第32卷第5期燃料化學(xué)學(xué)報(bào)JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGYOct文章編號:0253-24092004)5-062705萘油制備新型水煤漿添加劑的研究郭照冰,鄭正1,吳國光2,鄭壽榮1.南京大學(xué)環(huán)境學(xué)院,污染控制與資源化國家重點(diǎn)實(shí)驗(yàn)室,江蘇南京210093;2.中國礦業(yè)大學(xué)化工學(xué)院,江蘇徐州221008)摘要:研究了如何利用萘油中的有效成分合成出性能良好的水煤漿添加劑。通過合理的正交試驗(yàn)設(shè)計(jì)和多元線性回歸分析方法得到了合成萘油添加劑的較佳工藝條件即在75g的禁油中加入濃H2SO430mL在160℃時(shí)磺化2h加λHCHo25mL在105℃時(shí)縮合1.5h利用實(shí)驗(yàn)合成的萘油添加劑與純萘磺酸甲醛縮合物作添加劑分別對龐莊煤進(jìn)行制漿實(shí)驗(yàn)。結(jié)果表明萘油添加劑性能良好可顯著降低萘油添加劑的成本。應(yīng)用傅立葉變換紅外光譜對萘油添加劑的結(jié)構(gòu)進(jìn)行了分析測出萘油添加劑主要為含有-CH2-,-SO等基團(tuán)的芳香族化合物。對萘油添加劑改善水煤漿性能的作用機(jī)理進(jìn)行了初步探討。關(guān)鍵詞:萘油;水煤漿添加劑;性能中圖分類號:TQ530文獻(xiàn)標(biāo)識(shí)碼:A水煤漿添加劑的作用是改變煤粒表面性能使制1.3添加劑的制備影響制備添加劑的因素很多得的水煤漿具有高濃度、低粘度和良好的穩(wěn)定本文主要考察A磺化劑用量;磺化時(shí)間;縮合性4]。目前國內(nèi)使用的添加劑大多是純的有機(jī)物劑用量;D:縮合時(shí)間四個(gè)因子對合成添加劑的影〔萘磺酸甲醛縮合物、聚丙烯酸類等)價(jià)格昂貴。因響通過正交實(shí)驗(yàn)法確定該工藝的制備方案表1)此選擇原料來源廣泛、高效、成本低且普適性強(qiáng)的表1正交實(shí)驗(yàn)因素水平表水煤漿添加劑解決添加劑的價(jià)格和性能之間的矛Table 1 Level of factor in orthogonal desig盾已成為當(dāng)今水煤漿研究的重點(diǎn)H, SO4SulfonationHCHO萘油是煤焦油中重要的餾分其中萘及其同系物 No amount reaction time amount reaction time占80%工業(yè)上通常先用萘油制取精萘再用精萘合t/hg/ml成萘系水煤漿添加劑。由于存在著精萘的分離過程BD11必然增加水煤漿添加劑的成本。直接利用萘油中的2A230B22D32.0萘及其同系物等有效成分的磺化、水解、縮合和中和3A34C35D2.5反應(yīng)制取新型的水煤漿添加劑是一種新的嘗試A: H SO 4 amount B: sulfonation reaction time;C: HCHOamount,D: condensation reaction time1實(shí)驗(yàn)部分1.1原煤的煤質(zhì)分析實(shí)驗(yàn)使用的煤樣為徐州礦添加劑的制備將75g萘油加入500mL的四140℃時(shí)緩慢地滴務(wù)局龐莊爆礦提供在中國礦業(yè)大學(xué)化工學(xué)院化工加定量的濃HSo溫度至160℃計(jì)時(shí)恒溫達(dá)到規(guī)2煤粉的磨制及其粒徑的測定取塊煤經(jīng)初步定的磺化反應(yīng)時(shí)間。調(diào)節(jié)溫度至120℃加入適量破碎至粒徑小于3mm再置于烘箱(105℃)烘的水水解0.5h,調(diào)節(jié)反應(yīng)液的pH<3。水解反應(yīng)3h將其分為等質(zhì)量的兩份分別用XMB7型三后再調(diào)節(jié)溫度至95℃-100℃在2h內(nèi)分三次將定量的HCHO緩慢加入燒瓶升溫到105℃恒溫反輥四筒棒磨機(jī)磨粉。其中一份磨50min得到粗粉另一份曆2h得到細(xì)粉。將粗粉與細(xì)粉等量混合均應(yīng)至規(guī)定時(shí)間后停止加熱使物料冷卻到6℃緩勻得到級配的煤粉。用LS粒度儀( Fraunhofer光慢加入NaOH溶液待中和反應(yīng)快結(jié)東當(dāng)pH值為學(xué)模型遮蔽:1%測量時(shí)間0s)測試煤粉的粒7~9時(shí)即制得萘油添加劑的粘稠液體產(chǎn)品。1.4水煤漿性能測試制漿時(shí)采用定時(shí)電動(dòng)攪拌,徑分布。在1200r/min的轉(zhuǎn)速下攪拌5min。粘度使用NXS-收稿日期:2003-1108;修回日期:200407-14628燃料化學(xué)學(xué)報(bào)1A型旋轉(zhuǎn)度計(jì)測定選用C測量系統(tǒng)。水煤漿的2.3萘油添加劑的評價(jià)指標(biāo)C∫、。定義為定量的流動(dòng)特性用目測流動(dòng)性來表示根據(jù)其流動(dòng)性狀分添加劑制備的水煤漿在一定粘度下的質(zhì)量分?jǐn)?shù)值為A、BC、D等級。水煤漿穩(wěn)定性使用試管靜置法簡稱為定粘定量質(zhì)量分?jǐn)?shù)。它是比較水煤漿質(zhì)量或檢測將水煤漿置于試管中用凡士林密封靜置評價(jià)添加劑性能的一種指標(biāo)。通過制漿并利用其性48h后看其析水程度和沉淀情況。能檢測實(shí)驗(yàn)的結(jié)果得到添加劑用量水煤漿質(zhì)量分1.5水煤漿添加劑的FIR光譜分析取少量在數(shù)水煤漿粘度的對應(yīng)關(guān)系以添加劑用量和粘度為較佳條件下合成的萘油添加劑粉末粒徑<30目)縱坐標(biāo)質(zhì)量分?jǐn)?shù)為橫坐標(biāo)在添加劑用量-粘度-質(zhì)用 Avatar360型傅立葉變換紅外光譜儀(kBr壓片量分?jǐn)?shù)的坐標(biāo)中描出對應(yīng)各點(diǎn)然后采用多元線性法測定添加劑的紅外光譜?；貧w將曲線擬合得到擬合方程。從擬合方程中計(jì)2結(jié)果與分析算添加劑的用量為1.0%(漿基)水煤漿的粘度為2.1煤質(zhì)分析實(shí)驗(yàn)選用龐莊煤結(jié)果見表2。1200mPas時(shí)相應(yīng)各點(diǎn)的質(zhì)量分?jǐn)?shù)值即C,a值a值高說明煤的成漿性好。表2煤性質(zhì)分析2.4正交試驗(yàn)分析方法利用1934)交表設(shè)計(jì)Table 2 Analysis of coal properties實(shí)驗(yàn)除了選定的因素外其它條件固定。設(shè)計(jì)方案Proximate analysis w /%0Ultimate analysis wdf /%HGI及結(jié)果分析見表4與表5。1.3210.7936.5483.434.7010.291.300.27150064.81表4實(shí)驗(yàn)方案與結(jié)果Table 4 Exprimental design and result由表2可知龐莊煤屬于煙煤其煤化程度中等偏低。由于龐莊煤內(nèi)在水分較低哈式可曆指數(shù)較Exprimental factors高揮發(fā)分大于28%灰熔點(diǎn)(t2高于1250℃,可以預(yù)測該煤種是比較理想的制漿用煤。由煤炭成漿BBBBCCCD68.8性判別指標(biāo)公式D=7.5-0.05HGI+0.5M68.1C及C=77-1.2D(%)1,可以計(jì)算出D=4.9223456A68.4C=71.5%。預(yù)計(jì)可制漿的最高質(zhì)量分?jǐn)?shù)為71.5%。C68.3BBBBCA粉煤的粒徑分布為提高水煤漿的質(zhì)量分?jǐn)?shù)將煤粉磨制成具有一定粒徑分布的粒子小粒子占68.7據(jù)在大粒子之間的空隙中,可以顯著提高水煤漿中表5試驗(yàn)結(jié)果分析煤粉的堆積率降低水煤漿的粘度及改善水煤漿的Table 5 Analysis of exprimental results流動(dòng)性。因此絕大多數(shù)高濃度的水煤漿都是用具Factor有雙峰或多峰分布特征的煤粉制成的。本試驗(yàn)?zāi)ブ?04.4203,0203,4204.6的級配煤粉粒徑分布通過分析表明其符合雙峰分布204特征。其中對0.375m至948m的煤粉進(jìn)行算術(shù)k203.6205.1203.8203.9體積統(tǒng)計(jì)其結(jié)果見表3。Kr67.6767.8068表3算術(shù)體積統(tǒng)計(jì)68.3667Table 3 Arithmetic volume statistics0.43表5各列分別根據(jù)表4中C,值計(jì)算出四種<2,30<8.68<32.27<75.30<120.10<300.0diameter d/jm因素的三個(gè)水平相應(yīng)的質(zhì)量分?jǐn)?shù)和K1、K2、K3及其olume fraction op%9.24.8079049.6平均質(zhì)量分?jǐn)?shù)值k1、k2k3和極差R=k-k-m。極為提高煤炭的燃燒效率煤粒應(yīng)達(dá)到-一定的細(xì)差的大小反映了實(shí)驗(yàn)中各個(gè)因素影響的大小極差度。一般要求粒度的上限為300cm其中<74{m的大說明該因素的影響大是一個(gè)主要因素反之極郭照冰等∶萘油制備新型水煤漿添加劑的研究629的相對主次順序?yàn)閤BAD同時(shí)根據(jù)極差分析系一般可用Ma修正式表示1n]=KMF還可以得到萘油添加劑合成的較佳反應(yīng)工藝條件式中:Ka為常數(shù)與溫度有關(guān)也與聚合物為2B2C2D(表1)即在75g禁油中需加入溶劑體系的性質(zhì)有關(guān)。A主要依賴于溶液中大分子濃HSO30mL,l60℃磺化2h加入HCHO25m,的形態(tài)即大分子線團(tuán)的緊密程度在優(yōu)良溶劑中105℃縮合1.5h大分子鍵因溶劑化而很好地舒展。K的數(shù)量級一般結(jié)果表明在不同條件下制得的水煤漿通過擬為102。隨著M增加[η增加較快到達(dá)一定的數(shù)合計(jì)算出的C值不同。H2SO和HCHO用量對漿值時(shí)溶液粘度過大分子就開始卷縮不能充分發(fā)的粘度都有一個(gè)最佳值。這是由于隨著H2sO用量揮其分散性能,此時(shí),添加劑的分散力下降,故的增加添加劑中的磺酸根-S0增多使煤粒表HCHO用量也有一個(gè)較佳范圍面氬鍵締合水化膜加厚有利于煤粒之間的滑動(dòng)而5添加劑性能的評估為更好地進(jìn)行添加劑的粘度降低。當(dāng)H、O的用量過度增加時(shí)增加了磺性能評估選擇了純的素磺酸縮甲醛添加劑1”與化反應(yīng)中的副反應(yīng)在中和時(shí)形成了較多的NaSO的性能見表6較佳工藝條件下生產(chǎn)的添加劑2)相比較。他們晶體鹽所以適度的H2SO4用量對降粘有利。另外,添加劑在溶液中的粘度與其分子量有關(guān)其定量關(guān)表6水煤漿的性質(zhì)Table 6 Properties of coal water slurryAdditivebaI water sliSample No Addition amount w/% Concentration w /9 Viscosity n /mPa sFluidityStability t/48 h0.867.7deposit0.868.01.269.0l128eposition1.668.0900oft deposition0.868.7l1621.268.088069.4oft deposition1.6由表6的數(shù)據(jù)結(jié)合多元線性回歸的數(shù)學(xué)模型產(chǎn)需求的情況下成本為2707元/噸比純萘系添加分別計(jì)算其相應(yīng)的回歸方程及評價(jià)指標(biāo)Cf、(定量劑的出廠價(jià)格(5000元/噸還低。定粘質(zhì)量分?jǐn)?shù))結(jié)果見表7。2.6添加劑的結(jié)構(gòu)分析萘油添加劑的紅外光譜表7添加劑的用量水煤漿粘度質(zhì)量分?jǐn)?shù)的擬合方程圖見圖1。Table 7 fitting functions about the amount of additives and theoncentration and the viscosity of coal water slumyConstant ConstAdditivestant Coefficient Relativity CSv as60.361.740.00580.0060y=A+A1×x1+A2×x( y is the concentration of coalter slurry and xi x, the addition amount of additive and thecosity of coal water slurry.)由表7的1*、2*樣品比較可見在兩種添加劑圖1萘油添加劑的R譜圖Infrared spectrogram of additi燃料化學(xué)學(xué)報(bào)由圖1可知3422.65cm處的強(qiáng)吸收峰為羥3結(jié)語基的伸縮振動(dòng)峰。萘油添加劑為一種極性極強(qiáng)的物(1)通過正交實(shí)驗(yàn)與多元線性回歸分析得到質(zhì)磺酸根易與水形成水合物67 RSO Na.nH,Oo制備萘油添加劑的最佳實(shí)驗(yàn)工藝條件即在75g的3062.75cm處的吸收峰為萘環(huán)C-H的伸縮振動(dòng)萘油中加入濃H2SO430m在160℃時(shí)磺化2h加峰。2914.25cm處的吸收峰為亞甲基C-H的伸HCHo25mL在105℃時(shí)縮合1.5ho縮振動(dòng)峰l44.62cm處的吸收峰為亞甲基C-H(2)用萘油添加劑制漿,水煤漿的分散性能較的彎曲振動(dòng)吸收峰。1593.12cm-與1506.07cm1好穩(wěn)定性稍差。但可以明顯降低添加劑的成本。處的吸收峰為萘環(huán)C-C骨架伸縮振動(dòng)的吸收峰。3)由萘油添加劑的FTR光譜分析結(jié)果推測135245cm1-1055.45cm的吸收帶是磺酸根的出添加劑主要為含有-CH1-,-SO3等基團(tuán)的芳吸收區(qū)域1239.79cm處極強(qiáng)的吸收峰為磺酸鹽香族化合物的特征吸收峰?？梢耘袛噍劣吞砑觿┲饕獮楹蠧H2-,-SO3等基團(tuán)的芳香族化合物。參考文獻(xiàn)[Ⅰ]李永昕李保慶陳誦英籌等.添加劑分子結(jié)構(gòu)特征與靈琥煤水煤漿漿體各性質(zhì)間匹配規(guī)律硏究J].燃料化學(xué)學(xué)報(bào)1997,253)247-252(LI Yong-xin, LI Bao-qing CHEN Song-ying et al. Correlation between structural characteristics of additives and properties ofWS of Lingwu coa[ J ] Journal of Fuel Chemistry and Technology 1997, 253)247-252[2]孫成功謝亞雄李保慶等.分散劑分子結(jié)構(gòu)特征對煤漿流變特性的影咂J.燃料化學(xué)學(xué)報(bào),1997,253)213-217(SUN Cheng-gong, XIE Ya-xiong, LI Bao-qing et al. Characterization of dispersant structures and their effect on rheological be-haviour of Cws J ] Journal of Fuel Chemistry and Technology, 1997, 2<(3 )213-217.)[3] MISHRA S K, KANUNGO S B. Factors affecting the preparation of highly concentrated coal-water slurry HCCWS I J]. J Sci IndRes,2000,5910)765-790.[4]張榮曾何為軍.高濃度水煤漿的制備技朮J].佛山陶瓷,2003,(4)∶1-15.ZHANG Rong-zeng, HE Wei-jun. Preparation technology of high concentration of CwS J ] Foshan Ceramics, 1997, 253)247[5]吳國光.低階煤流化床低溫?zé)峤饨褂秃铣伤簼{添加劑的試驗(yàn)研究D]北京中國礦業(yè)大學(xué)996WU Guo-guang. Study on synthesis of additives for coal water slurry with low temperature pyrolysis tar from low rank coal fluidizedbed D ] Beijing: China University of Mining Technology ) 1996.)[6]謝晶曦.紅外光譜在有機(jī)化學(xué)和藥物化學(xué)中的應(yīng)瓶M]北京:科學(xué)出版社1987(XIE Jing-xi. Application of infrared spectroscopy in organic chemistry and medicinal chemistryL M ] Beijing: Science Press1987.)[7]洪山海.光譜分析法在有機(jī)化學(xué)中的應(yīng)瓶M]北京:科學(xué)出版社,1980( HONG Shan-hai. Application of spectroscopic analysis in organic chemistry[ M ] Beijing: Science Press, 1980郭照冰等∶萘油制備新型水煤漿添加劑的研究Synthesis of a new additive from naphthalene oilfor coal water slurryGUO Zhao-bing, ZHENG Zheng, WU Guo-guang, ZHENG Shou-rong(I. State Key Laboratory of Pollution Control and Resource Reuse, Environmental School2. School of Chemical Science and Technology, China University of Mining Technology Xuzhou 221008, ChinaAbstract The method using effective components of naphthalene oil to synthesize the additive for coal water slurry(CWS )was studied. Through proper experimental design and multianalysis of linear regress the optimum synthesisconditions were obtained. That is 30 mL H, SO4 was added into naphthalene oil( 75 g ) to initiate a sulfonation reaction at 160C for about 2 h. After hydrolysis 25 mL HCHO was put into the reactor to cause a condensation reactionat 105C for 1.5 h. Experiments of CwS preparation with the additive synthesized and with the pure naphthalenesulfonic acid formaldehyde condensation product indicate that the additive synthesized has good dispersive property andlow cost. The functional groups of the present additive are investigated by Fourier Transform Infrared Spectroscopy(FTIR), which indicates that the additive contains some aromatic compounds with-CH2SO functionalgroups. Finally the mechanism for improving the property of Cws by the additive is probed preliminarilyKey words naphthalene oil ; additives for coal water slurry i propertyFoundation item: National Natural Science Foundation of Chind 10075027 ) Shanghai Tongji GAO Ting-yao Environmental ScienceTechnology Development FoundationAuthor introduction: GUO Zhao-bing( 1972-), male, Ph. D. student, speciality of environmental engineeringE-mail:guocumt@sina.com