201018657 六、發明說明： 【發明所屬之技術領域】 本發明關於一種用於製備甲基丙烯醯胺水溶液之方法 。本發明進一步敘述一種用於進行該本發明方法之固體槽 【先前技術】 Ο 甲基丙烯醯胺被廣泛地用作製備聚合物的共聚單體。 因此，已知製備此單體之種種方法，雖然其亦可於市售取 得。 通常相對少量的甲基丙烯醯胺即足以改質許多聚合物 ，使得在使用場所直接製備甲基丙烯醯胺的設備操作在許 多情況中並不合乎經濟性。 因此，甲基丙烯醯胺係集中於大型設備中製備，然後 輸送到使用此單體的各種設備中。例如，該單體可以固體 ® 形式送到設備中，並於其中製備即用溶液。此可在慣常的 攪拌槽中進行。 在許多情況中，甲基丙烯醯胺係以水溶液形式使用。 然而，甲基丙烯醯胺與水接觸時易於形成團塊。而且，固 體在許多情況中包含微塵，這同樣是一個問題。在使用者 方面，此需要複雜的裝置來處置及計量材料，例如團塊壓 碎機及具有對應濾器之抽吸裝置。 就上述的理由，甲基丙烯醯胺在單獨的情況中係以水 溶液進行交易，以簡單且不貴的應用形式提供給使用者。 -5- 201018657 這些溶液典型地具有最大比例約15重量％之甲基丙烯醯 胺。爲了提高在溶液中的甲基丙烯醯胺濃度，已知各種被 詳述於例如 DE-B-10 2006 006 200 及 WO 2006/0027 1 7 中 的添加劑。 雖然甲基丙烯醯胺的濃度增加，但是此供應形式亦與 高成本有關，因爲必須輸送非常大量的水。此外，此輸送 類型亦造成環境危害，因爲在對輸送槽有損害的意外事件 中，甲基丙烯醯胺可輕易地進入流水中且被長距離擴散。 Q 關於此點，應指出甲基丙烯醯胺具有某種毒害神經的潛在 性。 從先前技藝已知用於溶解固體的裝置。例如， DE 1 0 2004 043 742敘述一種用於製備氰化鈉溶液之方法 。此外，US 4,40 7，7 79詳述一種用於溶解界面活性劑組成 物之裝置。用於溶解水溶性固體（尤其爲固體次氯酸鹽化 合物）的裝置被揭示於DE-A-24 22 08 8中。由於微塵問 題及甲基丙烯醯胺形成團塊的傾向，其中所述之裝置不適 @ 用於解決當前問題。 一種藉由將固體引入劇烈攪動之溶劑中以製備具有微 溶性及/或易於形成團塊之物質的溶液之方法述於 ΕΡ-Α-0 060 486中。然而，固體必須被加入此裝置中，結 果微塵問題仍存在。而且，該裝置的操作與高能量消耗有 關聯，因爲氣體流經溶劑。此外，加入裝置中的固體量係 完全溶解。因此，僅可製備既定量的甲基丙烯醯胺溶液。 在此缺點是甲基丙烯醯胺溶液的壽命比固體短。此具有過 -6- 201018657 量的甲基丙烯醯胺溶液必須常常予以處置的影響’因爲這 些溶液在一段時間之後不再符合規格。此外，不可能以此 設備連續製備溶液。由於以分批製備，必須預期會有不同 的品質，尤其是不同的溶液濃度。而且，此設備需要相對 大量的空間，因爲在可以開始消耗之前必須獲得全部想要 的量，雖然此導致時間延遲。以此方法無法達成連續製備 Ο 【發明內容】 有鑑於本文所討論的先前技藝，因此本發明的目的係 提供一種用於製備甲基丙烯醯胺水溶液之方法，其解決以 上詳述的問題。更特別的是，該方法應在甲基丙烯醯胺的 使用場所是可特別簡單且安全進行的。同時應避免微塵對 環境的危害。而且，該設備應可在不使用昂貴且不方便的 團塊壓碎機及抽吸裝置的情況下操作。此外，甲基丙烯醯 ® 胺水溶液應以低能量消耗方式獲得。 因此，本發明的進一步目的係指明一種用於提供甲基 丙烯醯胺水溶液之方法，其中可製備任何所欲量之溶液。 此尤其應避免製備過量的甲基丙烯醯胺溶液，而在一段時 間後由於衰退的品質而必須處置掉。另外，本方法應提供 一種非常實質固定的溶液品質。而且，應將溶液製備與溶 液消耗之間的時間減至最短。 可考慮的進一步目的是指明一種用於製備甲基丙烯醯 胺溶液之設備，其與特別低的投資成本有關聯。而且，該 -7- 201018657 設備應可輕易地整合到使用甲基丙烯醯胺溶液的現有設備 中。該設備因此應以非常節省空間的方式建構。 未明確地陳述但是以引介方式從本文所討論之關聯性 立即可衍生或分辨的這些目的及進一步的目的，係藉由具 有申請專利範圍第1項之所有特色的方法達成。根據本發 明方法之適當修改係受到引據申請專利範圍第1項之附屬 項的保護。關於進行本發明方法之固體槽及設備，申請專 利範圍第10及23項提供基本問題的解決辦法。 本發明據此提供一種用於製備甲基丙烯酸胺水溶液之 方法，其特徵在於使水通過包含甲基丙烯醯胺作爲固體的 固定床。 因此可以不可預見的方式提供一種製備甲基丙烯醯胺 水溶液之方法，其可以簡單且可靠地進行。 同時可避免微塵對環境的危害。而且，該設備可不使 用昂貴且不方便的團塊壓碎機及抽吸裝置而操作。此外， 甲基丙烯醯胺水溶液可以低能量消耗方式獲得。 而且，根據本發明的方法可製備任何所欲量之溶液。 此尤其可避免製備過量的甲基丙烯醯胺溶液，而在一段時 間後由於衰退的品質而必須處置掉。而且，有可能經由本 方法提供一種非常實質固定的溶液品質。 用於製備甲基丙烯醯胺溶液的本發明設備與特別低的 投資成本有關聯。而且，該設備可以特別節省空間的方式 建構，使得該設備可輕易地整合到使用甲基丙烯醯胺溶液 的現有設備中。 201018657 此外，本方法可連續進行，使得可確保固定的溶液品 質。此允許溶液的製備與消耗之間的時間減至最短。 根據本發明製備一種甲基丙烯醯胺水溶液。就此目的 所使用的水之品質不須有任何特殊的條件，而是僅由使用 者的需求決定。因此有可能使用泉水或較低品質的水，例 如自來水或在其他製程中釋出的水。 水可包含添加劑。這些添加劑尤其包括聚合抑制劑及 Φ 增加甲基丙烯醯胺在水中的溶解度之化合物。 聚合抑制劑爲技術領域中廣泛已知的，例如氫醌、氫 醌醚（諸如氫醌單甲醚或二-第三丁基焦兒茶酚）、啡噻 哄、4-羥基-2,2,6,6-四甲基六氫吡啶1-氧基、對-苯二胺 '亞甲藍、位阻酚或銅化合物（例如，二烷基二硫胺基甲 酸銅）。這些化合物可被單獨或以混合物形式使用，且通 常以市售取得。更多的細節參考標準的技術文獻，尤其爲 Rompp-Lexikon Chemie; Editors: J. Falbe，M. Regitz; ® Stuttgart, New York; 1 0th Edition (1 996)以·"抗氧化劑， 爲名；及其中引用之文獻。 增加甲基丙烯醯胺在水中的溶解度之化合物包括甲基 丙烯酸及N-羥甲基甲基丙烯醯胺。 引入固定床的含水液體之壓力可在寬廣的範圍內。本 身不明顯的特殊優點可藉由引入固定床的含水液體之壓力 在〇巴至100巴之範圍內，更佳地在1巴至10巴之範圍 內來達成。關於此點，應強調的是含水液體之壓力可藉由 其流經固定床時的流動阻力而降低。因此，此數値與液體 -9 - 201018657 流經固定床之前的壓力有關。201018657 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for preparing an aqueous solution of methacrylamide. The present invention further describes a solids tank for carrying out the process of the invention. [Prior Art] Methyl methacrylamide is widely used as a comonomer for the preparation of polymers. Thus, various methods of preparing such monomers are known, although they are also commercially available. Usually a relatively small amount of methacrylamide is sufficient to modify a large number of polymers, so that the operation of the apparatus for directly preparing methacrylamide at the place of use is not economical in many cases. Therefore, methacrylamide is concentrated in a large-scale apparatus and then delivered to various apparatuses using the monomer. For example, the monomer can be sent to the apparatus as a solid ® and a ready-to-use solution can be prepared therein. This can be done in a conventional stirred tank. In many cases, methacrylamide is used in the form of an aqueous solution. However, methacrylamide readily forms agglomerates upon contact with water. Moreover, the solid contains dust in many cases, which is also a problem. On the user side, this requires complex means for handling and metering materials, such as agglomerates and suction devices with corresponding filters. For the above reasons, methacrylamide is traded as a solution in a separate case and is provided to the user in a simple and inexpensive form of application. -5- 201018657 These solutions typically have a maximum proportion of about 15% by weight of methacrylamide. In order to increase the concentration of methacrylamide in solution, various additives which are described in detail in, for example, DE-B-10 2006 006 200 and WO 2006/0027 17 are known. Although the concentration of methacrylamide is increased, this form of supply is also associated with high costs because a very large amount of water must be delivered. In addition, this type of transport also poses an environmental hazard because methacrylamide can easily enter the running water and spread over long distances in the event of damage to the trough. Q In this regard, it should be noted that methacrylamide has some potential to poison nerves. Devices for dissolving solids are known from the prior art. For example, DE 1 0 2004 043 742 describes a process for preparing a sodium cyanide solution. Furthermore, US 4,40 7,7 79 details a device for dissolving a surfactant composition. A device for dissolving a water-soluble solid, especially a solid hypochlorite compound, is disclosed in DE-A-24 22 08 8. Due to the dust problem and the tendency of methacrylamide to form agglomerates, the device described therein is not suitable for solving the current problem. A method for preparing a solution having a substance which is slightly soluble and/or which is liable to form agglomerates by introducing a solid into a vigorously agitated solvent is described in ΕΡ-Α-0 060 486. However, solids must be added to the unit, and the dust problem still exists. Moreover, the operation of the device is associated with high energy consumption as the gas flows through the solvent. In addition, the amount of solids added to the unit is completely dissolved. Therefore, only a quantitative amount of the methacrylamide solution can be prepared. The disadvantage here is that the life of the methacrylamide solution is shorter than the solid. This methacrylamide solution with a quantity of -6-201018657 must be treated as often as 'because these solutions no longer meet specifications after a period of time. In addition, it is not possible to continuously prepare a solution using this apparatus. Due to batch preparation, different qualities must be expected, especially for different solution concentrations. Moreover, this device requires a relatively large amount of space because all the desired quantities must be obtained before the consumption can begin, although this results in a time delay. Continuous preparation cannot be achieved by this method. [Invention] In view of the prior art discussed herein, it is an object of the present invention to provide a process for preparing an aqueous solution of methacrylamide which solves the problems detailed above. More particularly, the method should be particularly simple and safe to carry out in the use of methacrylamide. At the same time, the harm of dust to the environment should be avoided. Moreover, the apparatus should be operable without the use of expensive and inconvenient briquetting crushers and suction devices. In addition, the aqueous solution of methacrolein® amine should be obtained in a low energy consumption manner. Accordingly, a further object of the present invention is to specify a process for providing an aqueous solution of methacrylamide wherein any desired amount of solution can be prepared. In particular, it should be avoided to prepare an excess of the methacrylamide solution, which must be disposed of after a period of time due to the quality of the decline. In addition, the method should provide a very substantially fixed solution quality. Moreover, the time between solution preparation and solution consumption should be minimized. A further object that can be considered is to specify an apparatus for preparing a solution of methacrylamide which is associated with a particularly low investment cost. Moreover, the -7-201018657 equipment should be easily integrated into existing equipment using methacrylamide solution. The device should therefore be constructed in a very space-saving manner. These and other objects which are not expressly stated, but which are immediately derivable or distinguishable from the relevance discussed herein, are achieved by a method having all the features of claim 1 of the patent application. Appropriate modifications in accordance with the method of the present invention are protected by the subclauses of item 1 of the scope of the patent application. With regard to the solid tanks and equipment for carrying out the method of the present invention, claims 10 and 23 of the patent scope provide solutions to the basic problems. The present invention accordingly provides a process for the preparation of an aqueous solution of an aqueous solution of methacrylic acid, characterized in that water is passed through a fixed bed comprising methacrylamide as a solid. Therefore, a method for preparing an aqueous solution of methacrylamide can be provided in an unpredictable manner, which can be carried out simply and reliably. At the same time, it can avoid the harm of dust to the environment. Moreover, the apparatus can be operated without the use of expensive and inconvenient briquetting crushers and suction devices. In addition, an aqueous solution of methacrylamide can be obtained in a low energy consumption manner. Moreover, any desired amount of solution can be prepared in accordance with the process of the present invention. This in particular avoids the preparation of an excess of the methacrylamide solution which must be disposed of after a period of time due to the quality of the decay. Moreover, it is possible to provide a very substantially fixed solution quality via the method. The apparatus of the invention for preparing methacrylamide solutions is associated with a particularly low investment cost. Moreover, the device can be constructed in a particularly space-saving manner such that the device can be easily integrated into existing equipment using methacrylamide solution. 201018657 In addition, the process can be carried out continuously to ensure a fixed solution quality. This allows the time between preparation and consumption of the solution to be minimized. An aqueous solution of methacrylamide is prepared in accordance with the present invention. The quality of the water used for this purpose does not require any special conditions, but is determined solely by the needs of the user. It is therefore possible to use spring water or lower quality water, such as tap water or water released in other processes. Water can contain additives. These additives include, inter alia, polymerization inhibitors and compounds which increase the solubility of methacrylamide in water. Polymerization inhibitors are widely known in the art, such as hydroquinone, hydroquinone ether (such as hydroquinone monomethyl ether or di-tert-butyl pyrocatechol), morphine, 4-hydroxy-2,2 6,6-tetramethylhexahydropyridine 1-oxyl, p-phenylenediamine 'methylene blue, hindered phenol or copper compound (for example, copper dialkyldithiocarbamate). These compounds can be used singly or in the form of a mixture, and are usually commercially available. For more details refer to the standard technical literature, in particular Rompp-Lexikon Chemie; Editors: J. Falbe, M. Regitz; ® Stuttgart, New York; 1 0th Edition (1 996) under the name "Antioxidant"; And the literature cited therein. Compounds which increase the solubility of methacrylamide in water include methacrylic acid and N-methylol methacrylamide. The pressure of the aqueous liquid introduced into the fixed bed can be in a wide range. A particular advantage that is not apparent by itself can be achieved by introducing a pressure of the aqueous liquid of the fixed bed in the range of from 100 bar to 100 bar, more preferably from 1 bar to 10 bar. In this regard, it should be emphasized that the pressure of the aqueous liquid can be reduced by the flow resistance as it flows through the fixed bed. Therefore, this number is related to the pressure before the liquid -9 - 201018657 flows through the fixed bed.
在本發明方法之特殊組態中，水可以脈衝方式通過固 定床。在此情況中，隨著水通過固定床之壓力可週期性地 增加及減少，以產生壓力突波。壓力差在此較佳地在大於 0巴至10巴之範圍內，更佳地在大於〇巴至3巴之範圍 內，壓力差係由至少4次週期之內達成的最大壓力及最小 壓力計算而得。脈衝頻率較佳地在1/分鐘至120/分鐘之 範圍內，更佳地在1/分鐘至60/分鐘之範圍內。 Q 爲了促進溶解速率，可使用超聲波產生器（20 kHz 至 1 0 GHz)。 含水液體通過固定床的速率本身並不重要。然而，特 別的優點可藉由先製備濃縮之甲基丙烯醯胺溶液而達成， 若需要時，可將其稀釋成所欲濃度。特別理想的是製備甲 基丙烯醯胺飽和溶液。 術語 > 濃縮溶液"意謂濃度較佳爲飽和限値的至少 80重量％，優先爲飽和限値的至少95重量％，亦即製備 甲基丙烯醯胺濃度對應於飽和甲基丙烯醯胺溶液濃度之至 少80%或95%之溶液。飽和限値取決於溫度且可以上述 的添加劑改變。用於測定飽和限値之方法爲技術領域中已 知。例如，飽和溶液可藉由將水引入過量的甲基丙烯醯胺 中經足夠長的時間，同時攪拌水而製備。爲了促進溶解， 在此可在相對高的溫度下完成溶解操作。接著可測定甲基 丙烯醯胺的濃度。在此情況中，應以適合的措施預防過度 飽和溶液的形成。 -10- 201018657 因此，較佳爲建立一種速度，使得水與甲基丙烯醯胺 接觸的時間足以獲得濃縮溶液，較佳爲飽和溶液。在此組 態中，水在固定床中的滯留時間較佳爲0.1 BV/h (每小時 之空床體積）至100 BV/h。特別的優點可以在1 BV/h至 5 BV/h之範圍內的滯留時間達成。 液體的溫度對所得甲基丙烯醯胺溶液的濃度具有重大 影響。加入固定床中的水溫度越高，則在所得溶液中的甲 基丙烯醯胺濃度越高。然而，高溫度的缺點爲甲基丙烯醯 胺會聚合。通入固定床的液體溫度較佳地在〇至100°C， 更佳地在5至70°c，而最佳地在25至50°C之範圍內。 本發明方法的基本特色在於使水通過固定床。術語^ 固定床'在本文係指使水通過包含甲基丙烯醯胺的固體之 配置。此固定床因此具有使水通過的開孔或渠道，其使水 與甲基丙烯醯胺接觸。 在本發明方法的特殊變型中，固定床可具有在大於〇 ® %至90%之範圍內，更佳地在40%至60%之範圍內的孔 隙度。孔隙度P爲固體的相對密度p (體密度，敲緊密度 )及純密度P 0 (粒子密度）之商數且典型地以百分比記 述。孔隙度P可由以下公式計算： P= 1--^- *100%In a particular configuration of the method of the invention, water can be passed through the fixed bed in a pulsed manner. In this case, the pressure can be periodically increased and decreased as the water passes through the fixed bed to generate a pressure surge. The pressure difference is here preferably in the range from more than 0 bar to 10 bar, more preferably in the range from more than mbar to 3 bar, and the pressure difference is calculated from the maximum pressure and the minimum pressure achieved in at least 4 cycles. And got it. The pulse frequency is preferably in the range of from 1/min to 120/min, more preferably in the range of from 1/min to 60/min. Q To promote the dissolution rate, an ultrasonic generator (20 kHz to 10 GHz) can be used. The rate at which the aqueous liquid passes through the fixed bed is not critical per se. However, a particular advantage can be achieved by first preparing a concentrated methacrylamide solution which can be diluted to the desired concentration if desired. It is particularly desirable to prepare a saturated solution of methyl acrylamide. The term > concentrated solution" means that the concentration is preferably at least 80% by weight of the saturation limit, preferably at least 95% by weight of the saturation limit, that is, the concentration of the methacrylamide is corresponding to the saturated methacrylamide. A solution of at least 80% or 95% of the solution concentration. The saturation limit depends on the temperature and can be varied by the additives described above. Methods for determining saturation limits are known in the art. For example, a saturated solution can be prepared by introducing water into an excess of methacrylamide for a sufficient period of time while stirring the water. In order to promote dissolution, the dissolution operation can be carried out here at a relatively high temperature. The concentration of methacrylamide can then be determined. In this case, the formation of an excessively saturated solution should be prevented by suitable measures. -10-201018657 Therefore, it is preferred to establish a speed such that the contact time of water with methacrylamide is sufficient to obtain a concentrated solution, preferably a saturated solution. In this configuration, the residence time of water in the fixed bed is preferably from 0.1 BV/h (empty bed volume per hour) to 100 BV/h. A particular advantage can be achieved with a residence time in the range of 1 BV/h to 5 BV/h. The temperature of the liquid has a significant effect on the concentration of the resulting methacrylamide solution. The higher the temperature of the water added to the fixed bed, the higher the concentration of methyl acrylamide in the resulting solution. However, a disadvantage of high temperature is that the methacrylamide can be polymerized. The temperature of the liquid introduced into the fixed bed is preferably from 〇 to 100 ° C, more preferably from 5 to 70 ° C, and most preferably from 25 to 50 ° C. An essential feature of the method of the invention is the passage of water through a fixed bed. The term ^fixed bed 'in this context refers to a configuration in which water is passed through a solid comprising methacrylamide. This fixed bed thus has openings or channels for the passage of water which brings the water into contact with methacrolimin. In a particular variant of the process according to the invention, the fixed bed may have a porosity in the range of more than % % % to 90%, more preferably in the range of 40% to 60%. Porosity P is the quotient of the relative density p (bulk density, knock tightness) and pure density P 0 (particle density) of the solid and is typically expressed as a percentage. The porosity P can be calculated by the following formula: P = 1--^- *100%
La」 其中P爲相對密度及Pg爲純密度。密度P及/〇〇可以例 如根據D IN IS Ο 1 3 0 6之方法測定。 固定床更佳地係經建構爲包含甲基丙烯醯胺的床形式 -11 - 201018657 。在本發明方法的此組態中’甲基丙烯醯胺較佳地可具有 在0.05毫米至100毫米之範圍內，更佳地在0.2毫米至2 毫米之範圍內的粒度’其係測量如DIN 661 65-1及 DIN 66165-2 。 固定床不但包含甲基丙烯醯胺’還可包含更多水溶性 化合物。這些化合物尤其包括以上詳述之聚合抑制劑及增 加甲基丙烯醯胺溶解度之化合物。 除了以上詳述之水溶性化合物以外，固定床可包含不 _ 溶於水中的物質。這些物質尤其包括微粒物質，例如砂或 聚合物纖維。 然而，爲了降低輸送成本，在許多情況中，僅少量不 溶於水之物質被加入固定床中。因此，尤其較佳的是其中 使水通過具有特別高比例之甲基丙烯醯胺的固定床之方法 。令人驚異的是本發明方法亦可在以乾固定床重量爲基準 計至少50重量％，更佳地至少85重量％，而最佳地至少 95重量％之固定床的甲基丙烯醯胺含量下進行。 _ 在本發明的一特定態樣中，水可從底部向上流經固定 床。因此，水流經固定床的方向具有與地球表面呈直角對 齊的組件。然而，流動方向亦可具有與地球表面平行的組 件。相對於地球表面的角度較佳爲至少40°，更佳爲至少 85、 本發明方法較佳爲使用包含固定床的固體槽進行，該 固定床包含甲基丙烯醯胺。這些槽同樣構成本發明標的的 一部分。 -12- 201018657 固體槽的形狀本身不重要。固定床在流動方向上的尺 寸對固定床體積之比較佳地在〇.〇1公尺/立方公尺至7公 尺/立方公尺之範圍內，更佳地在0.05公尺/立方公尺至 1.3公尺/立方公尺之範圍內。 固定床在流動方向上的尺寸在此係以水在流動方向上 行經的路徑長度來計算，在此不考慮微結構。該尺寸尤其 可從連接與流動表面呈直角的固定床表面（以下被稱爲截 〇 面積）中央之管線來計算。在圓柱（亦即以甲基丙烯醯胺 塡充之管子）的情況中，在流動方向上的固定床尺寸尤其 係從圓柱的高度或長度h來計算，固定床體積V係由公 式V = G*h來計算，其中G爲底面積且h爲高度。 在本發明固體槽的另一較隹組態中，其具有呈圓錐形 狀的區域。據此，較佳的固體槽可在以水流經固定床所行 經之距離上具有不同的截面積。在此具體例的特別組態中 ，在此截面積可增加至少兩倍，更佳地至少四倍。 ® 爲了進行根據本發明的方法，固體槽具有至少一個入 口孔及出口孔。兩個孔較佳地均可以可保持固定床的玻璃 料來封閉。在玻璃料中的孔徑較佳地在0.05毫米至〇.5 毫米，更佳地在0.2毫米至0.5毫米之範圍內，其係以 ISO 4793所測量。 令人驚異的優點尤其可藉由建構固體槽使得固定床可 經加壓或使得此壓力係由於固定床的結構所建立來達成。 一種使其達成的方式係設置於固體槽的孔之玻璃料中至少 —者係經建構爲可動式。例如，出口孔的玻璃料可具有特 -13- 201018657 別大的重量，由於此玻璃料的可移動性而使其施力於固定 床上。更佳地，入口孔的玻璃料亦經建構爲可動式，在此 情況中，含水液體之壓力使玻璃料壓抵固定床，而加壓於 固定床。 另外，固體槽的尺寸可經選擇使得由固定床的上部件 施加於下部件的重量引起足夠的壓縮。固定床的下部件在 此情況中較佳爲使得濃縮之甲基丙烯醯胺溶液已於此部件 ㈣胃° @ 固定床較佳地產生在0·05巴至10巴之範圍內，更佳 地在0.05巴到2巴之範圍內的壓力降，其係測量如 DIN 66126-1 。 特別適當的本發明固體槽具體例係以固體槽經建構爲 具有溫度控制爲特徵。此可以例如熱交換器經由固體槽壁 的方式達成。另外，有可能在固體槽內提供溫度控制元件 ，例如在固定床內或可設置於入口孔或出口孔的上述之玻La" where P is the relative density and Pg is the pure density. The density P and / / can be measured, for example, according to the method of D IN IS Ο 1 3 0 6 . The fixed bed is preferably constructed as a bed form comprising methacrylamide -11 - 201018657. In this configuration of the process of the invention, the "methacrylamide" may preferably have a particle size in the range of from 0.05 mm to 100 mm, more preferably in the range of from 0.2 mm to 2 mm. 661 65-1 and DIN 66165-2. The fixed bed may contain not only methacrylamide but also more water soluble compounds. These compounds include, inter alia, the polymerization inhibitors detailed above and compounds which increase the solubility of methacrylamide. In addition to the water-soluble compounds detailed above, the fixed bed may contain materials that are not soluble in water. These materials include, inter alia, particulate matter such as sand or polymeric fibers. However, in order to reduce the transportation cost, in many cases, only a small amount of water-insoluble matter is added to the fixed bed. Therefore, a method in which water is passed through a fixed bed having a particularly high proportion of methacrylamide is particularly preferred. Surprisingly, the process of the invention may also comprise at least 50% by weight, more preferably at least 85% by weight, and most preferably at least 95% by weight, based on the weight of the dry fixed bed, of the methacrylamide content of the fixed bed. Go on. In a particular aspect of the invention, water can flow from the bottom up through the fixed bed. Thus, the direction of water flow through the fixed bed has components that are aligned at right angles to the earth's surface. However, the flow direction can also have components that are parallel to the Earth's surface. Preferably, the angle relative to the surface of the earth is at least 40, more preferably at least 85. The process of the invention is preferably carried out using a solids tank comprising a fixed bed comprising methacrylamide. These grooves also form part of the subject matter of the present invention. -12- 201018657 The shape of the solid trough itself is not important. The size of the fixed bed in the flow direction is preferably in the range of 〇 1 / 1 m / m ^ 3 to 7 m / m ^ 3 , more preferably 0.05 m / m ^ 3 Up to 1.3 meters / cubic meter. The dimension of the fixed bed in the flow direction is here calculated as the path length through which the water travels in the direction of flow, without regard to the microstructure. This dimension can be calculated, inter alia, from a line connecting the center of a fixed bed surface (hereinafter referred to as the intercept area) at right angles to the flow surface. In the case of a cylinder (ie a tube filled with methacrylamide), the fixed bed size in the flow direction is calculated in particular from the height or length h of the cylinder, and the fixed bed volume V is determined by the formula V = G *h to calculate, where G is the bottom area and h is the height. In another relatively simple configuration of the solids tank of the present invention, it has a conical shape. Accordingly, preferred solid channels can have different cross-sectional areas over the distance traveled by the water through the fixed bed. In the particular configuration of this particular example, the cross-sectional area can be increased by at least two times, more preferably by at least four times. ® For carrying out the method according to the invention, the solids tank has at least one inlet opening and outlet opening. Preferably, both of the apertures can be closed by holding the glass of the fixed bed. The pore size in the frit is preferably in the range of 0.05 mm to 5.5 mm, more preferably 0.2 mm to 0.5 mm, as measured by ISO 4793. An amazing advantage can be achieved, inter alia, by constructing a solid trough so that the fixed bed can be pressurized or such that the pressure is established by the structure of the fixed bed. One way of achieving this is to provide at least the glass frit of the hole in the solids tank that is constructed to be movable. For example, the frit of the exit orifice may have a particularly large weight, which is applied to the fixed bed due to the movability of the frit. More preferably, the frit of the inlet aperture is also constructed to be movable, in which case the pressure of the aqueous liquid causes the frit to press against the fixed bed and pressurize the fixed bed. Additionally, the size of the solid trough can be selected such that sufficient weight is applied by the weight of the upper member of the fixed bed applied to the lower member. The lower part of the fixed bed is preferably in this case such that the concentrated methacrylamide solution has been present in the component (4) stomach. The fixed bed is preferably produced in the range of 0. 05 to 10 bar, more preferably The pressure drop in the range of 0.05 bar to 2 bar is measured as DIN 66126-1. A particularly suitable embodiment of the solid tank of the present invention is characterized in that the solid tank is constructed to have temperature control. This can be achieved, for example, by means of a heat exchanger via a solid channel wall. In addition, it is possible to provide a temperature control element in the solid tank, such as the above-mentioned glass in a fixed bed or which may be placed in the inlet or outlet hole.
璃料內。例如，可使加熱或冷卻管線通過玻璃料。特佳的 G 是其中固定床的溫度可與出口孔的溫度單獨控制的具體例 〇 用於進行本發明方法之設備同樣構成本發明標的的一 部分，該設備包含至少一個泵及至少一個固體槽。 在本發明的一特定態樣中，流動可從底部向上流經固 體槽。因此，經過固定床的液體路徑具有液體以相對於地 球表面的向上方向移動經過的區域。 固體槽較佳地基本上可以相對於地球表面爲垂直對齊 -14- 201018657 的，亦即傾斜角爲約90°，雖然在許多情況中可容許例如 小於1 0°，較佳地小於5 °之相對小偏差。在本發明方法的 特別適當的組態中，從底部向上流經基本上垂直對齊的固 體槽，使得流動方向具有與地球表面呈直角對齊的方向組 件。 這些設備更佳地具有用於測定在水溶液中的甲基丙烯 醯胺濃度的感測器。 φ 在特佳的組態中，設備可具有兩個使含水液體可交替 流經的固體槽。此組態允·許設備原則上不限時的連續操作 〇 現將參照二個圖式詳細說明本發明如下，但無意使本 發明受限於此。 圖1顯示用於進行本發明的圖解設備。可將具備添加 劑的水以泵2經由管線1泵抽到包含固定床4的本發明固 體槽3中，該固定床包含甲基丙烯醯胺。在本發明的具體 Φ 例中，固體槽具有設置於入口孔區域的玻璃料5及設置在 出口孔區域的玻璃料6。在本發明的具體例中，玻璃料5 係經建構爲可動式，使得此玻璃料壓迫固定床4。 將所得包含甲基丙烯醯胺的溶液經由具備用於測定甲 基丙烯醯胺濃度的感測器8之管線7從固體槽抽出。 在本發明具體例中，此設備另外具有入口 9，水可經 由此入口以混合閥1〇加入所得溶液中，以調整甲基丙烯 醯胺濃度至預設定値。因此獲得的混合物可經由管線11 從設備抽出。 •15- 201018657 本發明設備的第二具體例以參考圖2敘述於下，其基 本上類似於第一具體例，以至於僅將差異提出於下，以相 同的參考數字用於相同的部件且以上敘述相對適用。 與第一具體例一樣，圖2中所顯示之設備亦具有泵2 及具有固定床4的固體槽3。 與第一具體例比較，在圖2中所顯示之固體槽具有4 個呈圓錐構形的區域。此構形允許設備具有相對低的高度 。在此具體例中，尤其以固定床上區域中存在的物質施加 於固定床下區域上的固定床重量使固定床留在下區域中。 因此可以令人驚異的方式長時間提供濃縮之甲基丙烯醢胺 溶液，而完全不需要中斷設備的操作。 【實施方式】 實例1 將具有3公分內直徑及30公分長度的管子以120公 克甲基丙烯醯胺塡充。甲基丙烯醯胺在50%之孔隙度下 ❿ 具有0.8毫米之平均粒度。在入口及出口處所使用之玻璃 料材料爲玻璃絨塞。固定床的長度約爲其直徑的10倍。 空管體積爲200立方公分。 固定床管的溫度係以夾套與用作爲溶劑的水一起的方 式控制到3 〇 °c。1 〇毫升/分鐘之水從底部向上均勻地流經 固定床。在上床出口連續偵測甲基丙烯醯胺濃度。 以空管爲基準所計算之水的滯留時間在〇·9公尺/小 時之流速下爲3.0 BV/h (每小時之床體積）。在固定床入 -16- 201018657 口的壓力及越過固定床的壓力差二者<5 〇〇毫巴。 在供應1床體積的水（1 BV)之後’在30°c之選擇 溫度下飽和的甲基丙烯醯胺溶液（3〇重量％ )到達床出 口處。在3 BV之後，70質量％之所使用的甲基丙烯醯胺 已被溶解。在8BV之後，甲基丙烯醯胺被完全溶解。 實例2 φ 實例2基本上對應於實例1，除了溫度上升到7〇°C以 外。在供應1床體積的水（1 BV)之後’以55重量％之 甲基丙烯醯胺溶液到達床出口處。在3 BV之後，75質量 %之所使用的甲基丙烯醯胺被溶解。在5 BV之後’所有 的甲基丙烯醯胺被完全溶解。 實例3 將貯存槽內先裝入水及以10毫升/分鐘經由實例1中 • 所述之甲基丙烯醯胺固定床泵抽回到貯存槽中。此循環係 以控制到30°C之溫度進行。以680公克之供應水量與在 固定床中的120公克甲基丙烯醯胺量造成具有15重量％ 之甲基丙烯醯胺的溶液。在供應1 BV之後，在30°C之選 擇溫度下飽和的甲基丙烯醯胺溶液（30重量％)到達床 出口處。在2 BV之後，60質量％之所使用的甲基丙烯醯 胺已被溶解。在2至4 BV之範圍內，在床出口處的甲基 丙烯醯胺濃度快速接近於15重量％之甲基丙烯醯胺的最 終濃度。 -17- 201018657 【圖式簡單說明】 圖1爲進行根據本發明的方法之設備，其具有根據本 發明的固體槽的第一個具體例； 圖2爲進行根據本發明的方法之設備，其具有根據本 發明的固體槽的第二個具體例。 【主要元件符號說明】 @ 1 :管線 2 :泵 3 :固體槽 4 :固定床 5 :玻璃料 6 :玻璃料 7 :管線 8 :感測器 β 9 :入口 1 〇 :混合閥 1 1 :管線 -18-Inside the glass. For example, a heating or cooling line can be passed through the frit. A particularly preferred G is a specific example in which the temperature of the fixed bed can be individually controlled with the temperature of the outlet orifice. The apparatus for carrying out the process of the invention likewise forms part of the subject matter of the invention, the apparatus comprising at least one pump and at least one solids tank. In a particular aspect of the invention, the flow can flow from the bottom up through the solids slot. Therefore, the liquid path passing through the fixed bed has a region where the liquid moves in an upward direction with respect to the surface of the earth. Preferably, the solid trough is substantially vertically aligned with respect to the earth's surface from 14 to 201018657, i.e., the angle of inclination is about 90°, although in many cases it may, for example, be less than 10°, preferably less than 5°. Relatively small deviation. In a particularly suitable configuration of the method of the invention, the substantially vertically aligned solid slots are flowed from the bottom up such that the flow direction has a directional component aligned at right angles to the earth's surface. These devices more preferably have a sensor for determining the concentration of methacrylamide in an aqueous solution. φ In a particularly good configuration, the unit can have two solid tanks that allow the aqueous liquid to alternately flow through. This configuration allows the device to be continuously operated indefinitely in principle. The present invention will now be described in detail with reference to the two drawings, but is not intended to limit the invention. Figure 1 shows a diagrammatic device for carrying out the invention. The water with the additive can be pumped via pump 1 via line 1 to a solids tank 3 of the invention comprising a fixed bed 4 comprising methacrylamide. In the specific Φ example of the present invention, the solid groove has a glass frit 5 disposed in the inlet hole region and a glass frit 6 disposed in the outlet hole region. In a specific embodiment of the invention, the frit 5 is constructed to be movable such that the frit compresses the fixed bed 4. The resulting solution containing methacrylamide was taken out from the solid tank via a line 7 provided with a sensor 8 for measuring the concentration of methacrylamide. In a particular embodiment of the invention, the apparatus additionally has an inlet 9, through which water can be added to the resulting solution as a mixing valve 1 to adjust the concentration of methacrylamide to a predetermined enthalpy. The mixture thus obtained can be withdrawn from the apparatus via line 11. • 15-201018657 A second specific example of the apparatus of the present invention is described below with reference to FIG. 2, which is substantially similar to the first specific example, so that only the differences are given below, the same reference numerals are used for the same components and The above description is relatively applicable. As with the first specific example, the apparatus shown in Fig. 2 also has a pump 2 and a solid tank 3 having a fixed bed 4. Compared to the first specific example, the solid groove shown in Fig. 2 has four conical configurations. This configuration allows the device to have a relatively low height. In this particular embodiment, the fixed bed weight is applied to the lower region, particularly by the weight of the fixed bed applied to the area under the fixed bed. It is therefore possible to provide a concentrated solution of methacrylamide in an amazing manner for a long time without interrupting the operation of the apparatus at all. [Examples] Example 1 A tube having a diameter of 3 cm and a length of 30 cm was filled with 120 g of methacrylamide. The methacrylamide has an average particle size of 0.8 mm at a porosity of 50%. The frit material used at the inlet and outlet is a glass velvet. The length of the fixed bed is about 10 times its diameter. The empty tube volume is 200 cubic centimeters. The temperature of the fixed bed tube is controlled to 3 〇 °c by means of a jacket together with water used as a solvent. 1 〇ml/min of water flows uniformly from the bottom up through the fixed bed. The concentration of methacrylamide was continuously detected at the exit of the bed. The residence time of the water calculated on the basis of the empty pipe is 3.0 BV/h (bed volume per hour) at a flow rate of 〇·9 m/h. In the fixed bed, the pressure at the mouth of -16-201018657 and the pressure difference across the fixed bed are both <5 mbar. After supplying 1 bed volume of water (1 BV), a solution of methacrylamide (3% by weight) saturated at a temperature of 30 ° C reached the bed outlet. After 3 BV, 70% by mass of the methacrylamide used was dissolved. After 8 BV, the methacrylamide was completely dissolved. Example 2 φ Example 2 essentially corresponds to Example 1, except that the temperature rose above 7 °C. After supplying 1 bed volume of water (1 BV), the solution was passed to a bed outlet at 55 wt% methacrylamide solution. After 3 BV, 75 mass% of the methacrylamide used was dissolved. After 5 BV, all of the methacrylamide was completely dissolved. Example 3 The storage tank was first charged with water and pumped back to the storage tank via a fixed bed of methacrylamide as described in Example 1 at 10 ml/min. This cycle was carried out with a temperature controlled to 30 °C. A solution having 15% by weight of methacrylamide was produced at a water supply of 680 grams and an amount of 120 grams of methacrylamide in a fixed bed. After supplying 1 BV, a saturated solution of methacrylamide (30% by weight) at a temperature of 30 ° C reached the bed exit. After 2 BV, 60% by mass of the methacrylamide used was dissolved. In the range of 2 to 4 BV, the concentration of methacrylamide at the outlet of the bed is rapidly approaching the final concentration of 15% by weight of methacrylamide. -17- 201018657 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing an apparatus for carrying out the method according to the present invention, which has a first embodiment of a solid tank according to the present invention; FIG. 2 is an apparatus for carrying out the method according to the present invention. A second specific example having a solid tank according to the present invention. [Main component symbol description] @ 1 :Line 2 : Pump 3 : Solid tank 4 : Fixed bed 5 : Glass frit 6 : Glass frit 7 : Line 8 : Sensor β 9 : Inlet 1 〇: Mixing valve 1 1 : Pipeline -18-