第43卷第5期化學(xué)工程Vol. 43 No. 52015年5月CHEMICAL ENGINEERING( CHINA)May 2015水焦?jié){添加劑最佳用量的實(shí)驗(yàn)研究高夫燕'，蔣林’，張秀珍'(1.浙江大學(xué)寧波理工學(xué)院，浙江寧波315100; 2.寧波富爾頓熱能設(shè)備有限公司，浙江寧波315020)摘要:為了優(yōu)化石油焦的成漿效果并確定水焦?jié){添加劑的最佳用量,實(shí)驗(yàn)研究了某石油焦在分別加人3種不同類型添加劑后的成漿特性,考察了添加劑用量對(duì)水焦?jié){成漿性、流變性和穩(wěn)定性的影響。結(jié)果表明:當(dāng)添加劑用量為石油焦干基質(zhì)量的0. 8%時(shí),3種添加劑下石油焦均能獲得較好的成漿性;NSM(亞甲基蔡磺酸鈉苯乙烯磺酸鈉馬來酸鈉)和NC(亞甲基萘磺酸鹽甲醛縮合物)添加劑使水焦?jié){呈脹流性,而LS(木質(zhì)素磺酸鹽)添加劑使水焦?jié){呈假塑性,添加劑用量的多少對(duì)水焦?jié){流變性的影響不大;當(dāng)添加劑用量為石油焦干基質(zhì)量的0. 6% - -0.8%之間時(shí)，水焦?jié){具有相對(duì)較好的穩(wěn)定性。因此,添加劑用量為石油焦干基質(zhì)量的0. 8%時(shí),水焦?jié){的綜合成漿品質(zhì)最優(yōu)。關(guān)鍵詞:石油焦;水焦?jié){;添加劑用量;成漿性;流變性;穩(wěn)定性中圖分類號(hào):TQ 517.4文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):1005-9954(2015 )05-0063.05DOI:10. 3969/j issn. 1005 954.2015. 05. 014Experimental research of optimum additive dosage forpetroleum coke water slurryGAO Fu-yan' ,JIANG Lin2 , ZHANG Xiu-zhen2(1. Ningbo Institute of Technology ,Zhejiang University , Ningbo 315100 , Zhejiang Province, China;2. Ningbo Fulton Thermal Energy Equipment Co, Ltd. , Ningbo 315020 ,Zhejiang Province, China)Abstract :The slurryability of a petroleum coke was studied after adding three different additives for the sake ofslurry efct and optimum additive dosage. The efects of additive dosage on the slurryability, rheologicalcharacteristics and stability of petroleum coke water slurry ( PCWS) were investigated. The petroleum coke canachieve better slurryability with all three additives , when the additive dosage is 0. 8% ( mass fraction) of the air-dried pulverized petroleum coke. The PCWS performs dilatant fluid characteristic with NSM and NC, however ,pseudoplastic fluid characteristic with LS additive. The additive dosage has a lttle effect on the rheologicalcharacteristics of PCWS. The PCWS has better stability when the additive dosage is 0. 6% 0.8% ( mass fraction)of the air-dried pulverized petroleum coke. Therefore , the optimum additive dosage for PCWS can be intended to be0.8% ( mass fraction) of the air-dried pulverized petroleum coke , which can optimize the quality of PCWS.Key words: petroleum coke ;PCWS ;additive dosage ;slurryability ;rheological characteristics ;stability石油焦是石油加工的副產(chǎn)品,原油通過蒸餾作焦的清潔高效利用開辟了新途徑[)。用將輕重質(zhì)油分離,重質(zhì)油再經(jīng)過熱裂過程后剩余在水焦?jié){制備過程中,添加劑是必需的助劑,的固體殘?jiān)礊槭徒?3]。近年來,我國(guó)的石油水焦?jié){添加劑實(shí)質(zhì)上是一種表面活性劑，它可以改焦產(chǎn)量逐年增加,如何從技術(shù)和經(jīng)濟(jì)兩方面使石油變石油焦顆粒的表面特性,使焦粒能夠在水中分焦得到合理利用,成為企業(yè)和社會(huì)追求的目標(biāo)。以散,并使?jié){體具有良好的流動(dòng)性和穩(wěn)定性”9]。添石油焦為主要原料,配以水和添加劑制成水焦加劑不僅直接決定著水焦?jié){的質(zhì)量,還影響著水焦?jié){[4],水焦?jié){是-種新型清潔高效的液體代油燃漿的成本,其費(fèi)用是制漿成本的第二大因素[0]。因料,既可以緩解我國(guó)的石油需求壓力[5),又為石油此,在水焦?jié){制備過程中,除了要努力提高漿濃度收稿日期: 2014-09-15基金項(xiàng)目:寧波市自然科學(xué)基金資助項(xiàng)目(2012A610165 )中國(guó)煤化工作者簡(jiǎn)介:高夫燕( 1980- -),女 ,講師,博士,從事液體燃料研究, E-mail:gaofuyan@ nit..MYHCNMH G.高夫燕等水焦?jié){ 添加劑最佳用量的實(shí)驗(yàn)研究●65●1 750r添加劑用量/%。150000.471.0金150000.6 41.200.8直1250士LS& 1200008000s 1000花900一75087888余余500 -20406080100)61.2剪切速率/s"添加劑用量%圖5加入LS添加劑的流變特性圍2水焦?jié){的表觀貼度與添加劑用 之間的關(guān)系Fig.5 Rheological charateristics of PCWS added LS additiveig.2 Infuence of additive dosage on viscosity of PCWS2.2水焦?jié){的流變性從圖中可知,NSM和NC添加劑都使水焦?jié){剪流變性直接影響漿體的儲(chǔ)存、運(yùn)輸和霧切變黏,而LS添加劑則使水焦?jié){剪切變稀,并且這化1617]1 ,是水焦?jié){的重要質(zhì)量指標(biāo)之一。工程上,種流變特征隨添加劑用量的不同不會(huì)發(fā)生本質(zhì)改一般期望水焦?jié){具有剪切變稀的假塑性流變特征。變;剪切速率越大,水焦?jié){黏度變化趨勢(shì)越平緩。假塑性漿體在靜置存放時(shí)具有較高的黏度,有利于這是因?yàn)殡S剪切速率的加快,漿體分子和顆粒的排顆粒的穩(wěn)定懸浮,便于漿體的儲(chǔ)存;流動(dòng)時(shí),黏度又列有序化，漿體趨向牛頓流體轉(zhuǎn)型,牛頓流體的黏會(huì)隨流速的升高而降低，便于漿體的運(yùn)輸。度隨剪切速率基本不變。加入不同添加劑時(shí)水焦?jié){的流變特性曲線分添加劑類型主要影響焦粒表面改性的結(jié)構(gòu),從別如圖3- -5 所示。而導(dǎo)致水焦?jié){呈現(xiàn)不同的流變性;而添加劑用量主要影響焦粒表面改性的程度,一般對(duì)水焦?jié){流變性的影響不大。NSM和NC添加劑與石油焦顆粒具有二1500.Dσσ很強(qiáng)的吸附作用,漿體體系中含有的自由水少,易三1200-形成脹流性流體。LS添加劑是一種天然的芳香族高分子化合物，具有三維空間結(jié)構(gòu),對(duì)顆粒的分散00.4 01.0作用依靠陰離子基團(tuán)的靜電斥力,因其自身體積較0.6 41.200.大,對(duì)石油焦顆粒分散作用良好,易形成假塑性流20 4060 80 To0體,并且當(dāng)添加量為0.8%時(shí),水焦?jié){剪切變稀的假的切速度/s~塑性特征最為顯著。圉3加入NSM添加劑的流變特性2.3水焦?jié){的穩(wěn)定性Fig.3 Rheological characteristics of PCWS added NSM aditive采用落棒法和倒置法測(cè)定的結(jié)果分別如圖6和7所示。由圖6可知,使用NSM添加劑時(shí),在添加1200 r量為0.6% - -0. 8%之間時(shí),水焦?jié){產(chǎn)生的硬沉淀明金1000顯偏少,其穩(wěn)定性相對(duì)較好;使用NC添加劑時(shí),水.告800-焦?jié){的穩(wěn)定性隨著添加劑用量的增加而下降,并且當(dāng)添加劑用量超過0.8%時(shí)穩(wěn)定性開始迅速惡化;. 600彤400-。0.4口1.0使用LS添加劑時(shí),無論添加劑用量多少,水焦?jié){在°06 11.2成漿7 d后都只產(chǎn)生少量硬沉淀,表現(xiàn)出良好的穩(wěn)200定性。由圖7可見,使用NSM添加劑時(shí),在添加量為圈4加入NC添加劑的流變特性0.8%時(shí),水V”中國(guó)煤化工 穩(wěn)定性最好;使Fig.4 Rheological characerisics of PCWS added NC aditive用NC添加fHCNMH G增加,倒置殘留++投稿平臺(tái) Htp://imiyi. cbp. cnki.net ++高夫燕等水焦?jié){ 添加劑最佳用量的實(shí)驗(yàn)研究●67[3]鄧雨生.410/h循環(huán)流化床鍋爐混燒石油焦油頁(yè)巖熱[11] 高夫燕,劉建忠,王傳成,等.石油焦的成漿性及水焦力性能試驗(yàn)分析[J].動(dòng)力工程學(xué)報(bào),2011,31(6):漿的流變性和穩(wěn)定性[J].化工學(xué)報(bào), 2010,61(11):410415.2912--2918.[4]鄒建輝,楊麗波,龔凱峰,等.石油焦成漿性能的研究[12]李朋偉,楊東杰,樓宏銘,等.利用分散穩(wěn)定性分析儀[J].化學(xué)工程,2008 ,36(3) :22-25.研究水煤漿的穩(wěn)定性[J].燃料化學(xué)學(xué)報(bào), 2008,36[5] 李霞.中國(guó)石油對(duì)外依存度研究[J]經(jīng)濟(jì)研究導(dǎo)刊，(5) :524-529.2011(31):171-172.[13]全國(guó)煤炭標(biāo)準(zhǔn)化技術(shù)委員會(huì). GB/T 18856.5- -2008 水[6]高夫燕. 基于石油焦的漿體燃料制備及特性研究[ D].煤漿試驗(yàn)方法第5部分:穩(wěn)定性測(cè)定[S].北京:中國(guó)杭州:浙江大學(xué),2013.標(biāo)準(zhǔn)出版社,2008:1-5.[7]鄒立壯 ,朱書全,王曉玲,等.不同水煤漿分散劑與煤[14]鄒立壯,朱書全,支獻(xiàn)華,等.不同水煤漿添加劑與煤之間的相互作用規(guī)律研究( XI) :分散劑改性煤粒的界之間的相互作用規(guī)律研究( IV ) :分散劑用量對(duì)水煤漿面性質(zhì)及其對(duì)CWS性質(zhì)的影響[J].燃料化學(xué)學(xué)報(bào),流變特性的影響[J].中國(guó)礦業(yè)大學(xué)學(xué)報(bào), 2004,332006 ,34(2):160-165. .(4) :370-374.[8]鄒立壯,朱書全.不同水煤漿添加劑與煤之間的相互[15]胡維斌,韓敏芳,何國(guó)鋒,等.水焦?jié){流變特性的影響作用規(guī)律( I):復(fù)合煤顆粒間的相互作用對(duì)CWM表因素研究[J].潔凈煤技術(shù),2008 ,14(6) :29-31.觀黏度的影響[J].化工學(xué)報(bào),2004 ,55(5) :775-782.[16] MISHRA s K, SENAPATIP K, PANDA D. Rheological[9QIU Xueqing, ZHOU Mingsong, YANG Dongie, et al.behavior of coal-water slurry [J]. Energy Sources, 2002 ,Evaluation of sulphonated acetone-formaldehyde ( SAF )24(2): 159-167.used in coal water sluries prepared from diferent coals [17] CHENG Jun, ZHOU Junhu, LI Yanchang, et al. Effects[J]. Fuel, 2007, 86( 10/11): 1439-1445.of pore fractal stuctures of ulrafine coal water sluries on10]劉曉霞,屈睿,黃文紅,等.水煤漿添加劑的研究進(jìn)展rheological behaviors and combustion dynamics [J]. Fu-[J].應(yīng)用化工，2008, 37(1): 101-103.el, 2008, 87(12): 2620-2627.l上接第52頁(yè)][1]王凱，虞軍,戴季煌,等.化工設(shè)備設(shè)計(jì)全書一 攪[10] ZHANG Zhenzhen, QIAN Zhi, XU Lianbin, et al. Devi-拌設(shè)備[M].北京:化學(xué)工業(yè)出版社, 2003.ation of carbon dioxide-water gas-liquid balance from ther-[12] CALLETTI C, PACLIANTI A, LEE K C, et al. Rey-modynamic equilibrium in turbulenceI: experiment ancnolds number and impeller diameter effects on instabilitiescorrelation [J]. Chinese Journal of Chemical Engineer-in sirred vessels [J]. AIChE Journal, 2004, 50(9):ing, 2013, 21(7): 770-775.2050 2063.[.上接第62頁(yè)][19] AHLERSJ A, CRASSER J A, LOVELESS B T, et al.Catal A: Gen, 2009, 362(1/2)169-177.Room-temperature oxidation of reduced Cu/ZnO surfaces[22] WANCSG, LIAO X Y, CAO D B, et al. Factors con-by lttice oxygen difusion [J]. Catal Lett, 2007, 114tolling the interaction of CO2 with transition metal sur(3/4) :185-191.faces [J].」Phys Chem C, 2007， 111 (45):[20] JONESP M, MAYJ A, RETZJB, et al. Photoelectron16934-16940.spectroscopic and electronic structure studies of CH20YANG Y X, WHTE M C, LIU P. Theoretical study ofbonding and reactivity on ZnO surfaces: steps in the meth-methanol synthesis from CO2 hydrogenation on metal-anol synthesis reaction [J]. Inorg Chem, 2004, 43(11):doped Cu(111) surfaces [J]. J Phys Chem C, 2012,3349-3370.116(1) :248-256.21] VIINIKAINENA T, RONKKONENA H, BRADSHAWB[24] GRABOW L C, MAVRIKAKIS M. Mechanism of metha-H, et al. Acidic and basic surface sites of zirconia basednol synthesis on Cu through CO2 and CO hydrogenationbiomass gasification gas clean-up catalysts [J]. Appl[J]. ACS Catal. 201. 1(4) :365-384.中國(guó)煤化工HY HCNMHG投稿平臺(tái)Http://imiy. cbpt. cenki. net.