1230694 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種超臨界氧化系統，尤指一種適用於 處理有害廢料之超臨界氧化系統。 【先前技術】 企業追求永續經營、清潔生產，帶動了廢棄物清潔處 理技術之發展。傳統焚化法雖可達到廢棄物高度減量之目 的，但由於衍生戴奥辛等排放問題，而為民眾所話病，並 10 2此付出較高社會成本。超臨界流體處理技術，係利用流1230694 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a supercritical oxidation system, especially a supercritical oxidation system suitable for treating hazardous waste. [Previous technology] The company's pursuit of sustainable operation and cleaner production has driven the development of clean waste treatment technology. Although the traditional incineration method can achieve the goal of high waste reduction, it has caused problems for the public due to the emission problems such as dioxin, and it has a high social cost. Supercritical fluid processing technology
體（例如水）於超臨界狀態下對有機物進行分解、分離，1L 而達到減廢、減毒等目的，由於破壞效率高且為密閉系統， 故完全無二次污染之虞。 然而，無機鹽類水溶液於超臨界水狀態下因為其溶解 15度降低，常常沈澱而造成超臨界流體系統管路與設備堵 塞，並因而使得整個超臨界流體系統的壓力急速上升，導 致超臨界流體系統必須停止運轉，以免遭遇危險或故障。 目前超臨界流體系統之設計大都是利用反應器的特殊設計 或是裝設氣液分離器來處理無機鹽類，但是由於進料的廢 20液種類複雜且濃度不一，徒增系統處理的複雜度與成本。 另外’一般處理具腐蝕性酸性物質之方法為添加鹼液以中 和之，但極可能造成系統有爆發的危機。中華民國專利公 告第2391 13號提出將廢液系統經過預熱後再流經反應器 底部。中華民國專利公告第293078號將廢液由高壓泵經高 1230694 壓閥流入反應器中，廢液進料系統並無冷卻裝置。而中華 民國專利公告第459249號之廢液混合後經預熱裝置再流 入反應器中’與—般常見的超臨界氧㈣統是相同的方 法其W用熱進料方式。綜上所言，先前技藝對於無機 鹽=的結垢問題並無一簡單有效之處理方法或裝置，是以 ，而要種可有效避免無機鹽類結垢以防止管線及設備堵 塞、並具南運轉效益之超臨界氧化設備。 【發明内容】 10 15The body (such as water) decomposes and separates organic matter in a supercritical state, and achieves the purpose of reducing waste and attenuating by 1L. Since the destruction efficiency is high and the system is closed, there is no risk of secondary pollution. However, in the case of supercritical water, the solubility of inorganic salt solutions is reduced by 15 degrees, which often causes the supercritical fluid system's pipelines and equipment to become clogged. As a result, the pressure of the entire supercritical fluid system rises rapidly, resulting in supercritical fluids. The system must be stopped to avoid danger or malfunction. At present, most of the design of supercritical fluid systems use special reactor design or install gas-liquid separators to process inorganic salts. However, due to the complexity and concentration of the waste 20 liquids fed, the processing of the system is complicated. Degree and cost. In addition, the general method for treating corrosive acidic materials is to add lye to neutralize it, but it is very likely to cause a crisis in the system. The Republic of China Patent Publication No. 2391 13 proposes to preheat the waste liquid system and then flow it through the bottom of the reactor. Republic of China Patent Bulletin No. 293078 The waste liquid was flowed into the reactor from a high-pressure pump through a high 1230694 pressure valve. The waste liquid feed system did not have a cooling device. However, the waste liquid of the Republic of China Patent Publication No. 459249 is mixed into a reactor through a preheating device and then fed into the reactor. The method is the same as that of a common supercritical oxygen system, which uses a hot feed method. To sum up, the previous technology did not have a simple and effective treatment method or device for the problem of scaling of inorganic salts. Therefore, it is necessary to have a method that can effectively prevent the scaling of inorganic salts to prevent blockage of pipelines and equipment. Supercritical oxidation equipment with operating benefits. [Summary of the invention] 10 15
At本發明之主要目的係在提供一種超臨界氧化系統，俾 月匕=止無機鹽類於進料管路中沉殿與結垢，避免進料管路 =整個氧化系統之操作廢力穩定’同時提高廢液之 。’延長糸統之運轉操作時間，降低系統之維修操 作成本。 ’、 為達成上述目的，本發明超臨界氧化系統，係配合— 〉谷液5包括：—^ _ 器，係管接於該第Γ進=，用以加壓於該溶液；一冷卻 送媒質样，用以針以降低該溶液之溫度；—輪 '、」：一储存該超臨界氧化系統所使用之輸送媒 二、关拔ί 一進料泉’係與該輸送媒質槽連接，以加屡於該 二挺貝’一加熱^係用以加熱該輸送媒質；一反應器， 二該第二進料泵，以接受該溶液與該輪 以接為—I 合/夜，—冷凝器，係管接於該反應器， -乳化後之該溶液並予以冷卻；以及一氣液分離器， 20 1230694 伶s接於该冷凝器，以接收冷卻後之該溶液並予以氣、液 態分離。 本I明超g品界氧化系統使用之輸送媒質可為一般超臨 界不統常用之流體，較佳為水。因水之臨界點為374它、22〇 5 Mm，且無機鹽類在水的臨界點附近溶解度驟降，故本發明 ，臨界氧化系統之冷卻器較佳係將進入該反應器之該溶液 :度控制於350°C以下，以防止無機鹽類的沈澱與結垢。且 Q沖态較佳為位於靠近反應器之一側，以防止反應器之熱 、輸U媒貝槽與反應為間之輸送管路。冷卻器之種類無 1〇限制，可為任何習知之冷卻器，較佳為-水夾套冷卻器。 本1明之超g品界氧化系統較佳更包含至少一空氣或氧氣儲 存乜，以知供氧化需要之氧氣。本發明之超臨界氧化系統 較佳更包括有至少—壓力量測元件與至少—溫度量測元 件，以里測該系統之壓力與溫度。本發明超臨界氧化系統 15處理之溶液可為一般之工業與民生廢水、環境污泥、有機 氯化物、含戴奥辛之飛灰、或高能量物質等難分解廢液， 較佳為低熱值廢液。本發明之超臨界氧化系統較佳地可於 該低熱值廢液或該輸送媒質加入一醇類&質，㈣加自由 基的反應效#’並提南該溶液之氧化效率，較佳地該溶液、 2〇為一低熱值廢液，且該醇類物質於該反應器内之濃度較佳 為低於20 Wt%。更佳的，上述醇類物質係為異丙醇。本發 明超臨界氧化系統之反應器壓力較佳為高於3〇〇〇_，反應 器溫度較佳為高於3〇〇t。 1230694 2廢液的進料多採用熱進料方式，本創作是採用々 十一式’在廢液進㈣統與反應器之間增加冷卻: 抖般使用預熱器預熱廢液之熱進料方式大不相同 =系統增加冷卻裂置，主要可防止反應器所需的高二;; 並防止廢液中的無機鹽類在反應器前的 吕路、、，口垢與沉澱，避免管路堵塞。 【實施方式】 首先說明本發明超臨界液體之原理，請參閱圖1，一 1〇般純物質包含有氣、固、液三相，於氣_液共存日夺，0液相: 度大於氣相密度，當系統溫度及壓力達到某一特定點時： 其氣-液兩相密度趨於相同，兩相合併為一均勻相。此一特 定點即定義為上述物質之臨界點，其所對應之溫度、壓力 和密度則分別定義為該純物質之臨界溫度（Tc)、臨界壓力 15 (Pc)和臨界密度（Pc)。若超過此點時，無論壓力如何增加 白撕法使之液化、溫度如何升高亦無法使之返回氣相，我 們即稱此南於臨界溫度及臨界壓力的均勻相為超臨界流體 (Supercritical Fluid) 水為自然界中最重要的溶劑，許多化合物進行反應均 20需要水參與反應或作為介質，利用溫度或壓力的控制、可 改變水的各種物化性質。於超臨界狀態下，水具有類似氣 體的擴散性及液體的溶解性等雙重性質，故可應用於有害 物質之萃取分離。 超臨界水氧化（Supercritical Water Oxidation，SCWO) 25 處理技術具高效率之氧化反應特性，較傳I充焚化處理法更 1230694 具有反應時間短、破壞效率高、能量損耗低及低空氣污染 等優勢’且無機鹽類在SCWO反應條件下易沉澱、分離及 回收，因此先進國家紛紛積極投入研發工作。水的臨界溫 度為374 C，臨界壓力為220 atm，在超臨界狀態下可與非 5極性之流體完全互溶，而解離子亦具高移動性及高電導 性。一般超臨界流體具有下列的特性： 1 ·與液體相似的密度與擴散係數。 2·與氣體相似的黏度。 3 ·極高的反應速度。 10 4.極低的表面張力。 超臨界氧化法類似濕式氧化法（wet 〇xidati〇n)，一般的 濕式氧化法由於水中溶氧不足，易造成氧化不完全，其尾 氣有揮發性有機物（V0C)排放的困擾，因此通常須再安 裝活性碳或觸媒等裝置，以確保廢氣能符合環保標準。此 15外，由於氧化是在兩相中進行，氧化速率慢，反應器體積 大饭如將廢水提幵至超臨界狀態（一般系統條件約在、 24-35 MPa^400~650°〇 > ^ ^^ ^ ^ ^ ^ ^^ #J ^ 3為均相’因此氧化能力提高’污染物質迅速被破壞，； 溫度達525°C以上時破壞率更可達99.99%，所產生之炉〒田 2〇化物（s〇x)及氮氧化物（Ν0χ)極低。 ；u氧 與一般濕式氧化法比較，SCW〇可處理高濃度及含夕 種類有機物的廢水，不但破壞效率高並可減少或二制3 = 產物的生成，又屬密閉性作業，當系統不穩曰] 回流再處理。 十低日守可 1230694 ，臥界氧化可應用於降解有害廢棄物，主要應用於六 大類有害廢棄物之處理： 〜1.塑取與添加物：含自素塑膠'火談抑制劑、塑化劑 等。 2·有钱物·殺蟲劑、醫藥、溶劑、染料。 3·回旎材料：高爆藥、煙火藥、氣體推進劑。 4·廢水·紡織工廠或紙漿工廠廢水、漂白廢水、切削 廢液、皮革廢液。 5·下水污泥：都市下水污泥、工業污泥。 1〇 6·叉巧"染土壤：礦油、含鹵素有機物。 為此"襄貝番查委員能更瞭解本發明之技術内容，特 舉超臨界氧化系統較佳具體實射㈣明如下。 請參照圖2,圖2為本發明之超臨界氧化系統示意圖， 主要由廢液儲存槽10、空氣儲存槽20、水儲槽30、高壓進 15料泵31，32,33、水夾套冷卻器4〇、加熱器82、超臨界氧化 反應器50、冷凝器60、氣液分離器7〇以及數個溫度偵測元 件與壓力偵測元件等所組成。空氣進料經進料泵32壓縮至 可進入反應器50的壓力，再進入反應器5〇 ;輸送媒質（本 實施例為水）經進料泵33加壓，加熱器82加熱至可進入反 20應器50之壓力及溫度；廢液進料由進料泵31加壓至2〇〇atm 以上的壓力；水夾套冷卻器4〇可隔絕反應器的高溫，防止 反應器的熱傳到廢液進料管路8〇，並將進料溫度控制在35〇 C以下，因此廢液進料不易於進料管路中沈殿結垢，進 料管路80亦不會產生阻塞的問題。 10 1230694 此外，在低熱值的廢液（即其燃燒反應熱低於 2,0斷al/g)中加人異丙醇，可以促進廢液的氧化效率。例 如，本發明之實驗結果顯示，在桿樣酸廢液或水進料中予 力口 2 wt%的異丙醇之後，可以將檸檬酸廢液之破壞去除= 5毕由74.5%提南至99.9%。 本系統使用相同濃度的廢液比較熱式（4〇〇£>c以上）與 冷式〇贼以下）進料，得知冷式進料可以延長系統的㈣ 時間，防止無機鹽類於進料管路中沉殿與結垢，而轨（4〇〇 °c =上）的進料方式約2〜3小時後無機鹽類即大量的沉澱， 10堵塞廢液的進料系統，使系統無法運轉操作。所以本系統 採用冷（350°c以下）的進料方式，可以延長系統的運轉操作 時間，並降低維修操作成本。 上述實施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自.應以申請專利範圍所述為準’而^僅限 15 於上述實施例。 【圖式簡單說明】 圖1係本發明之超臨界流體原理示意圖。 圖2係本發明之超臨界氧化糸統示意圖。 【圖號說明】 10 廢液儲存槽 20 空氣儲存槽 30 水儲槽 3 1 進料泵 32 進料泵 33 進料泵 40 冷卻器 50 反應器 60 冷凝器 1230694 70 氣液分離器 80 進料管路 81 進料管路 82 加熱器The main purpose of the present invention is to provide a supercritical oxidation system. The moon dagger = stop inorganic salts sinking and scaling in the feed line to avoid the feed line = stable operation of the entire oxidation system. At the same time raise the waste liquid. ‘Extend system operation time and reduce system operation cost. 'In order to achieve the above-mentioned objective, the supercritical oxidation system of the present invention is matched with —> Valley fluid 5 includes: — ^ _ device connected to the first inlet to pressurize the solution; a cooling medium Samples are used to reduce the temperature of the solution;-Wheels ",": a storage medium used for the supercritical oxidation system; two, a feed spring; and a feed spring 'are connected to the transport medium tank to add Repeatedly, the two heating shells are used to heat the conveying medium; a reactor, two the second feed pump to receive the solution and the wheel are connected to—I go / night, —condenser, The system is connected to the reactor, the solution after emulsification and cooling; and a gas-liquid separator, 20 1230694, is connected to the condenser to receive the cooled solution and separate it from gas and liquid. The transport medium used in the super-g-class oxidation system of the present invention may be a fluid commonly used in the super-critical world, and preferably water. Because the critical point of water is 374, 2205 Mm, and the solubility of inorganic salts decreases sharply near the critical point of water, in the present invention, the cooler of the critical oxidation system is preferably the solution that will enter the reactor: The temperature should be controlled below 350 ° C to prevent the precipitation and scaling of inorganic salts. In addition, the Q impulse state is preferably located near one side of the reactor to prevent heat from the reactor, a transport pipeline between the U medium tank and the reaction. The type of the cooler is not limited to 10, and may be any conventional cooler, preferably a water jacket cooler. The super g-class oxidation system of the present invention preferably further includes at least one air or oxygen storage plutonium to know the oxygen required for oxidation. The supercritical oxidation system of the present invention preferably further includes at least a pressure measuring element and at least a temperature measuring element to measure the pressure and temperature of the system. The solution processed by the supercritical oxidation system 15 of the present invention can be general industrial and civilian wastewater, environmental sludge, organic chloride, dioxin-containing fly ash, or refractory waste liquid such as high-energy substances, and preferably low-calorific value waste liquid. . The supercritical oxidation system of the present invention can preferably add an alcohol & substance to the low-calorific value waste liquid or the transport medium, and increase the reaction efficiency of the free radicals and improve the oxidation efficiency of the solution, preferably The solution and 20 are a low-calorific value waste liquid, and the concentration of the alcohol substance in the reactor is preferably less than 20 Wt%. More preferably, the alcohol is isopropyl alcohol. The reactor pressure of the supercritical oxidation system of the present invention is preferably higher than 3000 °, and the reactor temperature is preferably higher than 300t. 1230694 2 The waste liquid is mostly fed by hot feed. This creation is based on the "Eleventh Style" to increase cooling between the waste liquid inlet system and the reactor: a preheater is used to preheat the waste liquid. The material method is very different = the system increases the cooling cracking, which can mainly prevent the high two required by the reactor; and prevent inorganic salts in the waste liquid in the front of the reactor, and the scale and precipitation, to avoid pipelines Clogged. [Embodiment] First, the principle of the supercritical liquid of the present invention will be described. Please refer to FIG. 1. A 10-like pure substance includes gas, solid, and liquid three phases, which are coexisted in the gas-liquid coexistence day. Phase density, when the system temperature and pressure reach a certain point: its gas-liquid two-phase density tends to be the same, and the two phases merge into a homogeneous phase. This specific point is defined as the critical point of the aforementioned substance, and the corresponding temperature, pressure and density are defined as the critical temperature (Tc), critical pressure 15 (Pc), and critical density (Pc) of the pure substance, respectively. If this point is exceeded, no matter how the pressure increases, the white tear method will liquefy it, and the temperature will not return to the gas phase. We call this homogeneous phase south of the critical temperature and critical pressure a supercritical fluid. ) Water is the most important solvent in nature. Many compounds react with water. 20 It requires water to participate in the reaction or as a medium. It can change the various physical and chemical properties of water by using temperature or pressure control. In the supercritical state, water has dual properties like gas diffusion and liquid solubility, so it can be used for the extraction and separation of harmful substances. Supercritical Water Oxidation (SCWO) 25 treatment technology has high-efficiency oxidation reaction characteristics. Compared with the conventional I incineration treatment method, 1230694 has the advantages of short reaction time, high destruction efficiency, low energy loss and low air pollution. In addition, inorganic salts are easily precipitated, separated, and recovered under SCWO reaction conditions, so advanced countries have actively invested in research and development. The critical temperature of water is 374 C and the critical pressure is 220 atm. It can be completely miscible with non-polar fluids in a supercritical state, and the dissociated ions also have high mobility and high electrical conductivity. General supercritical fluids have the following characteristics: 1 · Density and diffusion coefficient similar to liquids. 2. Viscosity similar to gas. 3 · Extremely high response speed. 10 4. Extremely low surface tension. The supercritical oxidation method is similar to the wet oxidation method (wet 〇xidati〇n). The general wet oxidation method is liable to cause incomplete oxidation due to insufficient dissolved oxygen in water, and its tail gas is troubled by volatile organic compounds (V0C) emissions, so it is usually Devices such as activated carbon or catalyst must be installed to ensure that the exhaust gas can meet environmental protection standards. In addition to this, because the oxidation is carried out in two phases, the oxidation rate is slow, and the reactor volume is large, such as lifting the waste water to a supercritical state (the general system conditions are about, 24-35 MPa ^ 400 ~ 650 ° 〇 > ^ ^^ ^ ^ ^ ^ ^^ #J ^ 3 is homogeneous, so the oxidizing power is increased, and the pollutants are quickly destroyed; when the temperature is above 525 ° C, the destruction rate can reach 99.99%. Compared with the general wet oxidation method, SCW0 can treat high-concentration and wastewater containing organic species, which not only has high destruction efficiency but also can reduce the amount of oxygen and nitrogen oxides (NOx). Or two systems 3 = Product formation, and it is a closed operation. When the system is unstable, it can be reflowed and reprocessed. The low-level protection can be 1230694. The horizontal oxidation can be used to degrade hazardous waste, which is mainly used in six major types of hazardous waste. Handling of materials: ~ 1. Plastic extraction and additives: containing self-plastic plastic 'fire talk inhibitors, plasticizers, etc. 2. Rich money, pesticides, medicines, solvents, dyes. High explosives, pyrotechnics, gas propellants. 4 · Wastewater · Wastewater from textile or pulp mills, Bleaching waste water, cutting waste liquid, leather waste liquid. 5. Sewage sludge: urban sewage sludge, industrial sludge. 106 · Fork Qiao " Dyeing soil: mineral oil, halogen-containing organic matter. To this end " Xiangbei Fancha members can better understand the technical content of the present invention, and the specific and practical implementation of the special supercritical oxidation system is as follows. Please refer to FIG. 2. FIG. 2 is a schematic diagram of the supercritical oxidation system of the present invention, which is mainly composed of a waste liquid storage tank. 10. Air storage tank 20, water storage tank 30, high-pressure feed 15 feed pump 31, 32, 33, water jacketed cooler 40, heater 82, supercritical oxidation reactor 50, condenser 60, gas-liquid separator 70 and several temperature detection elements and pressure detection elements. Air feed is compressed by the feed pump 32 to a pressure that can enter the reactor 50, and then enter the reactor 50; transport medium (this embodiment is Water) is pressurized by the feed pump 33, the heater 82 is heated to a pressure and temperature that can enter the reactor 20; the waste liquid is fed by the feed pump 31 to a pressure of more than 2000atm; the water jacket The cooler 40 can isolate the high temperature of the reactor and prevent the heat of the reactor from being transferred to the waste liquid feed The temperature of the feed pipe is 80, and the feed temperature is controlled below 35 ° C. Therefore, the waste liquid feed is not easy to foul in the feed pipe, and the feed pipe 80 will not cause blockage. 10 1230694 In addition, Adding isopropyl alcohol to waste liquid with low heating value (that is, its combustion reaction heat is lower than 2,0 cut al / g) can promote the oxidation efficiency of waste liquid. For example, the experimental results of the present invention show that After giving 2 wt% isopropanol in the liquid or water feed, the destruction of the citric acid waste liquid can be removed = 5 times from 74.5% to 99.9%. This system uses the same concentration of waste liquid to compare the thermal type (Above £ 400 and above) and cold type below 0) feeding, it is learned that cold feeding can extend the system's ㈣ time, prevent inorganic salts from sinking and scaling in the feeding pipeline, and The feeding method of the rail (400 ° c = up) is about 2 to 3 hours after which inorganic salts are precipitated in large quantities. 10 The waste liquid feed system is blocked, making the system inoperable. Therefore, this system adopts cold (less than 350 ° C) feeding method, which can prolong the operation time of the system and reduce the maintenance operation cost. The above embodiments are merely examples for the convenience of description. The scope of the rights claimed in the present invention is based on the scope of the patent application 'and is limited to the above embodiments. [Schematic description] Fig. 1 is a schematic diagram of the supercritical fluid of the present invention. FIG. 2 is a schematic diagram of a supercritical oxidation system of the present invention. [Illustration of drawing number] 10 Waste liquid storage tank 20 Air storage tank 30 Water storage tank 3 1 Feed pump 32 Feed pump 33 Feed pump 40 Cooler 50 Reactor 60 Condenser 1230694 70 Gas-liquid separator 80 Feed pipe Path 81 Inlet line 82 Heater
1212