1342865 九、發明說明： 【發明所屬之技術領域】 本發明係關於自鹼金屬氣酸鹽、酸和還原劑製造二氧 化氯的方法。 【先前技術】 二氧化氣係用於各種如紙漿漂白、脂肪漂白、水純化 及移除工業廢物的有機物質之類的應用。因為二氧化氣不 具貯存安定性’故其必須現場製造。 二氧化氣通常係藉由將鹼金屬氣酸鹽與還原劑在水反 應介質中反應製得。二氧化氣可自反應介質取出為氣體， 如美國專利5091 1 66、5091 1 67及歐洲專利61 2686所述之 方法中者。接者可將一氧化氣氣體吸收在水中，形成其水 溶液《這些係以需要龐大製程裝備及儀器的大規模製程較 佳。 對於在小規模單元中製造二氧化氣，如水純化應用或 小型漂白工廠，最好不要將二氧化氣與反應介質分開，而 疋直接自反應器回收含二氧化氣之溶液，視需要在以水稀 釋之後進行。14些方法係在美國專利2833624、4534952、 5895638、6790427、WO 〇〇/7691 9及美國專利申請公開案 第2004/01 75355號和公開案第2〇〇3/〇〇31621號中說明， 並在最近幾年成為商業方法。必要的製程配備及儀器遠不 如上述大規模製程者mi，仍有進—步改進的要求。 f小規模製程中，要獲得具有如許多應用如回收紙漂 白、菩、渣漂白或小規模紙聚漂白所希望的高濃度二氧化氣 5 1342865 的溶液，一直是困難的。 現有用於製造二氧化氣的小規模製程的另一個問題是 產物的二氧化氣濃度可能依據二氧化氣製造速率而變動。 【發明内容】 本發明的目的係提供製造二氧化氣的方法，其能夠直 接以具有高二氧化氣濃度之水溶液製得二氧化氣。 本發明的另一個目的係提供製造二氧化氣的方法，其 能夠直接以具有與二氧化氣製造速率無關而可維持不變之 ® 二氧化氣濃度的水溶液製得二氧化氣。 本發明還有的另一個目的係提供進行該方法的裝置。 本發明進一步的目的係提供新穎高濃度二氧化氣溶 液。 【實施方式】 已驚苛地發現以提供連續製造二氧化氣的方法有可能 符合這些目的，該方法包含連續的步驟：1342865 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing chlorine dioxide from an alkali metal gas salt, an acid and a reducing agent. [Prior Art] Dioxide gas is used in various applications such as pulp bleaching, fat bleaching, water purification, and removal of organic substances from industrial waste. Because dioxide does not have storage stability, it must be manufactured on site. The dioxide gas is usually obtained by reacting an alkali metal gas salt with a reducing agent in a water reaction medium. The oxidizing gas can be taken out from the reaction medium as a gas, as in the methods described in U.S. Patent Nos. 5,091,166, 5,091,1, and 6, 2,686. The receiver can absorb the oxidizing gas into the water to form its water solution. These are large-scale processes that require large process equipment and instruments. For the production of dioxide in small-scale units, such as water purification applications or small bleach plants, it is best not to separate the dioxide from the reaction medium, and to recover the solution containing the dioxide directly from the reactor, if necessary in water After dilution. 14 methods are described in U.S. Patent Nos. 2,836,324, 4,453,952, 5, 895, 638, 6, 904, 027, WO 〇〇/7691 9 and U.S. Patent Application Publication No. 2004/0175355, the disclosure of which is incorporated herein by reference. In recent years it has become a business method. The necessary process equipment and instruments are far less than the above-mentioned large-scale process, and there are still requirements for further improvement. In a small-scale process, it has been difficult to obtain a solution having a high concentration of sulfur dioxide 5 1342865 as desired for many applications such as recycled paper bleaching, pebbles, slag bleaching or small-scale paper poly-bleaching. Another problem with existing small scale processes for the manufacture of dioxide gas is that the concentration of dioxide in the product may vary depending on the rate of manufacture of the dioxide gas. SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a oxidizing gas which is capable of producing a oxidizing gas directly in an aqueous solution having a high concentration of a gas. Another object of the present invention is to provide a process for producing a oxidizing gas which is capable of producing a oxidizing gas directly from an aqueous solution having a concentration of a dioxin which can be maintained independently of the rate of manufacture of the oxidizing gas. Still another object of the present invention is to provide an apparatus for carrying out the method. A further object of the invention is to provide novel high concentration dioxide gas solutions. [Embodiment] It has been surprisingly found that a method for providing continuous production of a oxidizing gas is possible to meet these objectives, and the method comprises successive steps:
將酸、還原劑及鹼金屬氣酸鹽供給至反應器中；將鹼 金屬氣酸鹽與酸及還原劑反應，形成含有二氧化氣及酸之 鹼金屬鹽的產物流；及將來自反應器的該產物流攜帶至吸 收塔，使其在此與水流接觸，形成含有二氧化氣的水溶液。 已發現藉由將產料流攜帶至吸收塔，有可能獲得具有 高濃度二氧化氣的水溶液，以大於約3公克/公升較佳， 以大於約4公克/公升更佳’而無需先將二氧化氯氣體與 反應”貝刀開，然後將其吸收至水中。任何可溶性物種， 如酸的鹼金屬鹽及未反應之進料化學品，也被吸收在吸收 6 1342865 塔中。水往吸收塔的流速，無論驟冷與否，較佳為可調整 的如此可使一氧化氮濃度維持不變而與製造速度無關。 在吸收塔中所獲得的水溶液可具有寬廣的二氧化氣濃 度範圍，例如從約〇·】公克/公升至約12公克/公升，以 從約3公克/公升至約10公克/公升較佳，以從約4公克/ 公升至約8公克/公升最佳。在水溶液中的未反應氣酸鹽 濃度，依據轉化程度而定，係適合小於〇. 33莫耳/莫耳 Π〇2’以小於約0.u莫耳/莫耳cl〇2較佳以小於約〇 莫耳/莫耳C102最佳。鹼金屬鹽濃度係依據二氧化氣濃度 而定，並適合從約0.74毫莫耳/公升至約59毫莫耳/公升: 水溶液的pH可在從約〇」至約！，較佳從約〇 2至約U 的寬廣範圍内改變，部份係依據二氧化氣濃度而定。 如本文所使用的吸收塔術語代表使氣體在其中與液體 流接觸以吸收其中可溶性化合物的任何管柱或塔或類似 物。較佳係使氣體與液體以逆向流動。較佳係再吸收塔内 修放置如塔板或填充元件之類的㈣，以提供可進行在氣體 與液體之間的質量轉換的界面。有用的填充元件實例包括 拉西（Raschig)環、貝爾（Berl)鞍形填料、英特勒（Intai〇x) 較形填料等。可以使用的塔板實例為筛板及泡罩塔板。 較佳係將產生亞氣壓的設備與吸收塔連接，使產物流， 包括其中的任何液體、泡沫及氣體流入吸收塔中。未吸收 之氣體係以該設備自吸收塔柚取出來。可以使用任何常使 用的設備，如風扇、喷射器等，以喷射器較佳。在後者的 例子中，可自-個分開的儲槽及只服務於嘴射器的幫浦將 7 ⑧ 活動水供給至噴射器中。較佳係使儲槽通風，如此可移除 未吸收之製程氣體。 驗金屬氣酸鹽係適合以水溶液供給至反應器中。驗金 屬可為例如鈉、鉀或其混合物，其中以鈉最佳。酸係 機酸較佳，如硫酸、氫氣酸、硝酸、高氣酸或其混合物， 其中以硫酸最佳。可以使用數種還原劑，例如，過氧化氫、 甲醇、氣離子等，其中以過氧化氫最佳。在後者使用過氧 化氫的例子中，供給至反應器中的H2〇2對cl〇3_i莫耳比 適合從約0. 2 : 1至約2 :1，以從約〇. 5 : 1至約1. 5 : 1較佳， 以從約0. 5 :1至約1 :1最佳。鹼金屬氣酸鹽總是包括一些 為雜質的氣化物，但是完全有可能也使更多氣化物供給至 反應器中，如金屬氣化物或氫氣酸。然而，為了使氣的形 成降至最低，最好使供給至反應器的氣離子量維持低值， 適合小於1莫耳％，較佳係小於約〇·丨莫耳％，更佳係小於 約0· 05莫耳％，最佳係小於約〇, 〇2莫耳％來自㈠^-之cr。 在使用硫酸作為反應器進料的例子中，以具有從約6〇 至約98重量％之濃度較佳，以從約70至約85重量％最佳， 並以從約0至約8 0 C之溫度較佳’以從約2 〇至約6 0 °C最 佳，因為接著有可能以實質上絕熱方式操作製程。以製造 母公斤Cl〇2而言，以供給從約2至約7公斤較佳， 以伙約3至，約5公斤h2S04最佳。& 了使用高濃度硫酸， 較佳係使用如美國專利公開案第2〇〇4/〇1 75322號所述之 稀釋及冷卻方案。 在特別佳的具體實例中，將鹼金屬氣酸鹽及過氧化氫 8 1342865 乂預化合水溶液形式供給至反應器中，例如以w〇 〇 〇π69 j 6 二述之組合物，將其併入本文以供參考。這種組合物可為 含有從約1至約6.5莫耳/公升（以從約3至約6莫耳/公 升較佳）之鹼金屬氣酸鹽、從約丨至約7莫耳/公升（以從 約3至約5莫耳/公升較佳）之過氧化氫及保護膠體、自由 基清除劑或以膦酸為主之錯合劑中至少一種的水溶液，其 中水溶液的pH適合從約〇. 5至約4，以從約1至約3 5較 佳，以從約1.5至約3最佳。以至少一種以膦酸為主之錯 合劑存在較佳，以從約0.1至約5毫莫耳/公升的量較佳， 以從約0.5至約3毫莫耳/公升最佳。如果有保護膠體存 在時’則其濃度係以從約0. 001至約〇. 5莫耳/公升較佳’ 以從約0.02至約0· 05莫耳/公升最佳。如果有自由基清 除劑存在時，則其濃度係以從約〇. 〇丨至約1莫耳/公升較 佳，以從約0.02至約0.2莫耳/公升最佳。特別佳的組^ 物包含至少一種選自由卜羥基亞乙基-丨，卜二膦酸、卜胺 基乙烷-1，1-二膦酸、胺基三（亞曱基膦酸）、乙二胺四（亞 甲基膦酸）、六亞曱基二胺四（亞甲基膦酸）、二伸乙基= 胺五（亞曱基膦酸）、二伸乙基三胺六（亞曱基膦酸）、胺 基烷-1，1-二膦酸（如嗎啉甲烷二膦酸、N，N_二甲基胺灵_ 曱基二膦酸 '胺基甲基二膦酸）、其反應產物及鹽類（以鈉 鹽較佳）所組成群組之以膦酸為主之錯合劑。有用的保護 膠體包括錫化合物’如鹼金屬錫酸鹽，特別是踢酸納 (Na2 (Sn(0H)6)。有用的自由基清除劑包括。比。定竣醆，如 2 ’ 6 - °比《«定二叛酸。氣離子量適合小於約3 〇 〇毫莫耳/公升， ⑧ 9 1342865 以小於約50毫莫耳/公升較佳，以小於約5毫莫耳/公升 更佳’以小於約〇. 5毫莫耳/公升最佳。 將鹼金屬氣酸鹽還原成二氧化氣的作用在反應器中引 起產物流的形成，一般係包含液體及泡沫二者，並包含_ 氧化氣、酸之鹼金屬鹽，以及在大部份的例子中，還包人 一些剩餘未反應之進料化學品。如果使用過敦化氫作= 原劑，則產物流也包括氧。二氧化氣及氧可以同時以溶解 於液體中及以氣泡存在。如果使用硫酸，則驗金屬鹽為硫 酸鹽。頃發現有可能使鹼金屬氣酸鹽變成二氧化氯的轉^ 率達到從約75%至100%，以從約8〇至1〇〇%較佳以從約 95至100%最佳。 在反應器中的溫度在一般壓力下適合維持在反應物及 產物流的沸點之下，以從約2〇至約8(rc較佳，以從約Μ 至約60°C最佳。在反應器内維持的壓力適合為稍微低於大 氣壓者，以從約30至約1 〇〇kPa絕對壓力較佳，以從約65 至約95kPa絕對壓力最佳。 反應器可包含一或數種容器，例如，以垂直、水平或 傾斜排列的容器。可將反應物直接供給至反應器中或經由 分開的混合設備供給。適當而言，反應器以實質上為管狀 貫流式容器或管子較佳，以含有以實質均勻的方式混合反 應物的工具最佳。在例如美國專利6790427及美國專利公 開案第2004/0175322號說明這些用於混合的工具。 較佳係將包括酸、鹼金屬氣酸鹽和還原劑的進料在接 近反應器的一端供給’並且較佳係將產物流在反應器的另 ⑧ 10 1342865 一端取出。 所使用的反應器長度（在主要流 文机劫方向）係以從約1 5 〇 至約1 500毫米較佳，以從約3〇〇 υ主約9〇〇毫米最佳。頃 發現使用具有從約25至約300臺丰, 耄未，較佳從約50至約150 毫米内徑的實質上管狀的反應器是有利的。使用具有從約 12:1至約1:1，最佳從約8:1至約4:1之較佳長度對内徑 比的實質上管狀的反應器是特別有 X竹⑺有利的。在大部份的例子 中’在反應β中適合的平均停留時門技"，& J 7由吟間係從約1至約60秒， 以從約3至約2 0秒較佳。 本發明的方法特別適合以小規模製造二氧化氣，例如 從約0·5至約200公斤/小時，以從約1〇至約15〇公斤/ 小時較佳。典型的小規模製造單^般只包括—個反應 器，不過有可能以並行排列數個#高達肖15《更多個反 應器，例如成一束管路。如果使用一個以上的反應器時， 則視需要可選擇將每一個反應器與分開的吸收塔及產生低 於大氣麼之壓力的分開設備連接，或者將所有的反應器與 單一吸收塔及一個產生低於大氣壓之壓力的設備連接。 本發明進一步關於可經由如上述之方法製造的含二氧 化氣之新顆水溶液。在新賴水溶液中的二氧化氣濃度係從 約4至約12公克/公升，以從約4至約8公克/公升較佳， 以從約4公克/公升至約6公克/公升最佳。新穎二氧化氣 水溶液的pH係從約ο·!至約丨，以從約〇. 2至約〇. 8較佳。 在水溶液中的硫酸鹽濃度係從約I〗莫耳/莫耳ci〇2至約 3.8莫耳/莫耳C1〇2,以從約莫耳/莫耳ci〇2至約3 2 耳C在:溶液中殘留的氣酸鹽濃度適合小 莫耳 以小於約〇.11莫耳/莫耳U0 乂佳，以小於約〇·053莫耳/莫耳cl〇2最佳。 2 月進-步關於根據上述方法製造二氧化氣的裝 纟、置包括具備_或多個驗金屬氣酸鹽、過氧化氣和 =進料管線之反應器，反應器係與吸收塔連接。該裝置 進-：包括用於在反應器及吸收塔中產生低於大氣壓之壓 又備這種6又備較佳為以活動水供應的喷射器。 使本發明的方法有可能以簡單及容易操作的裝備製造 具有尚二氧化氯濃度的水溶液，即大於約3公克/公升，以 大於約4公克/公升較佳。 從以上的方法說明及以下參考圖式的說明可明白較佳 的裝置具體實例。但是，本發明不限於圖式中所示之具體 實例’且包含許多在申請專利範圍内的其它變化。 【圖式簡單說明】 圖1展示本發明具體實例的概要方法流程圖。 圖式詳細說明 參考圖1，將硫酸經由進料管線2及將氣酸鈉與過氧化 氮之預混合水溶液經由進料管線3供給至較佳為實質上管 狀的貫流式反應器1中。在反應器1中，將進料物流混合 及反應，形成含有二氧化氣、氡、硫酸鈉及一些剩餘硫酸 和氣酸鈉的液體、泡沫及氡體產物流。將產物流攜帶至吸 收塔4的下端，將水在塔頂6供給至塔中。使二氧化氣吸 收在水中，形成產物溶液，將其自吸收塔的塔底5取出。 12 1342865 為了在反應器1及吸收塔4中產生低於大氣壓的壓力， 故將噴射器7與吸收塔連接。以經由儲槽8循環及接著以 幫浦9經由喷射器泵送的活動水供給至噴射器7中。 使流動水儲槽通風，如此可移除未吸收在吸收塔中的 任何產物氣體，如氧。 【主要元件符號說明】 1.貫流式反應器 2 ·硫酸的進料管線 3·氣酸鈉及過氧化氫的進料管線 4. 吸收塔 5. 產物溶液的管線 6. 水的進料管線 7. 噴射器 8. 活動水儲槽 9. 活動水用幫浦 ⑧ 13Supplying an acid, a reducing agent, and an alkali metal sulphate to the reactor; reacting the alkali metal sulphate with an acid and a reducing agent to form a product stream comprising a oxidizing gas and an alkali metal salt of the acid; and The product stream is carried to an absorption column where it is contacted with a stream of water to form an aqueous solution containing dioxide. It has been found that by carrying the feed stream to the absorption column, it is possible to obtain an aqueous solution having a high concentration of dioxide gas, preferably greater than about 3 grams per liter, more preferably greater than about 4 grams per liter' without first The chlorine oxide gas reacts with the reaction and then absorbs it into the water. Any soluble species, such as alkali metal salts of acid and unreacted feed chemicals, are also absorbed in the absorption tower 1 1342865. Water to the absorption tower The flow rate, whether quenched or not, is preferably adjustable so that the concentration of nitrogen monoxide is maintained constant regardless of the manufacturing speed. The aqueous solution obtained in the absorption column can have a wide range of concentration of dioxide gas, for example Preferably, from about 3 grams per liter to about 10 grams per liter, preferably from about 4 grams per liter to about 8 grams per liter, preferably from about 4 grams per liter to about 10 grams per liter. The unreacted gas salt concentration, depending on the degree of conversion, is suitably less than 〇. 33 mol/mol 2' to less than about 0. u mol / mol cl〇 2 is preferably less than about 〇 mo Ear/Molar C102 is the best. The alkali metal salt concentration is based on Oxidizing gas on the concentration, and is suitable from about 0.74 mmol / liter to about 59 mmol well / L: pH of the aqueous solution may be from about square "to about! Preferably, it varies from a wide range of from about 2 to about U, depending in part on the concentration of the dioxide. Absorber column as used herein refers to any column or column or the like in which a gas is contacted with a liquid stream to absorb soluble compounds therein. It is preferred to cause the gas and the liquid to flow in the opposite direction. Preferably, the reabsorption column is provided with (4) such as trays or packing elements to provide an interface for mass conversion between gas and liquid. Examples of useful filling elements include Raschig rings, Berl saddle fillers, Intai〇x shaped fillers, and the like. Examples of trays that can be used are sieve plates and bubble trays. Preferably, the device that produces the sub-atmospheric pressure is coupled to the absorption column to cause the product stream, including any liquid, foam, and gas therein, to flow into the absorption column. The unabsorbed gas system is taken out of the absorption tower pomelo by the apparatus. Any commonly used equipment such as a fan, an ejector or the like can be used, and an ejector is preferred. In the latter case, the 7 8 active water can be supplied to the injector from a separate reservoir and a pump that only serves the mouthpiece. Preferably, the reservoir is vented so that unabsorbed process gases are removed. The metal gas salt is suitable for being supplied to the reactor as an aqueous solution. The gold test may be, for example, sodium, potassium or a mixture thereof, with sodium being most preferred. The acid acid is preferred, such as sulfuric acid, hydrogen acid, nitric acid, high gas acid or a mixture thereof, of which sulfuric acid is most preferred. Several reducing agents can be used, for example, hydrogen peroxide, methanol, gas ions, etc., with hydrogen peroxide being the best. In the latter example of the use of hydrogen peroxide, the H2〇2 to cl〇3_i molar ratio supplied to the reactor is suitably from about 0.2:1 to about 2:1, from about 〇. 5:1 to about 1. 5: 1 is preferred, preferably from about 0.5:1 to about 1:1. Alkali metal sulphates always include some vapors which are impurities, but it is entirely possible to also supply more gas to the reactor, such as metal hydride or hydrogen acid. However, in order to minimize the formation of gas, it is preferred to maintain the amount of gas ions supplied to the reactor at a low value, suitably less than 1 mol%, preferably less than about 〇·丨 mol%, more preferably less than about 0·05 Moer%, the best system is less than about 〇, 〇2 mol% is from (a)^-cr. In the case of using sulfuric acid as the reactor feed, it is preferred to have a concentration of from about 6 Torr to about 98% by weight, preferably from about 70 to about 85% by weight, and from about 0 to about 80 C. The temperature is preferably 'optimally from about 2 Torr to about 60 ° C because it is then possible to operate the process in a substantially adiabatic manner. For the production of the parent kilogram Cl2, it is preferred to supply from about 2 to about 7 kilograms, preferably from about 3 to about 5 kilograms of h2S04. &<>> using a high concentration of sulfuric acid, preferably using a dilution and cooling scheme as described in U.S. Patent Publication No. 2/4, No. 1,752,322. In a particularly preferred embodiment, an alkali metal sulphate and a hydrogen peroxide 8 1342865 乂 pre-formed aqueous solution are supplied to the reactor, for example as a composition of w〇〇〇π69 j 6 , which is incorporated This article is for reference. Such compositions may be an alkali metal sulphonate containing from about 1 to about 6.5 moles per liter (preferably from about 3 to about 6 moles per liter), from about 丨 to about 7 moles per liter ( An aqueous solution of at least one of hydrogen peroxide and a protective colloid, a radical scavenger or a phosphonic acid-based complexing agent, preferably from about 3 to about 5 mol/liter, wherein the pH of the aqueous solution is suitable from about 〇. From 5 to about 4, preferably from about 1 to about 3 5, and most preferably from about 1.5 to about 3. Preferably, at least one phosphonic acid-based complexing agent is present, preferably from about 0.1 to about 5 millimoles per liter, most preferably from about 0.5 to about 3 millimoles per liter. If the protective colloid is present, then the concentration is preferably from about 0.001 to about 〇. 5 m / liter, preferably from about 0.02 to about 0.05 mil / liter. If a free radical scavenger is present, the concentration is preferably from about 〇. 〇丨 to about 1 mole/liter, preferably from about 0.02 to about 0.2 moles/liter. A particularly preferred composition comprises at least one member selected from the group consisting of hydroxyethylidene-oxime, bisphosphonate, acetoethane-1,1-diphosphonic acid, aminotris(lindenylphosphonic acid), and B. Diamine tetra (methylene phosphonic acid), hexamethylene diamine tetra (methylene phosphonic acid), diexyl ethyl = amine penta (phosphinic acid), di-ethyltriamine (Asia) Mercaptophosphonic acid), aminyl-1,1-diphosphonic acid (such as morpholine methane diphosphonic acid, N,N-dimethylamine _ decyl diphosphonic acid 'aminomethyl diphosphonic acid) The reaction product and the salt (preferably sodium salt) are grouped by a phosphonic acid-based complex. Useful protective colloids include tin compounds such as alkali metal stannates, especially sodium chlorate (Na2(Sn(0H)6). Useful free radical scavengers include. 。, such as 2 ' 6 - ° It is better than "Definite acid. The amount of gas ions is less than about 3 〇〇 millimoles / liter, 8 9 1342865 is preferably less than about 50 millimoles / liter, preferably less than about 5 millimoles / liter." Preferably, the reduction of the alkali metal sulphonate to the sulphur dioxide causes the formation of a product stream in the reactor, generally comprising both liquid and foam, and comprises oxidizing Gas, acid alkali metal salts, and in most cases, some unreacted feed chemicals are also included. If Dunhua hydrogen is used as the original agent, the product stream also includes oxygen. And oxygen can be dissolved in the liquid and in the presence of bubbles. If sulfuric acid is used, the metal salt is sulfate. It has been found that it is possible to convert the alkali metal gasate into chlorine dioxide from about 75% to 100%, preferably from about 8〇 to 1〇〇%, preferably from about 95 to 100%. The temperature in the apparatus is suitably maintained below the boiling point of the reactants and product streams at a typical pressure, preferably from about 2 Torr to about 8 (rc is preferred, preferably from about Μ to about 60 ° C. in the reactor. The pressure maintained is suitably below a slight pressure, preferably from about 30 to about 1 kPa absolute, preferably from about 65 to about 95 kPa absolute. The reactor may contain one or several containers, for example, Containers arranged vertically, horizontally or obliquely. The reactants may be supplied directly to the reactor or via separate mixing equipment. Suitably, the reactor is preferably a substantially tubular tubular container or tube to contain A tool for mixing the reactants in a substantially uniform manner is described. These tools for mixing are described, for example, in U.S. Patent No. 6,790, 427 and U.S. Patent Publication No. 2004/0175322. Preferred are acids, alkali metal sulphonates and reducing agents. The feed is supplied near one end of the reactor and preferably the product stream is withdrawn at the other 8 10 1342865 end of the reactor. The length of the reactor used (in the main flow direction) is from about 15Preferably, it is about 1 500 mm, preferably about 9 mm from about 3 〇〇υ main. It is found to have from about 25 to about 300 units of feng, 耄, preferably from about 50 to about 150 mm. A substantially tubular reactor of the diameter is advantageous. A substantially tubular shape having an inner diameter ratio of from about 12:1 to about 1:1, preferably from about 8:1 to about 4:1 is used. The reactor is particularly advantageous with X. (7). In most of the examples, the average residence time in the reaction β is "&> J 7 from the daytime system from about 1 to about 60 seconds, Preferably, from about 3 to about 20 seconds. The process of the invention is particularly suitable for the manufacture of small scale gas, for example from about 0.5 to about 200 kg/hr, from about 1 Torr to about 15 Torr/hr. Preferably. A typical small-scale manufacturing process typically includes only one reactor, but it is possible to arrange several #多和肖15" more reactors in parallel, such as a bundle of tubes. If more than one reactor is used, then each reactor can be optionally connected to a separate absorber and separate equipment that produces a pressure below atmospheric, or all reactors can be combined with a single absorber and one Equipment connected to subatmospheric pressure. The invention further relates to a new aqueous solution of a oxidizing gas which can be produced via the process as described above. The concentration of dioxide in the aqueous solution of Xinlai is from about 4 to about 12 grams per liter, preferably from about 4 to about 8 grams per liter, preferably from about 4 grams per liter to about 6 grams per liter. The pH of the aqueous solution of the novel oxidizing gas is from about ··! to about 丨, preferably from about 〇. 2 to about 〇. The sulfate concentration in the aqueous solution is from about 1 mole/mole ci〇2 to about 3.8 mole/mole C1〇2, from about mole/mole ci〇2 to about 3 2 ears C at: The residual gasate concentration in the solution is preferably less than about 〇.11 mol/mole U0, preferably less than about 〇·053 mol/mol cl〇2. In February, the reactor for producing a gas oxide according to the above method comprises a reactor having _ or a plurality of metal sulphates, a peroxygen gas and a feed line, and the reactor is connected to the absorption tower. The apparatus includes: an apparatus for generating sub-atmospheric pressure in the reactor and the absorption tower, and further comprising an ejector which is preferably supplied with active water. It is possible to make the process of the present invention possible to produce an aqueous solution having a chlorine dioxide concentration in a simple and easy to handle apparatus, i.e., greater than about 3 grams per liter, preferably greater than about 4 grams per liter. Preferred device embodiments are apparent from the above description of the methods and the following description with reference to the drawings. However, the invention is not limited to the specific examples shown in the drawings, and includes many other variations within the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a flow chart of a summary method of a specific example of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to Figure 1, sulfuric acid is supplied via feed line 2 and a premixed aqueous solution of sodium carbonate and nitrogen peroxide via feed line 3 to a preferably substantially tubular tubular reactor 1. In Reactor 1, the feed stream is mixed and reacted to form a liquid, foam and steroid product stream containing dioxide, hydrazine, sodium sulphate and some residual sulphuric acid and sodium sulphate. The product stream is carried to the lower end of the absorption column 4, and water is supplied to the column at the top 6 of the column. The dioxide gas is absorbed in water to form a product solution which is taken out from the bottom 5 of the absorption tower. 12 1342865 In order to generate a subatmospheric pressure in the reactor 1 and the absorption tower 4, the injector 7 is connected to the absorption tower. The active water that is circulated through the sump 8 and then pumped by the pump 9 via the ejector is supplied to the ejector 7. The flowing water storage tank is vented so that any product gases, such as oxygen, that are not absorbed in the absorption tower can be removed. [Main component symbol description] 1. Tubular reactor 2 · Sulfuric acid feed line 3 · Sodium sulphate and hydrogen peroxide feed line 4. Absorption column 5. Product solution line 6. Water feed line 7 . Injector 8. Active water storage tank 9. Active water pump 8 13