第28卷第1期化學反應(yīng)工程與工藝Vol 28, No 12012年02月Chemical Reaction Engineering and TechnologyFeb.2012100L761(20124液哨超聲在循環(huán)水殺菌的應(yīng)用張陳成,呂效平,韓萍芳(南京工業(yè)大學化學化工學院,超聲化學工程研究所,江蘇南京210009:研究了一種新型液哨式超聲發(fā)生器,以循環(huán)水作為動力源,進行循環(huán)水的殺菌處理,同時探討了簧片哨結(jié)構(gòu)循環(huán)水水壓以及溫度對殺菌效果的影響,簧片響較好結(jié)構(gòu)為簧片厚度(mmx簧片長度(mm)x噴距(mm)04×12×2,聲強325Wm2,入口壓力07MP,流量24mh,水溫25℃,經(jīng)過60min的處理,殺菌率最高84%·該系統(tǒng)有結(jié)構(gòu)簡單、堅固耐用、處理量大、耗能小等優(yōu)點,具有工業(yè)化大規(guī)模的水處理的應(yīng)用前景關(guān)調(diào):超聲殺中圖分類號:TQ54文識碼:A在工業(yè)循環(huán)水系統(tǒng)中,由于水的不斷蒸發(fā)濃縮、物料泄露和適宜的水溫,造成了細菌的大量繁殖,而生物黏泥在設(shè)備上的附著會嚴重影響設(shè)備運行效率,增加了設(shè)備能耗。目前國內(nèi)通用的微生物控制方法主要是投加工業(yè)殺菌劑,這對人類和環(huán)境水生物都有不同程度的毒性,因此環(huán)境友好型的殺菌方法成為目前研究的熱點超聲殺菌是一種新型水處理技術(shù),根據(jù)超聲發(fā)生源的不同,目前主要有電功率超聲和機械式超聲田張帆等初步研究了電功率超聲處理循環(huán)冷卻水,通過實驗驗證了利用超聲殺菌有較好的滅菌效果。本研究主要探討機械式超聲滅菌方法,由于機械式超聲發(fā)生器結(jié)構(gòu)簡單、堅固耐用、處理量大、利用流程中的工業(yè)水泵提供超聲能量、耗能小和設(shè)備成本低等優(yōu)點隊,適合工業(yè)上大規(guī)模運用作為超聲殺菌的方法。1液哨結(jié)構(gòu)液哨超聲發(fā)生器,又稱簧片哨。液哨主要由噴嘴、噴距調(diào)節(jié)管和簧片組成,剖面結(jié)構(gòu)圖見圖1·該發(fā)生器是通過噴嘴的高壓水流沖擊簧片,使得簧片產(chǎn)生振動,產(chǎn)生超聲波噴面圖、嗩嘴簧片噴距調(diào)節(jié)管簧片槽固定螂栓8mm水流m圖1液哨剖面圖Fig 1 Section View of Reed whist收痛日2011-1209修訂日舞:201201-19作者筒介張陳成(1985),男,硫士研究生:呂效平(190),男,教授,博士生導(dǎo)師,通訊聯(lián)系人. E-maiLxpla@cd第28卷第1期張陳成等液哨超聲在循環(huán)水殺函的應(yīng)用2液哨殺菌機理當超聲波能量足夠大時,就會產(chǎn)生“超聲空化”現(xiàn)象,主要是液體中的微小氣核在超聲波的作用下被激活,表現(xiàn)在泡核的振蕩、生長、收縮、崩潰等一系列動力學過程刀。液體中的微小氣泡在超聲的作用下振動、生長并不斷聚集聲場能量,當能量達到某個值時,空化氣泡急劇崩潰閉合,這時會釋放出巨大的能量,并產(chǎn)生高速強勁的微射流,使碰撞密度極高?？栈瘹馀菰诩眲”罎⒌乃查g產(chǎn)生局部高溫高壓(5000K,1800MPa)。這些超聲波所攜帶的能量足以打開結(jié)合強勁的化學鍵啊另外由于液哨中水流速度極快,也會產(chǎn)生“水力空化”現(xiàn)象0,即水流內(nèi)部形成空穴、空洞或空腔當液體快速流動時,氣泡就會不斷的產(chǎn)生和潰滅,從而釋放能量,產(chǎn)生局部高溫高壓?？栈F(xiàn)象所產(chǎn)生的能量,可以對微生物細胞物質(zhì)產(chǎn)生損傷,破壞其細胞質(zhì)膜,從而導(dǎo)致細胞死亡1,因而也就能達到殺菌的效果。3實驗部分3.1實驗條件氯化鈉(NaCl):分析純,西隴化工股份有限公司;營養(yǎng)肉湯:國藥集團化學試劑有限公司;污水取自城市河流:精密電子天平:天津市天馬儀器廠:液哨超聲發(fā)生器:自制;高壓滅菌鍋:浙江新豐醫(yī)療器械有限公司;水聽器:型號CS3,中科院聲學研究所;示波器:江蘇揚中電子儀器廠,型號SR8;菌落總數(shù)測試片:廣州綠洲生化科技有限公司。驗使用自制的由液哨式超聲發(fā)生器組成的循環(huán)冷卻水殺菌系統(tǒng),見圖2。其中簧片的主要幾何尺寸見表2,材料均為不銹鋼。測定表明,該液哨超聲發(fā)生器的入口水壓為08MPa時,其流量最高為28m3h,殺菌實驗在盛有100L污水的水槽中進行。壓力長片明B區(qū)流量計泵循球冷卻水圖2循環(huán)冷卻水殺蔭系統(tǒng)Fig 2 Cooling water disinfection system化學反應(yīng)工程與工藝2012年02月裹2簧片的結(jié)構(gòu)參數(shù)Table Smctural parameters of Reed whistleLength/mmReed width/mm22222024ooomooo032液哨性能參數(shù)測定選取表2中的各種簧片,通過調(diào)節(jié)閥門改變出水口處的壓力,將CS-3水聽器直接放入液哨附近,另一端與示波器相連,讀取各個壓力下的振幅,利用下面公式求出聲強:e/刎)式中:z為聲強,Wm2;e為示波器顯示電壓幅值,V;m為換算系數(shù),31.6,與探頭本身的物理性有關(guān):四為媒質(zhì)的密度,kg/m3;c為媒質(zhì)中的聲速,m/s33殺菌實驗取一定量在一定條件下培養(yǎng)好的細菌倒入水槽中,加生理鹽水稀釋,水溫為26℃,調(diào)節(jié)液哨的性能參數(shù)1聞,根據(jù)性能測試的結(jié)果,使其達到最佳狀態(tài),開啟水泵,調(diào)節(jié)閥門,使其水壓維持在07MPa,運行60min。實驗前后每10min取一次水樣測其菌落總數(shù)。通過菌落總數(shù)測試片測試實驗前后污水的細菌總數(shù),殺菌率計數(shù)方法按下式w-wx100%M式中:形殺菌率:M,處理前菌落總數(shù):M,處理后菌落總數(shù)4結(jié)果與討論41簧片結(jié)構(gòu)優(yōu)化4.1入口水壓、簧片厚度與聲強的關(guān)系對表2中9組簧片進行逐測試,得出入口水壓、簧片厚度對聲強的影響,見圖3(圖中結(jié)構(gòu)參數(shù)表示為簧片厚度(mm)x簧片長度(m)x噴距(mm))。取液哨簧片長度為12mm,噴距為4mm,改變?nèi)肟趬毫?考察簧片厚度對液哨聲強的影響實驗過程中,當入口水壓為0IMPa和02MPa時,未聽見明顯的哨聲。這是因為入口壓力較小時水流沖擊簧片的力度很小,簧片的振動很弱,幾乎沒有明顯的線狀譜。從04MPa開始,開始有一種較為尖銳的聲音。從實驗數(shù)據(jù)可以看出,隨著水壓的增大,聲強逐漸變強,并在07MPa時達到最大。同時可以看出,資片厚度為04mm和0.5mm時,所得的聲強是比較大的,可以看出簧片的厚度會影響簧片的振動快慢和振幅大小。4.1.2入口水壓、簧片長度與聲強的關(guān)系保持液哨簧片厚度以及噴距不變,改變液哨入口壓力,考察簧片長度對液哨液哨聲強的影響從圖4實驗數(shù)據(jù)可以看出,簧片長度為12mm時,所得到的聲強是比較大的,約23Wm2左右?？梢姴⒉灰欢ㄊ情L度越長或越短,產(chǎn)生的聲強越大,而是存在一個最佳點。第28卷第1期張陳成等.液哨超聲在循環(huán)水殺菌的應(yīng)用04nmx 12mmx4 mmsmmx16mmx4t58有28品0.00.10203d.406070809Hydraulic pressure/MPa圖3簧片厚度對聲強的影響圖4簧片長度對產(chǎn)強的影響Fig 3 Relationship between thickness and sound intensityFig 4 Relationship between length and sound intensity4.3入口水壓、噴距與聲強的關(guān)系保持液哨簧片厚度和長度不變,逐步增加入口壓力,考察噴距不同時對液哨聲強的影響。從實驗數(shù)據(jù)可以看出,隨若確距改變得到的聲強數(shù)據(jù)明顯變化,所以噴距對空化強度有一定的影量響。并且簧片到噴口之間距離達到2mm時,所得的05聲強數(shù)據(jù)是最大的。這主要是因為簧片越靠近噴口04050607Ds09時,水流沖擊簧片的力度就越大,簧片的振幅也就越draulic pressure /MPa大,振動速度也越快。由圖5結(jié)果可知簧片結(jié)構(gòu)參數(shù)圖5簧片到噴口的距離對聲強的影響為04mm×12mm×2mm時聲強最大。Fig 5 Relationship between distance and sound intensity42殺菌實驗結(jié)果與討論421處理時間對殺菌效果的影響根據(jù)液哨最佳結(jié)構(gòu)參數(shù)優(yōu)化的結(jié)果,選取兩種簧片,一種性能最好的簧片04mmx12mmx2mm,另外一種性能次好的簧片尺寸為05mmx12mmx2mm,進行循環(huán)水殺菌實驗,其中被處理的污水量為80L此時入口流量24mh、水壓07MPa,。實驗結(jié)果如圖6。從圖6中可以看出,液哨對循環(huán)冷卻水滅菌是有效的,滅菌率分別達到了70%和84%可以看出結(jié)構(gòu)參數(shù)最優(yōu)的液哨對循環(huán)水起到較好的滅菌效果。圖6處理時間對殺菌效果的能響圖7處理溫度對殺菌效果的蟛響Fig. 6 The effect of processing time on sterilization rate Fig. 7 The ettect of processing temperature on sterilization rate4.22溫度對滅菌效果的影響考察溫度對滅菌效果的影響設(shè)置15、2025以及30℃四種溫度選取結(jié)構(gòu)參數(shù)為04mmx12mm×2mm化學反應(yīng)工程與工藝2012年02月的簧片,其中被處理的污水量為80L。考察不同溫度條件下的滅菌效果,結(jié)果見圖7。圖中結(jié)果表明,溫度升高對細菌的滅菌效果都有明顯的提高實驗數(shù)據(jù)表明,溫度越高,滅菌率越高。當溫度分別為15、20、25和30℃時,90min內(nèi),滅菌率分別為7%%、82%、85%和83%這主要是由于溫度升高將使液體的表面張力系數(shù)和粘滯系數(shù)下降,從而導(dǎo)致空化域值下降,使空化易于發(fā)生,但是并不是溫度越高越好,這是因為溫度升高,蒸汽壓將增大,使空化強度減弱。5結(jié)論a)根據(jù)液哨性能測試實驗的結(jié)果,液哨本身尺寸簧片長度(mm)×簣片厚度(mm)x噴距(mm)為12mm×04mm×2mm時,所得到的聲強是最高的,為325Wcm2。此時入口壓力07MPa,流量24m3hb)循環(huán)水最佳水溫為25℃,選取兩組簧片,其中一組簧片經(jīng)過性能測試,效果是最好的。殺菌處理60min,殺菌率分別是70%和84%參考文獻:[應(yīng)崇福超聲學M北京科學出版社,1990495506團2]張帆呂效平韓萍芳,等超聲用于循環(huán)冷卻水火菌化工進展20113071431-1434Zhang Fan, Lu Xiaoping, Han Pingfang, et al. 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Study on catalyzing germicidal efficacy of ultrasound and nanomete titanium dioxide[]).Chinesel王振瀲李敏常用滅菌方法與TO2光催化滅菌機理的研究團周口師范學院學報200.20592%ang Zhenling. Li Min. Progress in study of bactericidal methods and TiO photocatalysis killing [] Joumal of Zhoukou Teachers College,203、205)9294[17 Dadjour M F, Ogino C, Matsumura S. et al. Kinetics of disinfection of escherichiacoli by catalytic ultrasonic irradiation with Tio U.Biochemical Engineering Jouma, 2005, 25(3):243-248下轉(zhuǎn)86頁化學反應(yīng)工程與工藝2012年02月le xiaojing. Huang Xianliang, Wang Zhengbao. Characterization of acidic properties of AgNaZSM-5 catalyst [] Chemical ReactionEngineering and Technology, 2010, 26(4): 361-365,370I9陸銘,孫洪敏,郭螨等ZSMS沸石催化劑的失活歷程和活性穩(wěn)定性團石油學(石油加工2001,17(4)5963Lu Ming. Sun Hongmin, Guo Yu, et al. Study on deactivation process and actiwutu stability of ZSM-5 zeolite []. Acta Petroleiica(Petroleum Processing Section), 2001, 17(4): 59-631毛東淼,郭強勝,孟濤,等,水熱處理村納米H2SM5分子酸性及催化醇制丙烯反應(yīng)性能的影響物埤化學學報.2010,26(2)38344Mao Dongsen, Guo Qiangsheng Meng Tao, et al. Effect of hydrothermal treatment on the acidity and catalytic performance of nanosizedHZSM-5 zeolites for the conversion of methanol to propene [] Acta Phys. Chim. Sin, 2010, 26(21: 338-344Effects of the Impurities in LPG on H-ZSM-5 Catalyst for MTP ProcessGao Xiujuan, Chen Aiping Tong Shan, Li Debing, Chen Yuanying, Sun Xuguang, Mei Changsong'( 1. Datang Inner Mongolia Duolun Coal Chemical Co. Ltd. Inner Mongolia 027300, China; 2. Datang Intemational ChemicalTechnology Research Institute Co, Ltd, Beijing 100070, China)Abstract: The homemade LPG contains trace amounts of impurities. Apparently, due to the contents of theimpurities much higher than those of the impurities restricted by the Lurgi MTP(methanol to propylenetechnology, the LPG can not be used as the substitute for the cycling hydrocarbons without any expinvestigation. In this paper, the effects of the impurities in LPG on the structure and performance of H-ZSM-5catalyst for mTP process were investigated. The results of the performance test of H-ZSM-5 catalyst showed thatthe mTP catalyst exhibited a high activity, anti-coking capability, and regeneration property under the condition ofco-feeding with methanol and LPG ICP measurements showed that the deposition of impurities did not occur onthe catalysts. XRD tests suggested that the framework structure of the catalyst maintained well after repeatedreaction or regeneration NH,tpD characterizations showed that the amount of weak acid sites of the catalyst didnot change after reaction or regeneration. Therefore the homemade LPG can be verified as the substitute for thecycling hydrocarbon of MTP process.Key words: Lurgi MTP process; H-ZSM-5 catalyst; LPG impurity; regeneration接74頁Application of Liquid Whistle Ultrasonic Generatorfor Circulation Water SterilizationZhang Chencheng, Lu Xiaoping, Han PingfangNanjing University of Technology College of Chemistry and Chemical Engineering, Institute of Sonochemical Engineering.Nanjing 210009, China)Abstract: A new liquid whistle ultrasonic generator is studied. The sterilization experiments have been carried outwith this liquid whistle device, which use high-speed circulation water as a power source. We studied the effectsof different parameters, such as structure of reed whistle and the pressure of the circulating water, on sterilizationrate. The preferable structure of the reed whistle is 0.4 mmx12 mmx2 mm. The reed whistle operating conditionsshow as follows: 3.25 W/cm2sound intensity, 0.7 MPa water inlet pressure, 25 t water temperature and 2.4m/h water flow-rate for 60 min. Under these conditions, the sterilization rate reached up to 84%. The generatorhas various advantages such as simple structure, fine sturdiness, durability and large handing capacity as well aslow power consuming. Moreover, it is suitable for industrial applications.Key words: liquid whistle; ultrasound; sterilization