1 % 粒 子 内 部 為 具 髙 氣 孔 率 之 海 綿 狀 立 體 網 g 構 造 的 多 孔 質 物 〇 另 外 > 在 酸 性 溶 液 中 H 由 如 離 子 交 換 反 應 具 有 凝 膠 化 性 質 之 水 溶 性 高 分 子 (以下之其他製法皆相同）， 没 有 恃 別 的 限 定 例 如 有 藻 酸 鈉 角 叉 菜 m 聚 丙 烯 酸 鈉 0 聚 乙 烯 醇 之 濃 度 雖 役 有 特 別 的 限 制 9 一 般 而 ^v. 聚 乙 烯 醇 濃 度 愈 高 1 易 得 球 狀 粒 子 » 而 聚 乙 烯 醇 m 度 愈 低 時 易 得 含 水 凝 膠 狀 物 〇 此 等 之 粒 子 物 性 的 差 異 » 不 僅 是 依 存 於 聚 乙 烯 酵 之 濃 度 1 亦 受 其 他 因 素 的 影 m 1 惟 聚 乙 烯 醇 m 度 不 僅 曰 疋 受 球 狀 粒 子 中 之 含 水 凝 瘳 粒 子 影 礬 1 且 樹 脂 架 構 之 粒 子 亦 為 重 要 的 主 因 之 — 0 因 此 9 本 發 明 其 配 合 量 亦 極 為 重 要 0 本 發 明 中 聚 乙 烯 醇 濃 度 若 大 於 20 莫 耳 96 時 » 溶 液 之 粘 度 變 高 1 不 僅 變 得 不 易 處 理 9 於 滴 下 時 産 生 如 拉 纱 之 水 滴 狀 粒 子 > 無 法 製 得 均 直 徑 或 接 近 均 直 徑 之 球 狀 物 0 而 目. 聚 乙 烯 醇 濃 度 若 小 於 5 莫 耳 % 時 S ti 由 滴 入 後 之 縮 m 化 反 應 所 得 的 球 狀 )px h. 子 之 強 度 m 低 1 偽 不 為 所 18 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X2^7公釐） 4 2 16 5 8 * A7 B7 經濟部中夬樣準局員工消費合作社印裝 五、發明説明（ ) I 企 求 ΰ 所 以 » 聚 乙 烯 醇 濃 度 以 5〜20重量％為宜t 尤J 1 1 Ί〜 [5重量％最佳„ 惟以下述之申請專利範圍第20項之 1 1 製 法 製 造 中 空 粒 子 時 9 降 低 少 許 濃 度 者 易 為 *5ί=» 兀 美 的 粒 子 請 1 1 9 1〜7重 量 % 者 較 佳 〇 而 且 該 混 合 液 之 溫 度 没 有 的 限 閱 1 制 9 若 為 不 會 互 相 改 性 f 可 保 持 流 動 性 之 溫 度 即 可 » 即 背 1 I 之 1 使 在 常 溫 下 亦 没 有 什 麼 問 題 發 生 〇 意 1 I m 類 例 如 有 甲 、 苯 甲 m X 乙 m 丁 m 、 丙 烯 m 或 乙 事 項 I 1 1 二 等 脂 肪 族 t 芳 香 族 m 類 0 或 Η 由 共 存 之 酸 可 容 易 寫 本 .1 Λ 地 將 縮 m 變 換 為 m 類 予 以 利 用 t 就 考 慮 與 聚 乙烯醇之反 頁 1 1 應 性 、 水 溶 性 N 價 格 、 處 理 性 、 反 應 生 成 物 之 強 度 > 反 I 1 彈 性 及 反 應 後 之 容 易 處 理 性 等 而 言 t 尤 以 甲 m 最 佳 〇 1 1 類 之 濃 度 没 有 特 別 的 限 制 t 惟 影 逛 樹 脂 架 構 粒 子 之 1 訂 縮 醛 化 度 者 極 為 重 要 〇 本 發 明 中 m 類 之 廣 度 視 共 存 之 1 酸 觸 媒 濃 度 及 反 應 溫 度 而 定 必 須 選 擇 適 當 的 腠 度 0 m 類 1 1 濃 度 愈 问 時 V 可 缩 短 到 逹 所 企 求 的 縮 m 化 度 之 時 間 〇 惟 1 j 過 高 時 反 應 速 度 加 快 t 不 易 控 制 縮 化 度 〇 一 般 而 言 > 1 縮 醛 化 度 高 者 過 於 提 高 強 度 時 t 於 製 造 多 孔 質 物 時 會 降 線 [ 低 氣 孔 率 > 假 比 重 增 加 » 含 水 率 會 降 低 0 此 外 ) 伴 隨 殘 j 1 存 的 羥 基 之 減 少 t 親 水 性 降 低 〇 另 外 ♦ 粒 子 之 反 彈 性 亦 降 低 0 1 % 外 1 縮 m 化 度 如 上 所 述 以 3 0 85莫耳 % 為 宜 0 尤 其 1 1 使 用 於 必 須 具 梭 膠 jBb 性 與 較 硬 的 硬 度 之 流 動 床 型 撤 生 物 1 1 載 體 時 » 必 須 設 定 於 5 5 85莫耳 % 0 此 時 之 縮 的 濃 度 ! t 視 其 種 類 而 不 冏 * 惟 使 用 甲 時 以 設 定 為 3〜 • 1 ϋ重量％ 1 1 19 1 1 1 本纸張尺度適用中國國家標準（CNS ) A4規格（2〗OX 297公釐） 經濟·部中央標準局貝工消費合作社印製 421658 A7 B7 五、發明説明（β ) 較佳。 於酸性溶液中具凝嘐化性質之水溶性高分子，例如藉 由離子交換反應，具凝膠化性質之水溶性高分子，如上 所述抅有特別的限制，例如有藻酸鈉、角叉菜膠、聚丙 烯酸鈉等，惟考慮凝膠化達度、凝膠狀態等時，以藻酸 納最样，利用該物為所企求。藻酸納之分子量沒有待別 的限制、惟髙分子量者易於製造凝嘐化速度高且完美的 粒子。惟為高分子量時由於其溶液的粘度上升過髙，易 成水滴狀粒子偽不為企求。具體而言以使用在201, 4% 濃度具30dPa* sec之粘性的藻酸鈉為宜。惟本發明不受 此所限制。 而且，聚乙烯醇溶液中所含有的例藉由離子交換度 應之具凝朦化性質的水溶性高分子，如上所述可做為 氣孔形成劑及形狀維持劑，惟於該範圍中該濃度没有特 別的限制。一般而言若此等之濃度高時，溶液之粘度增 加、且於滴入時多會産生障害。另外，若濃度低時，凝 膠生成之反應速度慢、不易製得球狀粒子。若考慮該處 理時，該濃度視藻酸銷之分子量而定，惟上述範圍之分 子最時為0.5〜5重量％，尤以1〜5重量％較佳。尤其是 藻酸鈉小於0 . 5重量％時，相較下水面或水中之水溶性 高分子太身之表面張力，其分散力變強，致無法進入而 在水而上擴散。另外，若藻酸鈉之濃度大於5重量％時 ，在由供應口拉絲之狀態下注入溶液中，結果不易製得 均一直徑之球狀粒子。 -20- 本紙張尺度適用中國國家標準（CNS ) Α4規格（2!〇Χ 297公釐） — I ΐ衣 Iΐτ------.^ (讀£-閱讀背fi-之注意事項再填寫本買) 421658 - A7 B7 經濟部中央楼準局I工消費合作社印褽 五、發明説明（ (5 ) 1 1 為 促 進 聚 乙 烯 醇 與 m 類 反 應 * 本 發 明 之 製 造 工 程 中 以 1 1 使 用 酸 性 溶 液 較 佳 0 此 等 之 酸 類 有 持 别 的 限 制 例 如 I I 可 選 白 硫 酸 鹽 酸 > 磷 酸 及 顒 丁 烯 二 酸 等 之 無 機 酸 以 讀 1 先 1 及 有 4<# 微 酸 惟尤以強酸較佳。 尤其就處理f 衍言以硫酸 讀 1 最 佳 » 惟 視 併 用 的 多 價 金 屬 鹽 之 種 類 而 定 m 擇 必 須 的 背 1 [ 之 1 適 當 併 用 之 酸 種 類 0 意 1 事 1 對 多 價 金 屬 鹽 水 溶 液 亦 没 有 特 別 的 限 制 * 主 要 以 氣 化 項 -S' 1 鈣 氛 化 鋅 、 硫 酸 鋁 等 為 宜 〇 濃 度 偽 視 所 選 擇 的 金 屬 鹽 填 寫 本 1 裝 I 種 類 或 水 溶 液 之 溫 度 不 同 f 惟 若 使 用 氣 化 鈣 時 以 1 ' -2 0 頁 1 [ 重 童 % 為 宜 Q 而 且 * 於 如 請 專 利 範 圍 第 2 C 項 之 發 明 中 1 1 該 m 度 若 過 高 時 S 生 成 的 凝 膠 粒 子 變 大 同 時 易 與 鄰 接 1 1 的 其 他 粒 子 産 生 熔 融 的 現 象 i 産 生 不 良 的 現 象 0 而 且 $ 1 訂 在 如 申 請 專 利 範 圍 第 1 7 項 之 製 法 中 » 添 加 少 量 的 氮 化 鈣 1 等 之 多 價 金 屬 鹽 於 酸 性 水 溶 η 中 時 > 不 易 使 球 狀 粒 子 U_f 朋 1 1 糜 製 得 具 均 一 直 徑 之 球 狀 粒 子 0 1 I 藉 由 如 申 請 專 利 範 圍 第 17 項 第 2 0 項 之 製 法 所 製 得 的 1 1 聚 乙 烯 基 縮 m % 球 狀 粒 子 » 並 不 是 在 水 溶 性 高 分 子 之 含 A | 水 凝 膠 中 含 有 聚 乙 烯 基 縮 m » 而 是 聚 乙 烯 基 缩 m 之 樹 脂 | 架 構 内 含 有 藻 酸 納 等 之 水 溶 性 高 分 子 的 含 水 凝 膠 之 狀 1 態 下 製 得 之 〇 如 上 所 述 經 乾 燥 的 該 樹 脂 粒 子 偽 使 溪 酸 1 \ 納 等 水 溶 性 高 分 子 之 凝 謬 收 縮 » 而 成 微 細 孔 徑 之 多 孔 質 I I 0 藉 此 可 得 橡 膠 狀 彈 性 或 較 硬 的 多 孔 性 球 狀 樹 脂 粒 子 0 1 而 且 投 入 水 中 時 > 經 收 縮 的 m 酸 鈉 等 水 溶 性 高 分 子 之 ，1 I 凝 膠 回 復 成 含 水 凝 膠 9 且 為 多 孔 質 構 造 可 利 用 做 為 徹 生 1 I 物 之 住 處 0 另 外 i 排 除 該 粒 子 中 所 含 有 的 上 述 凝 膠 時 i 1 [ 二 2 1 - 1 1 本紙琅尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 4 2 1 b 5 8 A7 B7 經濟部中央標準扃員工消費合作社印製 五、發明説明（W) v I 可 得 外 部 開 孔 的 多 孔 質 球 狀 粒 子 〇 製 造 具 較 大 的 氣 孔 直 1 1 I 徑 及 氣 孔 率 之 粒 子 時 如 下 所 述 預 先 在 聚 乙 烯 醇 溶 液 中 1 1 加 入 粉 等 之 氣 孔 形 成 劑 予 以 製 得 0 氣 孔 直 徑 及 氣 孔 率 /*s 請 1 先 1 愈 大 時 * 愈 容 易 除 去 縮 m 反 應 後 之 殘 存 物 質 且 可 縮 短 閱 讀 1 | 洗 淨 時 間 〇 此 外 9 提 高 氣 孔 率 可 使 假 比 重 降 低 » 且 伴 隨 背 面 之 1 1 使 水 中 之 流 動 性 提 高 〇 1 堂 1 | 另 外 本 發 明 球 狀 粒 子 之 製 法 的 其 他 實 施 形 態 > 像 使 ψ 項 再 1 1 由 離 子 交 換 反 應 使 具 凝 膠 化 性 質 之 水 溶 性 古 同 分 子 與 聚 填 寫 本 1 裝 I 乙 烯 醇 混 合 溶 解 而 成 的 溶 液 滴 入 多 價 金 屬 鹽 水 溶 掖 中 t 頁 1 I 月. m 由 離 子 交 換 反 應 使 該 液 滴 形 成 含 凝 嘐 化 的 聚 乙 烯 醇 1 I 之 凝 m 狀 球 狀 Jr · 粒 子 然 後 再 將 該 凝 膠 狀 l|r * 粒 子 添 加 於 含 m 1 1 類 之 酸 性 溶 液 中 * 且 使 該 凝 膠 狀 粒 子 物 中 所 含 有 的 聚 乙 1 訂 烯醇與醛類反 瞧 1 以 製 得 縮 m 化 度 為 30 85莫耳妬 9 以 ( I 聚 乙 烯 基 縮 醛 % 樹 脂 為 架 構 之 多 孔 性 球 狀 粒 子 0 1 1 該 製 法 不 是 使 用 水 溶 性 高 分 子 之 含 水 凝 瞟 做 為 球 狀 粒 1 1 子 之 主 要 成 份 9 而 是 做 為 球 狀 粒 子 之 保 方 法 » 予 以 藺 1 1 線 1 BO 里 且 大 量 地 製 造 具 橡 膠 彈 性 或 較 硬 質 等 物 性 t 且 接 近 均 一 直 徑 之 聚 乙 烯 基 縮 % 架 構 球 狀 ib_t» 粒 子 0 換 言 之 Μ 由 1 1 m 整 形 成 聚 乙 烯 基 縮 m 之 架 構 Ji-L 粒 子 > 主 要 成 份 之 聚 乙 烯 \ 1 醇 1 及 逹 到 製 造 工 程 上 球 狀 粒 子 之 保 形 作 用 及 氣 孔 形 成 I 1 作 用 的 m 酸 納 等 水 溶 性 萵 分 子 之 各 配 合 量 bb 例 t 及 使 聚 1 I 乙 烯 醇 之 縮 化 度 調 整 為 上 述 之 配 合 比 例 可 簡 DB 早 且 大 1 暈 地 製 造 具 橡 瞟 彈 性 及 較 硬 質 等 物 性 ， 且 接 近 圓 球 » 均 ' 1 I 一 粒 子 直 徑 之 聚 乙 烯基縮醛糸架構球狀粒 子 〇 另 外 為 使 1 22 1 1 1 本紙用中《阄革榡率（CNS ) Λ4規格（210X297公釐） 421658 A7 B7 經濟部中央標隼局負工消費合作社印製 五、發明説明（y ) 1 縮 m 化 反 應 為 ~- 工 程 就 與 上 述 Φ 請 專 利 範 圍 第 17項 1 1 I 等 之 m 法 比 較 以 能 簡 CM-» .甲- 地 調 整 縮 醛 化 度 較 佳 0 縮 醛 化 1 1 度 之 m 整 可 m 由 m 整 反 應 液 之 類 配 合 量 * 反 應 液 之 溫 請 ! [ 度 反 瞧 時 間 予 以 控 制 〇 閱 I 1 I 另 外 m 造 具 m 異 耐 摩 擦 性 及 機 械 強 度 之 以 聚 乙 烯 基 背 面 1 I 之 1 縮 m 樹 脂 為 架 構 之 中 空 狀 多 孔 性 球 狀 粒 子 之 方 法 j 偽 注 意 重 1 1 如 Φ 請專利範圍第20項之 方 法 所 記 載 ， 使 多 價 金 靥 鹽 水 Ψ 項 再 1 1 I 溶 液 滴 入 iff 由 離 子 交 換 反 應 具 凝 膠 化 性 質 之 水 溶 性 高 分 寫 本 1 裝 子 與 聚 乙 烯 醇 混 合 溶 解 所 成 的 水 溶 液 中 * 且 藉 由 多 價 金 頁 \_-· t I m 鞔 之 液 滴 與 水 溶 性 古 问 分 子 反 應 予 以 凝 固 0 在 液 滴 之 外 1 1 1 圍 部 份 形 成 混 有 與 多 價 金 屬 鹽 反 腊 之 水 溶 性 高 分 子 凝 嘐 1 1 與 聚 乙 烯 醇 之 凝 膠 球 狀 粒 子 物 t 然 後 > 使 該 凝 膠 狀 粒 子 1 訂 物 加 人 含 m 類 之 酸 性 水 溶 液 中 * 藉 由 使 凝 m 狀 粒 子 物 中 1 所 含 的 聚 乙 烯 醇 與 m 類 反 應 製 得 0 1 1 本 發 明 之 製 法 俗 藉 由 使 多 價 金 展 m Jm 水 溶 液 滴 入 聚 乙 烯 1 1 醇 溶 液 中 * 使 液 滴 外 圍 部 份 凝 膠 化 9 且 因 此 使 聚 乙 烯 醇 1 1 線 1 溶 液 無 法 浸 入 液 滴 内 部 » 而 無 法 引 起 凝 膠 化 結 果 生 成 物 為 中 空 j·丄 WL 子 〇 1 上 述 之 各 種 m 法 所 得 的 球 狀 粒 子 為 多 孔 性 如 上 所 述 Ί 由 球 狀 粒 子 之 乾 燥 而 使 聚, 乙 烯 基 縮 醛 系 架 構 粒 子 中 所 1 存 在 的 凝 m 收 縮 0 而 且 ί 若 必 須 為 較 大 直 徑 之 氣 孔 時 t 1 I 或 平 之 内 而 與 外 而 没 有 分 佈 有 氣 孔 率 時 1 此 至 少 可 藉 I i 由 離 子 交 換 反 應 以 使 具 凝 膠 化 性 質 之 水 溶 性 高 分 子 與 聚 * 1 | 乙 烯 醇 混 合 溶 解 而 成 之 水 溶 液 中 加 人 氣 孔 形 成 劑 » 可 製 1 I 23 1 1 1 1 本紙译尺度適用中國國家標準（CNS ) A4規格（210X 297公茇） 經濟部中央標準局員工消費合作社印來 42165b A7 B7 五、發明説明（p ) 得孔徑大的多孔質物。氣孔形成劑沒有特別的限定，惟 澱粉之粒度較為均一，且粒子之大小最適於本發明多孔 性球狀粒子所企求的細孔直徑。另外，於洗淨多孔性球 狀粒子時以水較易予以洗淨、流動、粒子成形後之處理 較為容易。藉由添加該澱粉等之氣孔形成劑以製得的多 孔性球狀粒子，恃別適合利用做為流動床型微生物載體。 而且，可精極地自上逑以聚乙烯基縮醛糸樹脂為架構 之多孔性球狀粒子中除去凝腠。換言之，上述之多孔性 球狀粒子可藉由乾燥來收縮凝嘐以形成多孔質物，惟在 濕澗狀態下呈現多孔質構造且有回復成凝膠的傾向。因 此，藉由積極地除去該凝瞟，亦可使用為濕潤狀態下外 部開孔之多孔質物。凝膠之主成份傜為藉由酸性溶液具 凝圈化性質之水溶性髙分子之凝膠。例如去除藻酸等之 該水溶性高分子凝膠的方法，傺使粒子添加於含鈉離子 之溶液中，且藉由！I拌洗淨予以離子交換的方法，或對 乙二胺四醋酸（EDTA)與如磷酸緩衝劑之鈣離子而言利用 螯合削的方法，其他例如離心分離的方法。任一方法皆 為合適的凝膠除去方法。 而目.，含下述實施例之本發明氣孔直徑、氣孔率及縮 薛化度傜以下述之測定法為基準予以測定。 (氣孔直徑之測定） 氣孔肓徑之測定偽依A S T H (D e s i g n a t i 〇 n:: 0 4 4 0 4 - 8 4 ) 為基進予以_定。具體而言，使用P 0 R G U S M A T E R I A L S , I N C公司製測孔儀，藉由水銀壓入法細孔測定來求取平 本紙張尺度適用中國國家枒步-(CNS ] AWUA ( 210_X297公釐） --------▲------1T------^ (讀4-閱讀背&-之注意事項再填寫本頁〕 經濟部中央標準局員工消費合作社印製 421658 A7 B7五、發明説明（） 均氣孔直徑》 (氣孔率之測定） 使試樣為濕潤狀態，使用浮標測定3痼地方之直徑， 測定假體積（Va)及使用島津製作所製乾式自動密度計阿 比克（譯音）1 3 3 0 (商品名）測定直體積（V)。使用該值藉 由下述式來計算氣孔率e (%)。 E = { 1-Va/V) X 100 (縮醛化度之測定） 由重氫氣仿、三氟醋酸水溶液中之質子NMR測定、藉 由下式來算出縮醛化度F(% )。 F =(a/e)XlOO c :甲烯質子（例如4. 153、4.442 ppm)之波峰強度合計 a :鄰接於醚基之甲烯質子（例如，4.667、5.150、 5.313、5 . 3 2 6 ppm)之波峰強度合計。 於下述中以實施例詳細地說明本發明。惟本發明不受 此等所限制。而且，以下之實施例及比較例中之％係指 重量％。 (實施例1 ) (滴下液） 聚乙烯醇 7 · 5 % 藻酸鈉 1.0% 甲醛 4.0% 水 87.5% -2 5 - ----------¾衣------ΐτ------Λ (請先k讀背¾.之注意事項再填寫本頁) 本紙張尺度遠用中國國家標準（CNS ) A4規格（210X297公釐） 421658 經濟部中央標準局,工消費合作社印聚 A 7 B7五.、發明説明（-Μ (反應液） 硫酸 10.0% 水 90.0% 使平均聚合度為1 5 0 0 ,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷郤，且於其中添加另外諝製的藻酸鈉水 溶液，再加入甲醛水溶液予以均勻地混合。然後，使該 混合液滴入】0 %硫酸水溶液中。該硫酸水溶液之液溫為 硫酚水溶液中所形成的液滴以約5分鐘予以凝嘐 化，該狀態反應1 5分鏡後，使該粒子分離製得以聚乙烯 蓽縮醛為樹脂架構之彈性粒子物。使該物藉由水洗予以 充份洗淨、乾燥，製得粒子直徑3〜4ιπιβ之接近圓球的均 一粒子直徑之聚乙烯基縮醛条多孔性球狀粒子。 (實施例2 ) (滴下液） 聚乙烯醇 7.5% 藻酸鈉 1 · 〇% 水 9 1.5¾ (S應液） 硫酸 5.0% 甲薛 4.0% 水 91.0% 使平均聚合度為1 5 0 0 ,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷卻，且於其中添加另外調製的藻酸鈉水 溶液，予以混合。然後，使該混合液滴人甲醛水溶液與 - 2 6 - ----------ΐ衣------iT-------^ (請l閱讀背ώ·之：'Λ意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格< 2!fw ί 1 421658 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（ ) 1 硫 醅水 溶液 均 勻 m 合 者 中 〇 該 酸 性甲 溶 液 之 液 溫 為 1 1 6C )in „ 滴入 的 液 滴 以 約 5 分 鐘 予 以凝 膠 化 t 該 狀 態 反 應 1 1 約 30分 _後 I 製 得 以 聚 乙 烯 基 縮 醛為 樹 脂 架 構 之 强 性 tfl ΐι 粒 請 1 先 1 子 〇該 物與 實 施 例 1 所 得 者 約 相 同。 閱 讀 1 1 (比較例]) έ 之 1 (滴下液） 意 玄 I I 聚乙 烯醇 7 . 596 Ψ 項 再 I I 甲_ 4 . 096 4 寫 本 1 裝 I 水 8S . 5% 頁 1 I (反應液） 1 ί 硫酸 1 0 . 096 1 1 水 90 . 0% 1 訂 1 i 使平 均聚 合 度 為 15 00 t 1.ΙΓ» 兀 全 容 化的 聚 乙 烯 醇 樹 脂 溶 Λ73 m 於 熱水 後予 以 冷 卻 且 於 其 中 加 入甲 醛 水 溶 液 均 勻 地 1 1 予 以混 合。 然 後 > 使 該 混 合 液 滴 入液 溫 為 60 之 10% 硫 1 I 酸 水溶 液中 0 .但 疋 > 經 滴 入 的 混 合液 未 能 保 持 液 滴 之 形 J 1 線 ί 態 ,而 徐徐 地 擴 散 於 酸 性 水 溶 液 中* 由 於 同 時 進 行 反 應 生成 過多 的 雲 狀 固 形 物 J jnr Μ 法 製得 球 狀 粒 子 〇 I (比較例2 ) 1 (滴下液） 1 ί 聚乙 烯醇 8 . 0% 1 水 9 2 . 0% [ 1 (反應液） 1 硫酸 5 . 0% 1 I 27 1 1 i 1 本紙殃尺度適用t國國家標準（CNS ) A4規格U]〇X 297公嫠） 4 2 1 b 5 8 A7 B7 五、發明説明（4 甲醛 4.0% 水 9 1.0% 使平均聚合度為1 5 0 0 ,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷郤。然後，使該混合液滴.入另外調製的 甲薛水溶液與硫酸水溶液之均勻混合物中。該酸性甲醛 水溶液之液溫為S 0 1C。而且，會産生與比較例1相同的 現象，無法製得球狀粒子。 (實施例3) (滴下液 ) 氣化鈣 2 .0% 水 98 .0% (第1反 應 液） 聚乙烯醇 3 . .096 藻酸鈉 0 , .5% 水 96 , ,596 (第2反 應 液） 甲菘 8 . ，096 碕酸 10 , 096 水 82 . 0% 請 先— 閱 讀 背- 面 之 注 意 事 項 再 填I裝 頁421658 A7 B7 V. Description of the invention (Photospheres are spherulite-bearing and porous, and the polymorphic deconstructed framework is fat-removing, tree-resistant, 0Itt-condensed I-based ethylenic, resistant to light and strong hair. Maple. Locally loaded, the chemical fu 7 " Fine grain is the substance so that the quality is pores and more and more, ο as far as the description of the suitability of the combination is excellent, and the carrier material carrier organisms withdraw and regenerate For the attachment, it is «!, And the body is put on the table, but it is also........... The fg fixation of bio-removal is still inclusive. For the purpose of use, it can be adapted to the enterprise. It can be used as ft * t quantitative method to solidify biological organisms to produce sludge. ). Bags, materials, and τπ · 1 physical machines, where there is a fast-recovery high-return or water quality discharge line is described in the next step (please read the precautions on the back before filling this page): ° The accumulated material is removed, and the raw material is removed to make the solid material from 0 to 0. The fine material has many holes. The fixed solid light concentration of the body and the body can be removed and protected, and the nature is thorough-so that the weatherability and resistance, the sexuality and the friction and resistance of the friction-resistant material can be moved. The settled mud that is produced and removed by sex will be polluted and settled, and the low solids will be reduced. The borrowing, price recovery, or high-quality material and water schedule will be treated »C5. Ss S can be handled, and According to the Central Standards Bureau of the Ministry of Economic Affairs, the “Machinery and Consumer Cooperatives” prints the advantages and disadvantages of the legal entity, the physical property, the physical property, the physical property, the physical property, the solid material, the solid material, the solid material, the solid material, and the physical material. Serve, gram can be llr-7 and change-the acid-limiting algae should not be better than holding 0, the species are fixed with solid harvesting and withdrawal. The dosage can be set as the solid master. The substance is in vivo and contains acid-removing substances-the algal growth is to remove this-Rong Kezi has grains, and when spherical, the pores are formed into pores. The main part is well-filled and well-condensed. More than 0 methylene ethylene polymer is its special ball too * 1 «-ruler < _ elimination of the 00 ladder standards (0 milk> 8 4 specifications (21 〇 father 297 male *) central standard of the Ministry of Economic Affairs Bureau ’s consumer cooperation printed 421658 A7 B7 V. Description of the invention (*) The compatibility of the invention. And, especially in terms of friction resistance, use bioremoval fixatives to include immobilization, such as porous porous The mixed solution of the particles and the bioremoval fixing agent is impregnated, so that the above bioremoval fixing agent is not dissolved in the pores of the porous material, and it is achieved. The bioremoval carrier of the present invention can be applied to both the above-mentioned including The fixed type (including the fixed method) and the above-mentioned non-included fixed type (microbial membrane method), or the conventional fluidity, fixed bed carrier, can also be used for applications including sewage treatment equipment, various bioreactors. Withdrawal of the invention The biological carrier in the treatment tank can be applied to a fluidized bed type sewage treatment device for floating sinking and convective processing of the granular biological carrier of the present invention. The fluidized bed type bioreactor can be applied to, for example, the aforementioned carrier and the liquid to be treated. Contact, biological treatment, chemical treatment. Specifically, in addition to the decomposition of organic substances, etc., it is also suitable for the gasification reduction of nitrification and denitrification, or chemical reactions such as addition, substitution, transformation, and detachment. The porous spherical particles of the present invention are particularly desirable as compression-molded products as described above. 恃 Specifically, they are sponge particles with a moisture content of 10% or less, and the volume of the water is rapidly expanded. It is 2 times to 10 times, and the size of the water state is lmra ~ 20mm, and it is suitable to use porous polycondensed spherical particles of polyvinyl condensation K. The porous sphere based on the polyvinyl acetal resin of the present invention is used as a framework. Compressed porous spherical particles (hereinafter referred to as compressed -14- ------------ ^ ------ ΐτ ------ ^ '· ( (Please read the precautions on the reverse side before filling out this page) Home Standard (CNS) A4 Specification (2ΙΟχ 297 mm) 421658 A7 B7 Central Government Bureau of Standards, Ministry of Economic Affairs, Consumers' Cooperatives, Printing Gas V. Description of Invention () I particles) Can be manufactured by compression engineering and drying engineering < > When the compressed 1 I particles are put into the treatment tank as m bio-carriers *, they quickly absorb water to restore I 1 to its original shape and size, and at the same time are moistened, impregnated, and floatable by the treatment liquid. Porous spheroids without compression and compression read 1 »It is not easy to separate the air in them λ floats on the water surface» And it takes time to reach the flowable back surface 1 I 1 It also takes 1 to compress the volume of the porous material by compression m Italy 1 I Small 4 As mentioned above, it can also reduce the cost of transportation. Matter 1] In addition ♦ The compression and compression process here M is to be completed after the drying process. Compression and compression in mm state 9 will soon return to its original state Page 1 I, Μ Polyvinyl acetal porous spherical particles manufactured under the conditions of 1 d of pseudo-M by the moisture content of 10% or less Compressed in a dry state 1 1. Shrinking system 9 can be stored in a compressed state for a long time, and if put into water, it will expand rapidly and return to its original shape and size. The higher the shrinkage, the higher the shrinkage rate. As much as possible * 1/2 ~ 1/10 is better. Compressed granules compressed to 1/2 1/10 1 1 »Into the water, they will swell rapidly to 2 times and 10 times * 1 1 will return to its original shape and size. Porous spherical particles in a water-containing state 1 1 size 1 When used as a biological carrier > For the reasons stated above, 1, -2 0 em line I is better 〇 | And * when used immediately after being put into the treatment tank r Polyethylene shrinkable m% porous spherical particles in the water state 〇1 This porous spherical particle can be used as an enzyme-immobilized carrier 1 in addition to the above-mentioned 如上所述 biological carrier 1 | 1 Cultivation solution 1 1 Holding material or plant support, cultivation of artificial coffin cells 1 | Hydroponic soil 1 | Good soil, etc. 0 In addition * For special applications, it can be used for flowing water 1 15- 1 1 1 Standard Tongchuanzhong ^ 戌 Home Therapy t- (CNS) Λ4 specifications (2 丨 OX297 mm) 421 bb β A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (»4) 1 1-type cleaning materials Or in water Flow-type massage parts 〇1 1 I When porous spherical particles are used as a fixed carrier, 1 1 porous spherical particles are thrown into a liquid dispersed with active B mud for removal. First 1 thing attached m Read on the surface of the above porous spherical particles and / or in the pores, read 1 back 1 immobilization > Others > For example * When using a microbial immobilization agent surface-1 for biological removal, it can also be used in activated sludge Dispersing Fixing Agent »Attention 1 for porous spherical particles 1 Put it into place to fix it 0 At this time» When using m shrink particles, it is better because the sludge item penetrates into the particles 1 more quickly 0 Fill out this package I especially When sodium methane is used as a fixing agent, the above-mentioned porous spherical sheet 1 1 particle-like particle-removing carrier is impregnated with the organism-removing carrier. A mixed solution of sodium 1 1 liquid t is then added to the biological carrier obtained by impregnating the mixed solution of sodium alginate 1 1 A polyvalent aqueous solution of gold osmium salt such as an aqueous solution of vaporized calcium is added t so that the alginic acid 1 is ordered 1 1 sodium Insoluble in the surface of the porous material and / or in the pores 9 The above-mentioned particulate porous bioremoval carrier including immobilized organisms can be obtained. 0 and 1 1! Allow the bioremoval fixative to flow into the pores of the microorganism carrier. 9% It is better to perform 1 I under reduced pressure. 0 1 1 .. Spring 1 The bioremoval carrier of the porous particles of the present invention * Corresponds to any of the conventional retreat treatment devices. 1 1 Anaerobic treatment in the treatment tank * All aerobic treatments have an effective effect 1 〇 Also * The biological removal carrier of the present invention can be used in a fluidized bed or can be used to fix a 1 r hip in a reaction tank The so-called fixed body carrier 01 I The above-mentioned porous spherical oligomeric particles 9 can be obtained by the following production method 9 1 1 CltT can be produced in a highly productive manner 0 1 i Its-a method such as porosity The method of making spherical particles j 恃 m is to make 1 16 I 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 42 165 8 A7 B7 Staff consumption cooperation of the Central Bureau of Standards, Ministry of Economic Affairs Printing 5. Description of the invention () 1 An aqueous solution of a gel-soluble water-soluble polymer with polyvinyl alcohol 1 1 1 and m-type E in an intoxicating solution is dripped into an acidic solution to make the droplet coagulate At the same time, the polyvinyl alcohol in the droplets is reacted with m type at the same time * to obtain ^ -v please 1 first 1 porous spherical particles with polyvinyl m% resin as the framework. Read 1 I m Due to the simultaneous progress of this system Shrinking process of the back side of spherical particles 1 I-1 Forming process »Multi-stage engineering without the need of know-how * Simple and high-quality ancient 1 1 Production of porous balls with uniform particle diameters close to spheres The shape of the particles is 1 I. In addition, a film is attached to the surface of the j particles. * Once it has excellent mechanical strength. Fill in this 1 and install I. What to do in this method 1 傜 Make the solution containing polyvinyl alcohol and the acidic solution 1 1 should * be formed from the acidic solution that acts as a catalyst while forming the shape of the droplet 1 1 action * make the droplet The shrinkage of polyvinyl alcohol and aldehydes contained in the same time 1 1 began to work 〇 change-Λ ,. * The polyvinyl alcohol in the solution and m type >% and do not make acidic solution as a solvent It does not react when contacted. It is a bear that holds a solution. It starts to shrink when it comes into contact with an acidic solution. ≫ Open 1 1 to start curing. In addition, the acidic solution contained in the solution has gelling properties. No. 1 | Water-soluble polymer r, for example, gelling properties by ion exchange reaction 1 1 line 1 water m polymer by ion exchange immediately after acid action 1 to form m-like substances • viscous Prevents until polyvinyl alcohol and The m-type reaction I should end the deformation of the spherical shape and 1 in the production method of the present invention * 1 Ί can also be used to make the biological training in the aqueous solution of polyvinyl alcohol and water-soluble polymers with 1 m It can be made to include a fixed carrier, etc. depending on the use! I can use the giant to do the necessary ratio m, etc. 0 1! Iff The particles obtained by this method become porous 9 but M is made by the ball 1 | Shaped particle drying »Existing in polyvinyl acetal% structured particles» For example 1 17 1 1 1 1 This paper size applies Chinese National Standard (CNS) Λ4 叱 辂 i: m_y male ft) 421658 'A7 B7 Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards V. Description of the invention (< y) ί * It is formed by condensation of calcium acid, etc. r Shrinkage will form voids, and the reason for the formation of a film on the particle surface is% by ΐ No pore formation on the surface Functional substances (both water-soluble polymer gel, starch and other stomata-forming agents), which cannot be produced. The same structure as the inside of the particles that are rich in stomata-forming agents and Xue Xue forms the same structure. Result 1 The particle surface of the present invention that undergoes an acetalization reaction in the form of spherical particles. T is a porous spherical particle and a thin film having pores on the surface. The particle is provided on the surface of the particle. 1% The inside of the particle is a sponge with porosity. Porous material with a three-dimensional network g structure. In addition, in an acidic solution, H is a water-soluble polymer that has gelling properties such as ion exchange reactions (the other methods are the same below). There is no other limitation, such as sodium alginate. Carrageen m Sodium polyacrylate 0 Although the concentration of polyvinyl alcohol is subject to special restrictions 9 general and ^ v. The higher the concentration of polyvinyl alcohol 1 the easier to obtain spherical particles »and the polyvinyl alcohol m When the degree is lower, it is easy to obtain a hydrogel. The difference in the physical properties of these particles »It depends not only on the concentration of the polyethylene fermentation 1 but also by other factors m 1, but the degree of polyvinyl alcohol m is not only spherical. The water-condensed particles in the particles are alum 1 and the particles of the resin structure are also important. 0 Therefore 9 the blending amount of the present invention is also very important. 0 If the concentration of polyvinyl alcohol in the present invention is greater than 20 mol 96 hours »Solution The viscosity becomes higher. 1 Not only becomes difficult to handle. 9 Drop-like particles such as drawn yarn are produced when dripping. ≫ It is not possible to make spherical balls with an average diameter or close to the average diameter. 0. The polyvinyl alcohol concentration is less than 5 mol. % S ti is a spherical shape obtained from the shrinking reaction after dropping) px h. The intensity of the seed m is lower than 1 false. 18 The paper size applies the Chinese National Standard (CNS) Λ4 specification (210X2 ^ 7 mm) ) 4 2 16 5 8 * A7 B7 Printed by the Consumers' Cooperative of the Prospective Bureau of the Ministry of Economic Affairs. 5. Description of the invention () I want ΰ So »The concentration of polyvinyl alcohol is preferably 5 to 20% by weight. T J 1 1 Ί ~ [5% by weight is the best. However, when the hollow particles are manufactured by the 1 1 manufacturing method of the scope of patent application of the following application 9 9 It is easy to reduce the concentration by a small amount * 5ί = »For the particles of ugly beauty, 1 1 9 1 ~ 7% by weight is preferred. The temperature is not limited to 1 system 9 if it is a temperature that does not modify each other f can maintain fluidity »that is, back 1 I 1 so that no problems occur at room temperature. Benzene m X ethyl m butyl m, propylene m, or ethyl matter I 1 1 Second-class aliphatic t Aromatic m class 0 or Η It is easy to write from coexisting acids. 1 Λ is converted to m class m and used t Consider the opposite of polyvinyl alcohol. Soluble N price, handling property, strength of reaction product > inverse I 1 elasticity and ease of handling after reaction, etc. t is particularly preferably m m. The concentration of type 1 is not particularly limited t. It is very important to determine the degree of acetalization of the structural particles. The breadth of the m-type in the present invention depends on the coexistence of the acid catalyst concentration and the reaction temperature. The appropriate degree must be selected. 0 m-type 1 Shorten the time to the desired degree of shrinkage 惟 Only 1 j is too high when the reaction speed is increased t It is not easy to control the degree of shrinkage 一般 Generally speaking> 1 When the degree of acetalization is too high, the strength t is used to produce porous materials The line will drop when [low porosity > false specific gravity increase »moisture content will decrease 0 In addition) with the reduction of residual hydroxyl groups t 1 hydrophilicity reduction 〇 In addition ♦ the resilience of particles also decreased 0 1% The outer shrinkage degree is preferably 3 0 85 mol% as described above. 0 is especially 1 1 when it is used for fluid bed type bioremoval that must have shuttle rubber jBb and hard hardness 1 1 when the carrier »must be set to 5 5 85 mol% 0 Concentration of shrinkage at this time! T Depending on the type, it does not matter *, but when using nails, it is set to 3 ~ • 1 ϋ% by weight 1 1 19 1 1 1 This paper size applies Chinese national standards ( CNS) A4 specification (2〗 OX 297 mm) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 421658 A7 B7 5. The invention description (β) is better. Water-soluble polymers with gelling properties in acidic solutions, such as water-soluble polymers with gelling properties through ion exchange reactions, as described above, are not particularly limited, such as sodium alginate, carrageenan Vegetable gum, sodium polyacrylate, etc., but considering the degree of gelation, gel state, etc., sodium alginate is the best, and the use of this substance is sought. There are no other restrictions on the molecular weight of sodium alginate, but those with a high molecular weight can easily produce high-speed and perfect particles. However, since the viscosity of the solution is too high at high molecular weight, it is not desirable to easily form droplets. Specifically, it is preferable to use sodium alginate having a viscosity of 30 dPa * sec at a concentration of 201, 4%. However, the present invention is not limited thereto. In addition, the water-soluble polymer having a condensation property that is contained in the polyvinyl alcohol solution according to the degree of ion exchange can be used as a pore-forming agent and a shape-maintaining agent as described above, but the concentration is within this range. There are no special restrictions. In general, if these concentrations are high, the viscosity of the solution increases, and many obstacles may occur during dripping. In addition, if the concentration is low, the reaction rate of gel formation is slow and it is difficult to obtain spherical particles. If the treatment is considered, the concentration depends on the molecular weight of the alginic acid, but the molecular weight in the above range is 0.5 to 5% by weight, particularly preferably 1 to 5% by weight. Especially when the sodium alginate is less than 0.5% by weight, compared with the surface tension of the water-soluble polymer body in the water or water, its dispersing power becomes stronger, making it impossible to enter and spreading on water. In addition, if the concentration of sodium alginate is more than 5% by weight, the solution is injected into the solution while being drawn from the supply port, and as a result, spherical particles having a uniform diameter are not easily produced. -20- This paper size applies to Chinese National Standard (CNS) A4 specification (2! 〇 × 297 mm) — I ΐ 衣 Iΐτ ------. ^ (Read £ -read back fi- notes before filling out (Buy) 421658-A7 B7 Printed by I Industrial Consumer Cooperatives, Central Building Standard Bureau, Ministry of Economic Affairs. 5. Description of the invention ((5) 1 1 To promote the reaction between polyvinyl alcohol and m type. The solution is preferably 0. These acids have other restrictions. For example, II can choose white sulfuric acid, hydrochloric acid, and inorganic acids such as phosphoric acid and succinic acid. Read 1 and 1 and 4 <# slightly acid but especially strong acid. Especially when dealing with f fables, it is best to read 1 with sulfuric acid »Only depending on the type of polyvalent metal salt used in combination m Choose the necessary back 1 [of 1 the appropriate type of acid 0 meaning 1 thing 1 for polyvalent metals There are also no special restrictions on the saline solution. 1 Calcium aluminate zinc, aluminum sulfate, etc. are appropriate. 0 Concentration is based on the selected metal salt. Fill in this package. 1 The type or temperature of the aqueous solution is different. F When using calcium carbonate, 1 '-2 0 Page 1 [Heavy child % Is suitable for Q and * In the invention of item 2C of the patent application, 1 1 If the m degree is too high, the gel particles generated by S become larger and easily melt with other particles adjacent to 1 1 i Defective phenomenon 0 and $ 1 in the manufacturing method such as the scope of patent application No. 17 »Adding a small amount of calcium nitride 1 and other polyvalent metal salts in acidic water soluble η > It is not easy to make spherical particles U_f 1 1 Milled spherical particles with uniform diameter 0 1 I 1 1 Polyvinyl shrinkage% m Spherical particles made by the method of patent application No. 17 No. 20 0 »Not in water solubility Polymer containing A | Water Gel containing polycondensate »It is polycondensate-resin resin | Water-containing gel containing water-soluble polymers such as sodium alginate in the framework 1 It is prepared in a state of 0, dried as described above. This resin particle fakes the condensation of water-soluble polymers such as brook acid 1 \ nano to form a porous II 0 with a fine pore size, thereby obtaining rubber-like elastic or hard porous spherical resin particles 0 1 and When put into water > Of the water-soluble polymers such as sodium methane that has shrunk, 1 I gel returns to water-containing gel 9 and it has a porous structure. It can be used as a living place for the complete 1 I thing. In addition, i exclude the particles. When the above gels are contained i 1 [2 2 1-1 1 The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) 4 2 1 b 5 8 A7 B7 Central Standard of the Ministry of Economics 扃 Employee Consumer Cooperatives Printing V. Description of Invention (W) v I can obtain porous spherical particles with external pores. ○ When producing particles with large pore diameter and 1 1 I diameter and porosity, pore forming agents such as powder are added to the polyvinyl alcohol solution in advance as described below. 0 stomatal diameter and porosity / * s are obtained. 1 The bigger the first, the easier it is to remove the residual material after the shrinkage reaction and shorten the reading. 1 | Wash time. In addition, 9 increase the porosity to reduce the false specific gravity » And with the 1 1 on the back surface, the fluidity in water is improved. 01 1 | In addition, in another embodiment of the method for producing spherical particles according to the present invention, the ψ term is made 1 1 and the water having gelation properties is dissolved by ion exchange reaction. The solution of a homogeneous molecule and a polyfill is filled with a solution of vinyl alcohol mixed with polyvinyl alcohol, and the solution is dropped into a polyvalent metal salt solution. Page 1 I. m The solution is made by an ion exchange reaction. Drop-shaped m-shaped spherical Jr · particles containing condensed polyvinyl alcohol 1 I are then added to the gel-like l | r * particles in an acidic solution containing m 1 1 type * and the gel is formed. Polyethylene contained in the particle-like particles 1 and enols and aldehydes 1 In order to obtain a degree of shrinkage of 30 85 mol jealous 9 Porous spherical shape with (I polyvinyl acetal% resin as the framework) Particles 0 1 1 This method is not to use water-soluble polymers of water-soluble polymers as the main component of spherical particles 1 1 but as a method to protect spherical particles »Give 1 1 line 1 BO and a large amount of Manufacture of polyethylene based shrinkage with rubber elasticity or rigidity and close to uniform diameter. Structure spherical ib_t »particles 0 In other words, M is formed from 1 1 m to form a structure based on polyethylene shrinkage Ji-L particles > Main ingredients Polyethylene \ 1 Alcohol 1 and Phenol to the protection of spherical particles in manufacturing process Actions and stomatal formation I 1 action m Sodium acid and other water-soluble lettuce molecules, each compounding amount bb Example t and adjusting the degree of shrinkage of poly 1 I vinyl alcohol to the above-mentioned mixing ratio can be simplified DB early and large 1 halo manufacturing It has the properties of rubber elasticity and rigidity, and is close to a sphere. »All '1 I. Polyvinyl acetal with a particle diameter. Spherical particles. In addition, 1 22 1 1 1 (CNS) Λ4 specification (210X297 mm) 421658 A7 B7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives. V. Description of the invention (y) 1 Shrink the reaction into ~-The project is in line with the above. Item 1 1 I and m method comparison can simplify CM- ». A-to adjust the degree of acetalization is better 0 acetalization 1 1 degree of m can be adjusted by m to adjust the amount of reaction solution and the like * reaction solution Please warm it! [Degrees look at the time to control 〇 read I 1 I and m Method for manufacturing hollow porous spherical particles with polyethylene back surface 1 I to 1 m shrinkable resin with m different abrasion resistance and mechanical strength j Pseudo attention to weight 1 1 If Φ, please refer to item 20 of the patent scope According to the method, a 1 1 I solution of polyvalent gold 靥 brine is added dropwise into an aqueous solution of iff, which is gelatinous with ion-exchange reaction, and a water-soluble high-resolution copy 1 of a package mixed with polyvinyl alcohol and dissolved * And by the polyvalent gold sheet \ _- · t I m 鞔 droplets react with the water-soluble archaeological molecules to be solidified. 0 1 1 1 outside the droplets are mixed with polyvalent metal salts Water-soluble polymer gel 1 1 and polyvinyl alcohol gel spherical particles t then > add the gel-like particles 1 to an m-type acidic aqueous solution * by making the m-shaped particles Polyvinyl alcohol contained in 1 is produced by reacting with m type 0 1 1 According to the method of the present invention, the polyvalent gold exhibition m Jm aqueous solution is dripped into the polyethylene 1 1 alcohol solution * The peripheral part of the droplet is gelled 9 and therefore the polyvinyl alcohol 1 1 line 1 solution cannot be immersed Inside the droplet »The gelation result cannot be obtained. The product is hollow j · 丄 WL. 〇1 The spherical particles obtained by the above various m methods are porous as described above. The spherical particles are dried to polymerize them. The condensation m existing in the acetal-based framework particles 1 shrinks 0 and ί if it must be a larger diameter pores t 1 I or flat inside and outside without porosity distribution 1 This can be borrowed at least I i Ion exchange reaction to make gel-soluble water-soluble polymer and poly * 1 | Aqueous solution formed by mixing and dissolving vinyl alcohol with a pore-forming agent »1 I 23 1 1 1 The scale applies to the Chinese National Standard (CNS) A4 (210X 297 gong). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 42165b A7 B7 V. Description of the invention (p) A porous material with a large pore size was obtained. The pore-forming agent is not particularly limited, but the particle size of starch is relatively uniform, and the particle size is most suitable for the pore diameter desired by the porous spherical particles of the present invention. In addition, when the porous spherical particles are washed, it is easier to wash, flow, and handle the particles after forming with water. Porous spherical particles prepared by adding a pore-forming agent such as starch are suitable for use as a fluidized bed type microbial carrier. In addition, condensate can be removed from the porous spherical particles of polyvinylacetal resin as the framework. In other words, the above-mentioned porous spherical particles can be condensed by drying to form a porous substance, but in a wet state, they have a porous structure and tend to return to a gel. Therefore, by actively removing the condensate, a porous material having external pores in a wet state can also be used. The main component of the gel is a gel of water-soluble fluorene molecules that have coagulating properties through an acidic solution. For example, the method of removing the water-soluble polymer gel such as alginic acid allows particles to be added to a solution containing sodium ions, and by! I. Washing and ion exchange, or a method using chelation for ethylenediaminetetraacetic acid (EDTA) and calcium ions such as a phosphate buffer, and other methods such as centrifugation. Either method is a suitable gel removal method. In addition, the pore diameter, porosity, and shrinkage degree 本 of the present invention including the following examples were measured based on the following measurement methods. (Measurement of Stomatal Diameter) The measurement of stomatal diameter is based on A S T H (D e s i g n a t 〇 n :: 0 4 4 0 4-8 4). Specifically, a porosimeter manufactured by P 0 RGUSMATERIALS, INC was used to determine the size of the plain paper by mercury indentation method for pore size measurement. Applicable to China's national step- (CNS) AWUA (210_X297 mm) --- ----- ▲ ------ 1T ------ ^ (Read 4-Read Back & -Notes before filling out this page] Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 421658 A7 B7 V. Description of the invention () Average porosity diameter (Determination of porosity) Make the sample in a wet state, use a buoy to measure the diameter of the 3 痼 place, measure the false volume (Va), and use a dry automatic density meter made by Shimadzu Corporation. (Transliteration) 1 3 3 0 (brand name) Measure the straight volume (V). Use this value to calculate the porosity e (%) by the following formula. E = {1-Va / V) X 100 (acetalization Measurement of degree) Proton NMR measurement in heavy hydrogen imitation and trifluoroacetic acid aqueous solution, and the degree of acetalization F (%) was calculated by the following formula. F = (a / e) X100 c: methylene proton (for example, 4 153, 4.442 ppm) total peak intensity a: The sum of the peak intensities of methylene protons (eg, 4.667, 5.150, 5.313, 5. 3 2 6 ppm) adjacent to the ether group In the following, the present invention will be described in detail by way of examples. However, the present invention is not limited by these. In addition, the% in the following examples and comparative examples refers to% by weight. (Example 1) (Drip Solution ） Polyvinyl alcohol 7.5% sodium alginate 1.0% formaldehyde 4.0% water 87.5% -2 5----------- ¾ clothing ------ ΐτ ------ Λ ( Please read the notes before you fill in this page before filling in this page.) This paper size is far from the Chinese National Standard (CNS) A4 size (210X297 mm) 421658 Central Standards Bureau of the Ministry of Economic Affairs, Industrial and Consumer Cooperatives, A7 B7. Description of the invention (-M (reaction liquid) sulfuric acid 10.0% water 90.0% so that the average degree of polymerization is 15 0, the completely saponified polyvinyl alcohol resin is dissolved in hot water and then cooled, and a further prepared An aqueous solution of sodium alginate was added to the formaldehyde aqueous solution and mixed uniformly. Then, the mixed solution was dropped into a 0% sulfuric acid aqueous solution. The liquid temperature of the sulfuric acid aqueous solution was about 5 minutes. After condensing, the state reacts after 15 minutes of separation, so that the particles can be separated to obtain the elasticity of polyethylene acetal as the resin structure. The object was thoroughly washed and washed with water, and dried to obtain porous spherical particles of polyvinyl acetal strips having a uniform particle diameter close to a sphere having a particle diameter of 3 to 4 μm β. (Example 2) (Dripping solution) Polyvinyl alcohol 7.5% Sodium alginate 1.0% Water 9 1.5¾ (S reaction solution) Sulfuric acid 5.0% Methylalcohol 4.0% Water 91.0% So that the average degree of polymerization is 1 500, completely saponified polyethylene The alcohol resin is dissolved in hot water and then cooled, and an additional prepared sodium alginate aqueous solution is added thereto and mixed. Then, make the mixed droplets of human formaldehyde aqueous solution and-2 6----------- ΐ 衣 ------ iT ------- ^ (Please read back free of charge : Please fill in this page again for “Λ 意 事”) This paper size applies the Chinese National Standard (CNS) A4 specifications < 2! Fw ί 1 421658 A7 B7 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention () 1 Sulfur醅 The aqueous solution is homogeneous. The temperature of the acidic formazan solution is 1 1 6C) in „The dropped droplets are gelatinized in about 5 minutes. The reaction in this state is 1 1 about 30 minutes. Vinyl acetal is a strong tfl particle of resin structure. Please take 1 first and 1 child. This is about the same as that obtained in Example 1. Read 1 1 (comparative example). Hand 1 (dropping solution) Yi Xuan II polyethylene Alcohol 7. 596 Ψ item II II A_ 4. 096 4 Writing 1 Pack I Water 8S. 5% Page 1 I (Reaction liquid) 1 ί sulfuric acid 1 0. 096 1 1 water 90. 0% 1 order 1 i so that the average degree of polymerization is 15 00 t 1. 1 Γ The fully encapsulated polyvinyl alcohol resin is dissolved in 73 m of hot water and cooled in it An aqueous formaldehyde solution was added and mixed uniformly 1 1. Then, the mixed liquid was dropped into a 10% sulfur 1 I acid aqueous solution having a liquid temperature of 60. However, the dropped liquid mixture failed to maintain the droplets. Shaped as J 1 line, and slowly diffused in the acidic aqueous solution * As a result of simultaneous reactions, too many cloud-like solids were produced J Jnr Μ method spherical particles 〇I (Comparative Example 2) 1 (dripping solution) 1 ί poly Vinyl alcohol 8. 0% 1 Water 9 2. 0% [1 (reaction liquid) 1 Sulfuric acid 5.0% 1 I 27 1 1 i 1 The paper standard is applicable to the national standard (CNS) A4 specification U] 〇X 297 Public badge) 4 2 1 b 5 8 A7 B7 V. Description of the invention (4 Formaldehyde 4.0% Water 9 1.0% The average degree of polymerization is 15 0. The completely saponified polyvinyl alcohol resin is dissolved in hot water and then cooled. Then, the mixed liquid was dropped into a uniformly prepared homogeneous mixture of an aqueous solution of mexyl and sulfuric acid. The liquid temperature of the acidic formaldehyde aqueous solution was S 0 1C. Moreover, the same phenomenon as in Comparative Example 1 occurred, and spherical particles could not be obtained. (Example 3) (Drip solution) Calcium vaporized 2.0% water 98.0% (First reaction liquid) Polyvinyl alcohol 3. .096 Sodium alginate 0, .5% Water 96,, 596 (No. 2 Reaction solution) Formamidine 8., 096, acetic acid 10, 096, water 82.0% Please first — read the back-side precautions before filling in I
1T 經濟部中央標隼局—工消費合作社印製 使平均聚合度為1 500 ,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷卽。於其中添加另外調製的藻酸鈉水溶 液，做為t量為2 0 0 0 m 1溫度為室溫之混合溶液。以氰化 钙水溶液慢慢地滴入混合溶液中，該滴液會開始凝固約 5分鏔後完全凝膠化，生成半透明的球狀粒子。將此凝 _ 2 S - 本紙張尺度適用中國國家標準（CNS) AOU ( 2!〇x 297公釐） 42 165 8 A7 B7五、發明説明（W ) 瞭狀粒子分離、回收、再添加由甲醛與硫酸所成，液溫 為6 Ο T之混合水溶液。於添加的同時半透明的凝膠狀粒 子開始白濁，約10分鐘後完全白化，製得以聚乙烯基縮 薛為樹脂架構具橡膠彈性球狀粒子。使該物以水充份洗 淨，製得粒子直徑3〜4mn之接近圓球的均一粒子直徑之 聚乙烯基縮醛条中空粒子。 (比較例3 ) (滴下液） 聚乙烯醇 氛化鈣 水 (第1反應液） 藻酸鈉 水 (第2反應液） 甲醛 硫醅 水 2.5% 5.0% 87.5¾ 0.5% 99.5%8.0¾10.0% 82.0¾ ---------裝------1玎------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局—工消費合作社印製 使平均聚合度為1500,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷卻。於其中添加另外調製的氯化鈣水溶 液，做為全最為2〇〇〇m丨之混合溶液。使其慢慢地滴入 藻酸納水溶液中，該溶液會沈降且凝膠化，生成半透明 的紐狀凝膠，、然後，使該紐凝_分離、回收、再添加由 甲薛與硫酸所成，液溫為6 0 °C之混合水溶液。於添加的 29- 本紙張尺度適用中KW家樣窣（CNS ) Λ4規格{ 210X297公釐） 421658 A7 B7 經濟部中央榇準局男工消費合作杜印製 五、發明説明（ ^ ) 同 時 半透明 的 凝 膠 狀 粒 子 開 始 白 濁， 約 1 0分 鐘 後 兀 全 白 化 y 目.所得 具 橡 瞟 彈 性 者 不 是 球 狀粒 子 亦 不 曰 疋 中 空 0 (吐較例4 ) ί滴下液） 聚 乙烯醇 5 · 096 氯 化鈣 2 . 0% 甲 m 3 . 096 硫 酸 4 . 096 水 86 . 096 (1 g 1反應液） m 酸鈉 0 . 596 水 96 . 5% (第2反應液） 水 使 平均聚 合 度 為 1500 > *±=» 兀 金 苌 化的 聚 乙 烯 醇 樹 脂 及 氯 化 鈣 、甲醛 硫 酸 所 成 的 混 合 液 慢慢 地 滴 入 藻 酸 納 水 溶 液 中 ,該溶 液 會 沈 降 且 凝 膠 化 0 使該 粒 子 分 離 t 且 添 加 於 60 t之湯 裕 中 ， 予 以 反 應 30分 鐘後 t 可 得 彈 性 粒 子 〇 而 目 ,該粒 子 不 為 中 空 粒 子 且 強度 較 賁 施 例 3 所 得 者 為 样 〇另外 I 猙 判 明 滴 入 殘 3P^} 甶 的 滴下 液 1 5分 鐘 後 會 固 形 化 y 因此調 整 滴 下 液 後 必 須 極 早 使用 〇 (實施例4 ) (滴下液） 聚 乙烯醇 7 . 5% 30 訂 線 本紙張尺度適用乍國國家標隼（CNS ) A4規格（210X297公釐） 請 先' 閱 讀 背 面， 之 注 意 事 項 再 填 J裝 頁 421658 A7 B7五、發明説明（θ ) 落酸 納 1 .0¾ 水 9 1 .596 (第1 反 陴 液） 氣化 鈣 3 .096 水 97 ' .096 (第2 反 m 液） 甲眹 3 . .096 硫酸 4 , .096 水 93 , .096 經濟部中央標準局貝工消費合作社印裝 使平均聚合度為1500,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷卻。於其中添加另外諝製的藻酸鈉水溶 液而成全量為2000ml之混合溶液。使其慢慢地滴入氮化 15水溶液5000η丨中，該液滴馬上凝固，開始失去流動性 ，约3分鐘後完全凝膠化且生成半透明的球狀粒子。然 後，使該凝瞜狀粒子分離、回收，再添加於甲醛濃度為4% 、硫酸濃度為5%之混合水溶液中。於添加的同時半透 明的凝醪狀粒子白濁，開始約3分鐘後完全白化，製得 具橡_彈性之球狀粒子。以水使其充份地洗淨，且可得 粒子直徑為3〜4ram,接近圓球均一粒字直徑之聚乙烯基 縮薛糸多孔性球狀粒子。使該球狀粒子乾燥後，以掃描 電子顯檝鏡觀察内部構造，可知多數具2〜4wn之氣孔 ，任一皆為連通氣孔。 (實施例5 ) -31 - ----------f-------ΐτ------^ (請先.S讀背面之注意事項再填寫本頁) 本紙張尺度速用中國國家梯準（CNS > ί ：：丨0 < 297公赘） 經濟部中央標準局員工消費合作社印製 以與實施例4相同的操作方法製得凝膠狀粒子後，使 該凝膠狀粒子分離、回收，再添加於由甲醛8%、硫酸 10 %所成的8(TC之混合水溶液中。在該狀態下反應5分 鐘後，可得不具彈性之3〜4mm球狀粒子。該球狀粒像 具有徹細的平坦狀之凹凸。以水使其充份地洗淨後予以 乾燥，且以掃描電子顯微鏡觀察内部構造，可知為具2〜 4yni之多數氣孔、任一皆為連通孔β (實施例6 ) (滴下液） 聚乙烯醇 7,5% 藻酸鈉 1.0% 水 9 1.5% (第1反應掖） -3 2 - 42 165 8 A7 A7 B7 五、發明説明（v ) (滴下液） 聚乙烯醇 7.5% 藻酸納 1.0% 水 91.5% (第1反應液） 氣化鈣 3.0% 水 97.0% (第2反應液） 甲醛 8.0% 硫酸 10.0% 水 82.0% 本纸張尺度適用中國國家標準（CNS ) Α4規格（21〇κ 297公釐） ----------^------ΐτ------0 (請先閲請背赶之注意事項再填寫本頁) 421658 A7 B7 五、發明説明（^ ) 氛化鈣 水 (第2反應液i 甲醛 碕酸 水 3.0% 97.0% 8.0% 10.0% 93.0¾ 以與實施例5相同的操作方法，使凝瘳狀粒子添加於 甲薛8%及碕酸10%之20t的混合溶液中，反應15小時 後，可得與實施例2相同的硬質球狀粒子，其粒子表面 較奮施例5所得者為平滑。 (實施例7 ) 經濟部中央標準局員工消費合作社印製 (滴下液） 聚乙烯醇 藻酸鈉 澱粉 水 (第1反應液） 氣化鈣 水 (第2反應液） 甲眹 硫醉 水 7 .5% 1 .096 5,0% 86.5% 3.0% 97.0% 10.0% 15.0% 75.0% 使以與宵施例4相同的操作方法所諝製的混合液，滴 -33- 本紙張尺度適用中國國家標準（CNS ) Λ4规格（210ΧΓ97公) ---------淋衣------1Τ------0 (請先，閱讀背面之注意事項再填寫本頁) 42 165 8 經濟部中央標準局—工消費合作社印製 五、發明説明（> ) 入70^,5 00〇1111氣 分鏵後可得完金凝 該凝P狀粒子添加 藉由反應約60分鏡 以攪拌、該粒子容 的流動件。而且， 約為67莫耳％。 (實施例8) (滴下液） 聚乙烯醇 藻酸納 澱粉 水 (第1反應液） 氣化鈣 水 (第2反應液） 甲薛 硫酸 水 使以與實施例4 5 0 0 0 m 1、 7 0 ΊΠ 氛化 鐘後完全凝膠化而 瞹狀粒子添加於由 A7 B7 化鈣水溶液中，該溶液開始凝固，1 5 膠化，半透明的彈性粒子。然後，使 於由甲醛與硫酸所成的6 0 t水溶液， ，可得白色球狀粒子。在該狀態下予 易流動，且呈現較實施例4所得者高 本實施例所得的球狀粒子之縮醛化度 7 . 5% 1 . 0% 5.0% 86.5% 3 , 0% 97.0% 10.0% 15.0¾ 75.0% 相同的操作方法所諝製的混合液滴入 鈣水溶液中，該溶液開始凝固，，1 5分 得半透明的彈性粒子。然後，使該凝 甲K與硫酸所成的7 5 1C水溶掖中，藉 -34- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） ---------^------訂------0 (請€讀背面之注意事項再填寫本頁) 421658 A7 B7五、發明説明（V〇 由反曉約15分鐘後，可得白色球狀粒子。在該狀態下tS 拌、該粒子容易流動，且呈現較實施例4所得者為高的 流動件。而且，本實施例所得的球狀粒子之縮醛化度約 為β 5莫耳％。 (比較例5 ) (滴下液） 聚乙烯醇 10.0% 藻酸鈉 1 .〇% 水 89.0% (反應液） 氣化鈣 3.0% 水 9 7.0% 使平均聚合度為1500,完全皂化的聚乙烯醇樹脂溶解 於熱水後予以冷卻，且於其中添加另外調製的藻酸鈉水 i容液.而成全量為2000m丨之混合溶液。使其慢慢地滴入 5000ral氣化鈣3%之水溶液中，該溶液馬上開始凝固， 失去流動性約3分鐘後完全凝瘳化，粒子的形狀為水滴 狀，而不為圓球狀。 (比較例6 ) I---------^------1T------^ (祷先閱讀背*之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作杜印製 (滴下液） 聚乙烯醇 8.0% 水 92,096 (反應液） 氣化鈣 3.0% -35- 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 421658 A7 經濟部中央揉準局s貝工消費合作社印製 B7 五、發明説明（料） 氷 97.0% 使平均聚合度為1500,完全皂化的聚乙烯醇樹脂溶解 於水中而成8%水溶液，使其慢慢地滴人5000m〗氯化鈣 3¾之水溶液中，該液滴廣佈於氣化鈣水溶液之水面上， 卽使在該狀態下放置10分鐘，該溶液亦不會凝固，無法 製得凝膠化物。 (tb較例7 ) (滴下液1 聚乙烯醇 7.5% 藻酸鈉 1.0% 澱粉 5.0% 水 86.5% (第1反應液） 氮化鈣 3.0% 水 9 7.0% (第2反應液） 甲醛 10.0% 硫酸 15.0% 水 75.0% 使以與實施例4柑同的操作方法所調製的混合液滴入 5 0 0 0 m 1、7 0 TO氯化鈣水溶液中，該溶液開始凝固，1 5分 鏡後完令凝嘐化，可得半透明的彈性粒子。然後，該凝 膠狀粒子添加於由甲醛與硫酸所成的6 0 t之水溶液中， 薛由砭應約1 5分鐘後製得白色球狀粒子。在該狀態下醍 -36 - I---------赛------1T------0 (請先S：讀背面之注意事項再填寫本買) 木度適用中國國家榡準（CNS ) Λ4规格（210X 297公釐） 經濟部中央標隼局員工消費合作社印製 421658 A7 B7五、發明説明（W ) 拌，該粒子容易流動，且呈現較實施例4所得者為高的 流勖忡。惟本比較例所得的球狀粒子之縮醛化度約為30 莫耳％,於下述之耐久性試驗中可確認其摩擦性。 各窖施例所得的球狀粒子為具網目構造，連續氣泡之 海舖狀物，親水性佳，濕潤時富含柔軟性及彈性。於該 多孔質物中選取1 0個試樣，且測定其特性，氣孔率在 80〜95%之間均勻地分散，平均氣孔率為90%。而且， 氣孔首徑散佈於30〜lOO/im之間。平均為60Wm。該範 圍之氣孔直徑傜可使多孔質内之撒生物維持之適當尺寸 。摘合利用於載體。 另外，各實施例所得的多孔性球狀粒子之含水狀態的 假比重、10個試樣約為1.017〜1.019。而且，中空粒子 之實施例3粒子的比重更小，約為1 . 0 0 8。予以離心脱水 後之水份率為50.4%，50%壓縮應力為20乂103^</|112。 使20粒投入振盪的燒杯水中.，暫時浮游於水面1 , 3分28 秒後全而的粒子皆穩定地下沈在水面下。 (壓製試驗） 然後，使各實施例所得的多孔性球狀粒子在6 0它下乾 燥1小時，水份率為3,0%。使其在4,9xi06H/m2之 壓力下予以壓製，壓縮至直徑為0.75〜1.5min。使於此 等之中20粒投入振盪的水中，快速地吸水，膨脹，8秒 後今部沈在水面下。取出沈澱的粒子，水份率50%,在 水中濕澗狀態予以測定。全部皆復原為投人水中後原來 形狀的大小^如上可知，投入水中後快速地膨脹成體積 -37- (請4閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X297公釐） 經濟部中央標準局負工消費合作杜印製 4 2 1 R 5 8 A7 B7 五、發明説明（# ) 成2倍〜4倍。 對眈而言，使壓製前經乾燥的試樣中之20粒投入振盪 的燒杯之水中，全部的粒子浮游於水面，即使粒子的表 而吸水後仍無法核除其中的空氣，故即使振盪2小時， 仍無粒子沈在水面下。 (耐久性試驗> 另外.以生物反應器内之流動做為理論槙擬試驗，使 在直徑15 0mm,高度400ns!之容器内所得的各實施例及比 較例7的多孔性球狀粒子琪充對水量而言10%體積，且 曝氣流動於水中，該粒子均勻地分散、流動。使該流動 連鑛進行1個月，且運轉後，取出該粒子予以觀察，實 施例之粒子完全不因摩擦而産生摩損或破損的情形，可 確認其為含耐摩擦性。惟縮醛化度不充份的比較例7之 粒子可見其受到摩損。 另外，為了與其他原料所成的單體比較耐摩擦性能之 促淮試驗，俱在與上述相同的試驗容器側壁内面上阽附 耐水性砂狨（100號Λ且使各載體以對水最而言10%體 稹各予以《充，在水中攪拌、流動。檷拌係設定使投入 水槽内之檷拌翼以30〇γρβι之速度回轉，使載醱機械性流 動，與内壁産生摩擦。使該流動連鑲進行1週.經時的 觀察載髓狀態完全沒有本發明之多孔性球狀粒子因摩擦 所産生的摩損，可確認富含耐摩擦性。 對此而言，其他原料偽遘擇直徑為之聚氛基甲酸 乙酯海綿、撖維素海绵、藻酸’好球狀凝膠，可確知在2 4 -3 8 - 本紙張尺度適用，丨，WW家梂肀（CNS >以说格（210X297公釐） (請先閱讀實面之注意事項再填寫本頁) -裝·1T Printed by the Central Bureau of Standards, Ministry of Economic Affairs—Industrial and Consumer Cooperatives. The average degree of polymerization is 1,500. The fully saponified polyvinyl alcohol resin is dissolved in hot water and cold-rolled. A separately prepared sodium alginate aqueous solution was added thereto as a mixed solution having a t amount of 2000 m 1 and a temperature of room temperature. The calcium cyanide aqueous solution was slowly dripped into the mixed solution, and the drop began to solidify for about 5 minutes, and then completely gelled to form translucent spherical particles. This condensed _ 2 S-this paper size applies Chinese National Standard (CNS) AOU (2! 〇x 297 mm) 42 165 8 A7 B7 V. Description of the invention (W) Separated particles are separated, recovered, and then added by formaldehyde A mixed aqueous solution of sulfuric acid and a liquid temperature of 60 ℃. At the same time of adding, the translucent gel-like particles began to become cloudy, and after about 10 minutes, the particles were completely whitened to produce polyvinyl-based resin particles with rubber elastic spherical particles. This material was thoroughly washed with water to obtain hollow particles of polyvinyl acetal strips having a uniform particle diameter close to a sphere having a particle diameter of 3 to 4 mn. (Comparative Example 3) (Dropping solution) Polyvinyl alcohol-calcified calcium water (the first reaction liquid) Sodium alginate water (the second reaction liquid) Formaldehyde and sulfuric acid water 2.5% 5.0% 87.5¾ 0.5% 99.5% 8.0¾10.0 % 82.0¾ --------- Installation ------ 1 玎 ------ ^ (Please read the precautions on the back before filling this page) Central Standards Bureau of the Ministry of Economy—Industrial and Consumer Cooperatives The average degree of polymerization was printed to 1500, and the completely saponified polyvinyl alcohol resin was dissolved in hot water and then cooled. A separately prepared calcium chloride aqueous solution was added thereto as a mixed solution of 2,000 m in total. It is slowly dropped into an aqueous solution of sodium alginate, and the solution will settle and gelatinize to form a translucent button-shaped gel. Then, the button is coagulated_separated, recovered, and then added by mexyl and sulfuric acid The resulting mixed aqueous solution has a liquid temperature of 60 ° C. At the time of adding 29- This paper size is applicable to the KW home sample (CNS) Λ4 specification {210X297 mm) 421658 A7 B7 Printed by the male laborer's consumer cooperation department of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (^) Simultaneously transparent The gelatinous particles started to become cloudy, and after about 10 minutes, they were completely whitened. The obtained rubber elasticity was not spherical particles or hollow 0 (Tucile Example 4) ί dripping solution) Polyvinyl alcohol 5 · 096 calcium chloride 2.0% methyl m 3. 096 sulfuric acid 4. 096 water 86. 096 (1 g 1 reaction liquid) m sodium 0. 596 water 96. 5% (second reaction liquid) average polymerization degree of water Is 1500 > * ± = »The mixed solution of Vulcanized Polyvinyl Alcohol, Calcium Chloride and Formaldehyde Sulfuric Acid is slowly dropped into the aqueous solution of sodium alginate. Settle and gelatinize the particles to separate them t and add them to Yu Yu in 60 t. After reacting for 30 minutes, t can obtain elastic particles. The particles are not hollow particles and have a strength higher than that obtained in Example 3. 〇 In addition, it is determined that the residual 3P ^} is dripped, and it will solidify after 15 minutes. Therefore, after adjusting the drip, it must be used very early. (Example 4) (Drip) Polyvinyl alcohol 7. 5% 30 The size of the paper for this guideline is applicable to the national standard (CNS) A4 (210X297 mm) of the country. Please read 'Notes on the back, and then fill in J page 421658 A7 B7. 5. Description of the invention (θ) 0¾ Water 9 1 .596 (1st anti-liquid solution) Calcium vaporized 3.096 Water 97 '.096 (2nd Anti-m liquid) Formamidine 3. .096 Sulfuric acid 4, .096 Water 93, .096 Central Ministry of Economic Affairs Standard Bureau Shellfish Consumer Cooperatives printed with an average degree of polymerization of 1500. Alcohol resin is dissolved in hot water to be cooled. To this was added a separately prepared aqueous solution of sodium alginate to make a mixed solution of 2000 ml in total. It was slowly dripped into 5000 η 15 aqueous solution, and the droplets immediately solidified and began to lose fluidity. After about 3 minutes, they completely gelled and formed translucent spherical particles. Then, the coagulated particles were separated, recovered, and added to a mixed aqueous solution having a formaldehyde concentration of 4% and a sulfuric acid concentration of 5%. The semi-transparent coagulated particles were turbid at the same time as the addition, and completely whitened after about 3 minutes from the start, to obtain rubber-elastic spherical particles. It was thoroughly washed with water, and polyethylene spherical particles having a particle diameter of 3 to 4 ram, close to the uniform diameter of a sphere, were obtained. After the spherical particles were dried, the internal structure was observed with a scanning electron microscope, and it was found that most of the pores had 2 to 4 wn of pores, and any of them were communicating pores. (Example 5) -31----------- f ------- ΐτ ------ ^ (Please read the precautions on the back of S before filling in this page) The paper scale is quickly used by the Chinese National Standard (CNS > ί: 丨 0 < 297). After printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the gel-like particles were prepared by the same operation method as in Example 4. The gel-like particles were separated and recovered, and then added to a mixed aqueous solution of 8 (TC) made of 8% formaldehyde and 10% sulfuric acid. After reacting for 5 minutes in this state, 3 to 4 mm balls with inelasticity were obtained. The spherical particles have fine flat unevenness. They are thoroughly washed with water and dried, and the internal structure is observed with a scanning electron microscope. All are communication holes β (Example 6) (dropping solution) Polyvinyl alcohol 7,5% Sodium alginate 1.0% Water 9 1.5% (First reaction 掖) -3 2-42 165 8 A7 A7 B7 V. Invention Explanation (v) (drop) Polyvinyl alcohol 7.5% Sodium alginate 1.0% Water 91.5% (First reaction solution) Calcium vapor 3.0% Water 97.0% (Second reaction solution) Formaldehyde 8.0% Sulfuric acid 10.0% Water 82.0% Paper The standard is applicable to China National Standard (CNS) Α4 specification (21〇K 297mm) ---------- ^ ------ ΐτ ------ 0 Please note this page and fill in this page again) 421658 A7 B7 V. Description of the invention (^) Aqueous calcium water (2nd reaction solution i Formaldehyde acetic acid water 3.0% 97.0% 8.0% 10.0% 93.0¾ Same operation as in Example 5 Method: The condensed spheroidal particles were added to a mixed solution of 8t of methylxelol and 20% of osmic acid, and after reacting for 15 hours, the same hard spherical particles as in Example 2 were obtained. The result obtained by 5 is smooth. (Example 7) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (dropping solution) Poly (sodium alginate) starch water (first reaction solution) Calcium carbonated water (second reaction solution) Sulfur water 7.5% 1 .096 5,0% 86.5% 3.0% 97.0% 10.0% 15.0% 75.0% The mixed solution prepared by the same operation method as in Example 4 was used. Paper size applies Chinese National Standard (CNS) Λ4 specification (210 × Γ97 male) --------- Linyi ------ 1T ------ 0 (Please read the precautions on the back before (Fill in this page) 42 165 8 Central Ministry of Economic Affairs Printed by the quasi-station-industrial and consumer cooperatives V. Description of the invention (>) After entering 70 ^, 500 001111 gas dehydration, the coagulated P-shaped particles can be added. After the reaction is about 60 minutes to stir, the Particle-containing flowing pieces. Moreover, it is about 67 mol%. (Example 8) (Dripping solution) Polyalcohol sodium alginate water (first reaction solution) Calcium carbonate water (second reaction solution) Methyl sulfate aqueous solution was used in accordance with Example 4 5 0 0 0 m 1. After 7 0 Ί Π, the gelatinous particles were completely gelatinized and 瞹 -shaped particles were added to the aqueous solution of A7 B7 calcium chloride, the solution began to solidify, and 15 gelled, translucent elastic particles. Then, a 60 t aqueous solution of formaldehyde and sulfuric acid was used to obtain white spherical particles. In this state, it is easy to flow, and exhibits a higher degree of acetalization of the spherical particles obtained in this example than that obtained in Example 4. 5% 1.0% 5.0% 86.5% 3, 0% 97.0% 10.0% 15.0¾ 75.0% The mixed solution prepared by the same operation method was dropped into an aqueous calcium solution, the solution began to solidify, and 15 minutes were obtained to obtain translucent elastic particles. Then, the 7 5 1C water-soluble hydrazone formed by the condensed methyl K and sulfuric acid was borrowed -34- This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) --------- ^ ------ Order ------ 0 (Please read the notes on the back and fill in this page again) 421658 A7 B7 V. Description of the invention (V〇 about 15 minutes from anti-dawn, you can get a white ball In this state, tS is stirred, the particles are easy to flow, and show a higher flow rate than the one obtained in Example 4. In addition, the degree of acetalization of the spherical particles obtained in this example is about β 5 Molar (Comparative Example 5) (Drip solution) Polyvinyl alcohol 10.0% Sodium alginate 1.0% Water 89.0% (Reaction liquid) Calcium vaporized 3.0% Water 9 7.0% The average degree of polymerization was 1500, and the completely saponified polymer The vinyl alcohol resin was dissolved in hot water and then cooled, and a sodium alginate solution was added to the solution to form a mixed solution with a total volume of 2000m. It was slowly dripped into 5000% of 3% of gasified calcium gas. In the aqueous solution, the solution immediately began to solidify, and after about 3 minutes of loss of fluidity, it completely condensed, and the shape of the particles was water droplets, not spherical. (Comparative Example 6 ) I --------- ^ ------ 1T ------ ^ (Please read the notes on the back first before filling in this page) Printed (dropping solution) Polyvinyl alcohol 8.0% water 92,096 (reaction liquid) calcium carbonate 3.0% -35- This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X297 mm) 421658 A7 Central Bureau of Economic Affairs, Ministry of Economic Affairs B7 printed by s Beigong Cooperative Co., Ltd. 5. Description of the invention (material) Ice 97.0% makes the average degree of polymerization of 1500, completely saponified polyvinyl alcohol resin dissolved in water to form an 8% aqueous solution, which slowly drips 5000m of people.〗 In an aqueous solution of calcium chloride 3¾, the droplets were widely spread on the water surface of an aqueous solution of calcium chloride, and the solution was left to stand for 10 minutes in this state, and the solution would not solidify, and no gel could be obtained. (Tb comparative example 7) (Drip liquid 1 Polyvinyl alcohol 7.5% Sodium alginate 1.0% Starch 5.0% Water 86.5% (First reaction liquid) Calcium nitride 3.0% Water 9 7.0% (Second reaction liquid) Formaldehyde 10.0% Sulfuric acid 15.0% Water 75.0% The mixed solution prepared in the same manner as in Example 4 was dropped into a 5 0 0 m 1,7 0 TO calcium chloride aqueous solution, and the solution was opened. After solidification, after 15 minutes of spectroscopy, the condensation is completed, and translucent elastic particles can be obtained. Then, the gel-like particles are added to a 60 t aqueous solution of formaldehyde and sulfuric acid. After 5 minutes, white spherical particles were obtained. In this state --36-I --------- 赛 ------ 1T ------ 0 (Please S: Read the precautions on the back before filling in this purchase) Applicable to China National Standard for Standards (CNS) Λ4 (210X 297 mm) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 421658 A7 B7 V. Description of the invention (W) The particles are easy to flow, and they are more comparable to Example 4 The gain is high. However, the degree of acetalization of the spherical particles obtained in this comparative example was about 30 mol%, and the friction properties were confirmed in the durability test described below. The spherical particles obtained in the examples of each cellar are seabeds with a mesh structure and continuous air bubbles, which have good hydrophilicity and are rich in softness and elasticity when wet. Ten samples were selected from the porous material and the characteristics were measured. The porosity was uniformly dispersed between 80 and 95%, and the average porosity was 90%. Moreover, the first diameter of the stomata is scattered between 30 and 100 / im. The average is 60Wm. The diameter of the pores in this range is an appropriate size for the organisms in the porous body to maintain. Abstraction is used in the carrier. In addition, the pseudo specific gravity of the water-containing state of the porous spherical particles obtained in each example was about 1.017 to 1.019 for 10 samples. Moreover, the specific gravity of the particles of Example 3 of the hollow particles is smaller, being about 1.08. After centrifugal dehydration, the moisture content was 50.4%, and the 50% compressive stress was 20 乂 103 ^ < / | 112. Put 20 capsules into the shaking beaker water, temporarily floating on the water surface for 1 minute, 3 minutes and 28 seconds, all the particles are stable and sink below the water surface. (Compression test) Then, the porous spherical particles obtained in each example were dried at 60 ° C for 1 hour, and the moisture content was 3,0%. It is pressed under a pressure of 4,9xi06H / m2 and compressed to a diameter of 0.75 ~ 1.5min. Twenty of these were thrown into the oscillating water, quickly absorbed water, swelled, and after 8 seconds this part sank under the water. The precipitated particles were taken out and the moisture content was 50%, and they were measured in a wet state in water. All are restored to their original shapes after being thrown into the water ^ As can be seen from the above, they quickly swell into volume after being thrown into the water -37- (Please read the precautions on the back before filling out this page) The paper dimensions apply to Chinese National Standards (CNS) A4 specifications (2! 0X297 mm) Du printed by the Central Bureau of Standards of the Ministry of Economic Affairs 4 2 1 R 5 8 A7 B7 Fifth, the description of the invention (#) is 2 to 4 times. For plutonium, put 20 of the dried samples before pressing into the water of the shaking beaker, all the particles float on the water surface, even if the surface of the particles cannot absorb the air after absorbing water, so even if shaking 2 For hours, no particles sink under the water. (Durability test> In addition, the flow in the bioreactor was used as a theoretical simulation test. The porous spherical particles of each of the Examples and Comparative Examples 7 obtained in a container with a diameter of 150 mm and a height of 400 ns! The filling is 10% by volume, and the aerosol flows into the water, and the particles are evenly dispersed and flowed. The flowing ore is allowed to run for one month, and after running, the particles are taken out for observation, and the particles in the examples are not In the case of abrasion or breakage due to friction, it can be confirmed that it contains abrasion resistance. However, the particles of Comparative Example 7 with insufficient acetalization were found to be subject to abrasion. In addition, for comparison with monomers formed from other raw materials The anti-friction test of the friction resistance performance is carried out with a water-resistant sand on the inner surface of the side wall of the same test container as described above (No. 100 Λ and each carrier is filled with 10% of the water for the most part). Stirring and flowing. The mixing system is set to rotate the mixing blades into the water tank at a speed of 30oγρβι to cause the load to flow mechanically and cause friction with the inner wall. This flow is continuously mounted for 1 week. Observation load over time No marrow status The abrasion caused by friction of the porous spherical particles of the present invention can be confirmed to be rich in friction resistance. In this regard, other raw materials are pseudo-selected with a diameter of a polyurethane sponge, a vitamin sponge, and algae. Acid 'good spherical gel, it can be confirmed that 2 4 -3 8-This paper size is applicable, 丨 WW House (CNS > Yigege (210X297 mm) (Please read the precautions of the real side before (Fill in this page)
、1T 經濟部中央標準局員工消費合作社印製 421658 A7 B7五、發明説明（Μ ) 小時後表而皆受到剝削、摩損。另外於1週後進Θ摩損、 全部原料之大小皆減小一半以上。而且，有關藻酸鈣凝 腐偽使用使濃度之藻酸鈉水溶液滴入2 %濃度之氯 化鈣水溶液中，藉由凝固所作成者。 ί載體之撤生物分解性試驗） 此外，使該粒子充焴約10%於具2mm篩目之多數孔的 聚丙烯容器，Μ該容器浸漬於活性污泥法曝氣槽内。一 年後取出該容器，觀察容器内聚乙烯基縮醛粒子，完全 沒有因摩擦所引起的礬化。而且，在該粒子表面上高密 度地附箸有好氣性撒生物，藉由此等之擻生物可知無截 體之浸蝕。 (包括固定化載體之製诰） 以體積比1 : 1之比例，混合經離心分離法製得5 0 g / I 左右濃编的活性汚泥與2%藻酸納所成之混合液，且使 其含浸於砍上述操作製造的各實施例所得之多孔性球狀 粒子中。為使含浸量增加，故在減壓下使該混合液流入。 在該多孔性球狀粒子中含浸藻酸納與撒生物之混合溶 液所得的微生物包括物，將其添加於5 %氮化鈣水溶液 並予以攪拌，且在該狀態下反應約3小時。藉此，含於 聚乙烯基縮薛糸多孔質物中之藻酸銷傺不溶化且以包含 微生物的狀態被固定。 如此所得的撒生物包括固定化載體，係為在上述之多 孔性球狀粒子之細孔中及表面上附著有藻酸糸凝膠者， 與該聚乙烯基縮醛糸多孔質物相同地具良好的親水性， -39- ----------^.------1Τ------^ (請先¾¾背面之注意事項再填寫本頁) 本紙張尺度適_用中國國家標準（CNS ) A4規格（2!Οχ2ξ>7公釐} 經濟部中央樣隼局貝工消費合作社印製 4 2 丨。5 8 A7 B7 五、發明説明（W ) 月濕澗時富含柔軟性及彈性。此外，由於為多孔性球狀 粒子聚乙烯基甲醛、富含親水性，故多孔性粒子易與凝 腰産生親和，粒子中存在均勻的凝膠。另外.由於氣孔 率窩，為立體網目構造，粒子中凝膠之比例維持於高比 例。 預測生物反應器内流動之模擬試驗，偽在直徑150mm、 高度400ιηπι之容器内，充填所得的上述徹生物包括固定 載髀，且於水中曝氣流動時使該載體均勻地分散流動。 使該流動連廉蓮轉1値月後，取出該粒子觀察，完全沒 有因摩擦産生的摩損或破損，可確知富含耐摩擦性。而 且，多孔性球狀粒子完全沒有受到徹生物浸蝕、惡化、 可確知仍雒持長的載睦赛命。 由上述之S施例，比較例可知.為以本發明之製法來 製造多孔性球狀粒子時，必須使具凝_化性質之水溶性 分子以適度的濃度配合，且為了維持其形狀則必須進行 縮醛化^例如，在S施例1與比較例1,或實施例2與 比較例2之比較中，可知由於滴下液中不含藻酸納，因 滴入無法雒持液滴形狀，結果變成雲吠粒子。 另外，如實施例3所示，例如將實施例1之第1反應 液與滴入液相反地予以滴入時，可知可得中空狀粒子。 此時聚乙烯醇之濃度低者，容易形成完美的粒子。 此外，由實施例7及賓施例8可知，藉由在滴下液中 加人躱粉等之氣孔形成劑，可控制球狀粒子之氣孔率及 氣孔直徑。使用澱粉做為氣孔形成劑時，將第1反應液 -40- 本紙張尺度適用中國國家榡準（CNS ) Λ4^柢/ 2V7公釐) " ：— (讀先閱讀背曲之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the 1T. 421658 A7 B7 V. Description of the invention (M) After the hour, the tables were all exploited and damaged. In addition, after one week, Θ wear was reduced, and the size of all raw materials was reduced by more than half. In addition, the calcium alginate coagulation method uses a solution of a sodium alginate solution having a concentration of 2% to a solution of a calcium chloride solution having a concentration of 2%, and is prepared by solidification. ί Carrier biodegradability test) In addition, the particles were filled with about 10% of a polypropylene container with a plurality of holes of 2 mm mesh, and the container was immersed in an activated sludge method aeration tank. After one year, the container was taken out, and the polyvinyl acetal particles in the container were observed. There was no aluminization caused by friction. In addition, aerobic scatter organisms are attached to the surface of the particles at a high density, and it can be seen that there is no erosion of the body by such a scavenger organism. (Including the preparation of immobilized carrier) At a volume ratio of 1: 1, a mixed solution of about 50 g / I of concentrated activated sludge and 2% sodium alginate was prepared by centrifugation and impregnated. In the porous spherical particles obtained by cutting each example produced by the above operation. In order to increase the impregnation amount, the mixed solution was allowed to flow under reduced pressure. The porous spherical particles were impregnated with a microorganism solution obtained by mixing a mixed solution of sodium alginate and biocide, added to a 5% calcium nitride aqueous solution and stirred, and reacted in this state for about 3 hours. As a result, the alginic acid pin contained in the porous material of polyvinylacetate is insoluble and is fixed in a state containing microorganisms. The thus-obtained stinger includes an immobilized carrier, and the alginate gel is attached to the pores and the surface of the porous spherical particles described above, and has the same good properties as the polyvinyl acetal porous material. The hydrophilicity of the paper, -39- ---------- ^ .------ 1Τ ------ ^ (Please fill in this page with the notes on the back first) _Printed in China National Standard (CNS) A4 (2! 〇χ2ξ > 7 mm) 4 2 丨. 5 8 A7 B7 5. The description of the invention (W) Rich in softness and elasticity. In addition, because it is a porous spherical particle of polyvinyl formaldehyde and rich in hydrophilicity, porous particles easily have affinity with condensed waist, and there is a uniform gel in the particles. In addition, due to porosity The nest is a three-dimensional mesh structure, and the proportion of gel in the particles is maintained at a high ratio. The simulation test for predicting the flow in the bioreactor is pseudo-filled in a container with a diameter of 150 mm and a height of 400 μm. And when the water is aerated and flowing, the carrier is evenly dispersed and flowed. After Dianlian Lianlian turned 1 month, the particles were taken out and observed. There was no abrasion or damage due to friction, and it was confirmed that they were rich in friction resistance. Moreover, the porous spherical particles were not completely eroded, deteriorated, and damaged. It is confirmed that the long-term race is still supported. From the above-mentioned S examples and comparative examples, it is known that in order to produce porous spherical particles by the production method of the present invention, it is necessary to make water-soluble molecules with coagulation properties to a moderate degree. It must be acetalized in order to maintain its shape. For example, in the comparison between S Example 1 and Comparative Example 1, or Example 2 and Comparative Example 2, it can be seen that the drip solution does not contain sodium alginate. Because the shape of the droplet cannot be held by the drop, it turns into cloud bark particles. In addition, as shown in Example 3, for example, when the first reaction liquid of Example 1 is dropped in the opposite direction to the drop liquid, it can be seen that Hollow particles. At this time, the lower the concentration of polyvinyl alcohol, it is easy to form perfect particles. In addition, it can be seen from Example 7 and Example 8 that by adding a pore-forming agent such as osmium powder to the dropping solution, Control the porosity and pores of spherical particles Diameter. When starch is used as a pore-forming agent, the first reaction solution is -40- This paper size is applicable to China National Standards (CNS) Λ4 ^ 柢 / 2V7mm) " (Fill in this page again)
D 5 8 A7 B7 經濟部中央標準局員工消费合作社印製 五、發明説明（ >ή ) 1 之 溫 度 做 稍 許 提 髙 的 設 定 可 使 m 粉 膨 脹 且 澱 粉 需 消 ! 1 r 耗 硫 酸 故 稍 許 提 高 設 定 第 2 反 m 液 之 硫 酸 配 合 量 可 得 1 1 較 佳 的 結 果 〇 而 且 可 知 使 第 2 反 應 液 溫 度 稍 許 提 高 t 請 1 先 1 可 大 Φη 地 縮 短 縮 醛 時 間 0 閱 t 而 目- 此 等 實 施 例 所 得 的 粒 子 全 部 可 做 為 撤 生 物 固 定 背 面 之 I 1 載 體 1 具 有 優 異 的 流 動 性 能 、 fcb 重 耐 摩 擦 性 耐 候 注 意 古 i I (光） 性 I 耐 撤 生 物 分 解 性 〇 此 外 * 藉 由 壓 縮 本 發 明 之 球 事 項 再 1 1 狀 粒 子 可 提 高 與 水 之 浸 透 性 \ 使 用 便 利 〇 惟 縮 m 化 度 低 填 寫 本 頁 1 裝 至30莫 耳 % 以 下 時 * ^s 曰 使 耐 摩 擦 性 降 低 0 1 I 商 業 上 之 利 用 價 值 1 1 本 發 明 之 多 孔 性 球 狀 粒 子 * 由 於 為 以 聚 乙 烯 基 缩 m % 1 1 樹 脂 為 架 構 之 多 孔 性 球 狀 粒 子 » 具 有 高 的 機 械 強 度 及 耐 1 訂 摩 擦 性 9 可 使 用 於 微 生 物 載 體 或 農 作 物 水 耕 栽 掊 之 溶 液 1 保 持 材 與 棺 物 支 持 材 9 動 植 物 細 胞 之 栽 培 地 9 人 工 水 苔 1 1 » 土 壤 改 良 材 水 中 流 動 型 洗 淨 部 材 % 水 中 流 動 型 按 摩 1 I 部 材 等 各 種 用 途 〇 尤 其 » 做 為 微 生 物 載 體 (特別是流動 1 1 線 I 床 型 m 生 物 載 體 時 因 載 體 動 時 所 産 生 的 載 體 間 摩 擦 或 與 反 應 槽 内 壁 之 摩 擦 > 亦 不 tS> 有 所 摩 損 其 載 體 壽 命 1 長 〇 外 除 與 撤 生 物 之 親 和 性 優 異 外 » 亦 具 有 優 異 的 J 流 動 性 能 比 重 耐 候 (光）性 f 耐 徹 生 物 分 U73 m 性 1 極 適 於 做 為 流 動 床 型 撤 生 物 載 體 * 徹 生 物 包 括 固 定 載 體 0 1 I 此 外 » 若 以 具 接 近 圓. 球 之 均 一 粒 子 直 徑 的 聚 乙 烯 基 縮 * i 1 m 樹 脂 為 架 構 之 多 孔 性 球 狀 粒 子 時 » 容 易 填 充 於 各 種 1 I 容 器 内 * 可 更 向 上 — 層 提 古 问 耐 摩 擦 性 » 且 可 提 髙 做 為 流 1 41 1 1 1 i 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 421658 A7 B7 五、發明説明（# ) 動體型撤生物載體之流動性。 另外，本發明之多孔性球狀粒子之製法，由於使以液 滴形狀一次反應，故各可大輻地缩短皮應時間及後加工 工程，大量連鑛地製造該球狀粒子。因此，可大幅地縮 短製造時間，及製得優異強度的材料.另可得具任意粒 徑之均一直徑之球狀物。而且，至少可減少習法之後工 程的損耗.且可缩小反應時必要的空間。另外，可製得 中空狀聚乙烯基缩醛糸多孔性球狀粒子，尤其是適合使 用為流動床型撤生物載體。 (請先时谈^命之注意事項再填寫本頁) -裝. -訂 經濟部中央樣準局員工消費合作社印製 42 本紙張尺度適用中國围家橾率（CNS > A4規格（210X297公釐）D 5 8 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (> price) 1 Setting the temperature slightly can make m powder swell and starch needs to be consumed! 1 r Sulfuric acid consumption is slightly increased A better result can be obtained by setting the sulfuric acid content of the second anti-m liquid to 1 1. Furthermore, it can be seen that the temperature of the second reaction liquid is slightly increased t 1 1 1 can shorten the acetal time by a large Φη. All the particles obtained in the examples can be used as the I 1 carrier on the back surface of the bioremoval agent. The carrier 1 has excellent flow properties, fcb, heavy friction resistance, and weather resistance. Note that I (light) property I is resistant to biodegradability. Furthermore, * by compression The ball matters of the present invention can improve the permeability to water with 1 1 particles. \ Easy to use. 〇However, the degree of shrinkage is low. Fill out this page. 1 When it is installed below 30 mol% * ^ s means that the friction resistance is reduced. 0 1 I Commercial use value 1 1 Porous spherical particles of the present invention * Because they are made of polyethylene based m% 1 1 Resin-based porous spherical particles »Has high mechanical strength and abrasion resistance 9 Can be used as a solution for microbial carriers or crop hydroponic cultivation1 Retaining materials and coffin support materials 9 Cultivation sites for animal and plant cells 9 Artificial water moss 1 1 »Soil improvement materials Water flowing type washing parts% Water flowing type massage 1 Various applications such as I materials 〇 Especially »As a microbial carrier (especially the flowing 1 1 line I bed type m biological carrier due to the friction between the carrier when the carrier moves or the friction with the inner wall of the reaction tank > nor tS > Yes Damaged its carrier life 1 long. In addition to excellent affinity with organisms »also has excellent J flow performance specific gravity weather resistance (light) resistance f U73 m property 1 is very suitable as a fluidized bed type bioremoval carrier. * The whole organism includes a fixed carrier. 0 1 I In addition »if it is made of polyethylene with a uniform particle diameter close to a circle. * 1 m resin as the framework Porous spherical particles »Easy to fill in various 1 I containers * Can be further upwards-layered ancient and rubbing resistance» and can be used as a stream 1 41 1 1 1 i This paper size applies to Chinese national standards (CNS ) Λ4 specification (210X297 mm) 421658 A7 B7 V. Description of the invention (#) The mobility of the living body type biological carrier. In addition, in the method for producing porous spherical particles of the present invention, since the reaction is performed once in the shape of a droplet, the skinning time and the post-processing process can be shortened by a large amount, and the spherical particles can be produced in a large number of continuous ore fields. Therefore, the manufacturing time can be greatly shortened, and a material with excellent strength can be obtained. In addition, a ball having a uniform diameter with an arbitrary particle diameter can be obtained. Moreover, at least the loss of engineering after the practice can be reduced, and the space necessary for the reaction can be reduced. In addition, hollow polyvinyl acetal fluorene porous spherical particles can be obtained, and are particularly suitable for use as a fluidized bed type biological carrier. (Please talk about the precautions for life before filling out this page) -Packing. -Ordered by the Central Consumer Procurement Bureau, Ministry of Economic Affairs, Printed by the Consumer Cooperatives 42 This paper size is applicable to China's furniture ratio (CNS > A4 size (210X297) %)