第30卷第4期煤炭轉(zhuǎn)化Vol.30 No. 42007 年10月COAL CONVERSIONOct. 2007神府煤制備磺化煤的研究及應(yīng)用廖曉蘭”汪曉芹2) 周安寧3) 姚天 國"摘要 討論了神府煤制備磺化煤的反 應(yīng)中,磺化溫度、時(shí)間對(duì)煤磺化度和酸性基的影響,用FTIR對(duì)磺化煤進(jìn)行結(jié)構(gòu)表征,用體積溶脹法研究了磺化煤在苯胺中的溶脹特性.結(jié)果表明,煤的磺化度隨著磺化溫度的升高磺化時(shí)間的延長而增大,煤經(jīng)過磺化反應(yīng)后其在苯胺中的溶脹性能也得到了改善.關(guān)鍵詞神府煤,磺化反 應(yīng),溶脹中圖分類號(hào)TQ536上生成磺化煤.煤的磺化反應(yīng)如下:0引言RH+HOSO2H一→R- -SO,H+H2O磺化煤是煙煤經(jīng)發(fā)煙硫酸或濃硫酸處理,再經(jīng)同時(shí)濃硫酸在加熱的條件下也是一種氧化劑，洗滌篩分而得到的外觀為黑色不規(guī)則細(xì)粒的產(chǎn)品，可把煤分子結(jié)構(gòu)中一CH,(甲基)和-CxH,(乙基)等它是一-種制備簡單.價(jià)格低廉、原料廣泛的多官能團(tuán)基團(tuán)氧化生成- CO0H(羧基),并使C- -H鍵氧化陽離子交換劑,它的用途廣泛,可以用作軟水劑,在成酚羥基.因此,磺化煤的分子結(jié)構(gòu)可表示為:SO,H污水處理中可作吸附劑以回收污水中的稀有金屬和有機(jī)酸,還可以用作有機(jī)化學(xué)反應(yīng)的催化劑,如催化R- -OH烯酮反應(yīng),烷基化或脫烷基反應(yīng)、酯化反應(yīng)及縮合反COOH應(yīng)等;另外,也可作淀粉水解劑，鉆井泥漿添加劑、環(huán)其三種活性基團(tuán)的氫均能電離產(chǎn)生H+離子,對(duì)氧樹脂聚合劑等.而本文是用制備出的磺化煤做高聚苯胺進(jìn)行摻雜.具體過程如下:分子模板,同時(shí)又作為質(zhì)子酸摻雜劑，制備導(dǎo)電型磺-C00H一COOHNO+引發(fā)劑化煤基聚苯胺復(fù)合材料,當(dāng)磺化煤的百分含量為口-Nm絲t SO-HNA-OROHN'-50% ,該復(fù)合材料的電阻率可達(dá)10.53∩. cm,與原煤相比,降低近10個(gè)數(shù)量級(jí).凹其機(jī)理首先是磺化tO-wO-:OxOh煤的酸性基團(tuán)與苯胺的氨基形成的離子鍵或氫鍵[2],使苯胺很好地吸附與鏈合在煤的表面與煤的孔隙中聚合,煤起到聚合載體的作用，當(dāng)苯胺聚合到一定程度時(shí),磺化煤的酸性基與聚苯胺醌環(huán)的N形2實(shí)驗(yàn)部分成離子對(duì),達(dá)到摻雜的目的,賦予聚苯胺的導(dǎo)電性.并能改善苯胺溶液聚合后過量酸的后處理過程,減2.1原料和儀器少環(huán)境污染,降低成本.煤樣有神府煤(簡稱SFC)、綠水洞原煤1磺化機(jī)理(LSDYC).綠水洞洗精煤(LSDXC)和黃陵店頭煤煤是含有多種側(cè)鏈和官能團(tuán)的多環(huán)芳香化合(HLDTC),主要工業(yè)分析與元素分析見第26頁表物,用發(fā)煙硫酸或濃硫酸處理煤時(shí),發(fā)生磺化反應(yīng)，1.煤樣都經(jīng)過超細(xì)粉碎,最大粒徑小于16 um,中值反應(yīng)結(jié)果把一SO.H 引入到煤的縮合芳香環(huán)和側(cè)鏈為5.中國煤化工m..教育部科羋技術(shù)研兗重點(diǎn)項(xiàng)目(0232).1)碩士.講師,天津城市建設(shè)學(xué)院材料科學(xué)與工程系,300384天津;2) 博士、嗣數(shù)夜13)博士生爭卿教慣.四女科技大學(xué)材料工程系，710054西安;4)酗教授,天津城市建設(shè)學(xué)院能意與機(jī)憾工程弱,300384天津收稿日期:2007 -05-18;修回日期:2007-06-2226煤炭轉(zhuǎn)化2007年表1原料煤的工業(yè)分析與元素分析Table 1 Ultimate and proximate analysis of coalsProximate analysisUltimate analysisCoal sampleMdAcharacteristicHSFC7. 294.27 36.42 60. 8781.13 4.79 11.95 1.10 0.75LSDYC0.8616.8323. 0963. 9687.814.63 4.63 1.29 2.08LSDXC0.7769. 0088.63 4. 692.23 1.38 2. 16HLDTC3.2113. 3034. 9556. 4081.75 4. 789.85 1.17 0. 55主要儀器有Z89- -1型電動(dòng)攪拌器、TD- -18型H,然后加人2 mL~3 mL苯胺,用不銹鋼細(xì)棒徹底調(diào)電熱套、三口燒瓶、抽濾瓶、布氏漏斗、ZX-1型攪拌,垂直靜置24 h后,再次以同樣的方式離心，測(cè)真空干燥器、KZDL-3B型快速智能定硫儀和定溶脹后煤層的高度Hz,磺化煤溶脹率Q= H2/H.TDL-4型低速抬式離心機(jī)等.3)紅外光譜分析.在美國Nicolet生產(chǎn)的60SXR傅里葉變換紅外光譜上進(jìn)行,采用KBr壓片.2.2磺化煤的制備超細(xì)煤樣先經(jīng)烘干以驅(qū)出其毛細(xì)孔中的水分，3結(jié)果與討論稱量后放入反應(yīng)器內(nèi),按預(yù)定的酸/煤比(質(zhì)量比6:1)加入濃硫酸,升溫至反應(yīng)溫度后保溫,達(dá)到預(yù)定的3.1磺化因素對(duì)神 府煤酸性基的影響反應(yīng)時(shí)間后冷卻,再減壓過濾,洗滌至中性,然后在.磺化因素對(duì)神府煤酸性基的影響見表3.從表350 C下真空干燥至恒重.中的極值可知,磺化溫度的影響大于磺化時(shí)間的影響,并且隨著磺化溫度的升高,神府煤的總酸性基與2.3磺化反應(yīng)的因素與水平磺酸基的含量增加,同時(shí),隨著反應(yīng)時(shí)間的延長,神由文獻(xiàn)[3,4]可知,在煤磺化反應(yīng)中,最大影響府煤的總酸性基與磺酸基含量也增加.磺化作用的主要因素有磺化時(shí)間磺化溫度和煤種，衰3磺化因素對(duì)神府煤酸性基的影響本實(shí)驗(yàn)是不考慮煤種的情況下,磺化反應(yīng)采用二因Table 3 Analysis of functional group of素三水平正交,其因素與水平見表2.sulfonated Shenfu coal表2磺化反應(yīng)的因素與水平ExptrinentalGeneral acid groups- -SOzH conten/nomber1content/mmol*g 1 (mmol.g-')Table 2 Factors and levels of sulfonation reaction4.81000.7125Level Sulfonation temperature/ CSulfonation time/h5. 003 10.737 01205.641 40.774 3.1406.274 50. 901 9806.4095.1. 024 56.734 81. 356 12.4性能測(cè)試6.351 6.1.165 36.763 01.466 4.1)磺化煤酸性基的測(cè)定.通過測(cè)定磺化煤的總6. 836 41. 710 8Factor酸性基的含量.羧基的含量和磺酸基的含量來分析5.1515 0.74130. 9266煤的磺化度,總酸性的測(cè)定采用鋇離子交換法5,羧Kz 6.4729 1. 09416. 05851.076 0基的測(cè)定采用乙酸鈣交換法[5,磺酸基采用磺化煤.6.6503 1.447 56. 40421.280 4中硫含量的方法測(cè)定.磺酸基的含量用KZDL--3B1.5015 0.706 20.592 20.353 8型快速智能定硫儀來測(cè)定,磺酸基的含量=磺化煤3.2煤種變化對(duì)磺化 反應(yīng)的影響中全硫的含量-磺化前原煤中全硫的含量,這種測(cè)定方法會(huì)導(dǎo)致磺酸基含量偏小,原因是煤在磺化反在神府煤磺化的基礎(chǔ)上,對(duì)其他煤進(jìn)行磺化,磺應(yīng)中會(huì)除去-部分黃鐵硫礦.化溫度為140 C,磺化時(shí)間為4 h.原煤與磺化煤的2)磺化煤在苯胺中的溶脹度的測(cè)定.室溫下，總酸中國煤化工第27頁表4.由表.在內(nèi)徑5 mm,長120 mm的平底玻璃試管中進(jìn)行,首4可Y片CNM H G活性有一定的關(guān)先裝人煤樣,煤樣高度在20 mm左右為宜,在水平聯(lián)性,也與礦物質(zhì)的量有關(guān),磺化作用隨著礦物質(zhì)的方向3 000 r/min下離心15 min后測(cè)定煤層高度量的增加而減弱,磺化作用與C/H含量無關(guān)聯(lián)性.第4期廖曉蘭等神府煤制 備磺化煤的研究及應(yīng)用27表4原煤與磺化煤的總酸性基.羧基和磺酸基的含 量(mol/g)Table4 General ecid groups content .carbonyl content and - SO,H content of coal and slonated cal(mmol/g)Raw coalSulfonated coaCoal smpleGenersl ecidCarbonylSs/%General acidSOHgroups content/content/Sa/%《mmol'g~ 1) (mmol. g-1)(mmol.g")(mmol *g-1)(mmol.g~1)SFC2.81500.095 50.756.40952.51 85. 081.0246LSDYC0.61800.04252.084. 865 91.8994. 800.850 00.590 00.071 82.164.085 01.6014.90.881 2HLDTC1. 884 00.021 70.55 .4. 950 02.07 0_2.90. 762 53.3煤在苯胺中的溶 脹度分析et Col溶脹是利用煤所具有的供氫能力和受氫能力，o Sufoated coal在親電、親核試劑的作用下,打破小分子相與網(wǎng)絡(luò)結(jié)構(gòu)之間的氫鍵,脫除煤分子內(nèi)部氫鍵的束縛,使煤結(jié)構(gòu)中較弱的鍵斷裂,從而降低煤結(jié)構(gòu)的交聯(lián)度,使交聯(lián)網(wǎng)絡(luò)結(jié)構(gòu)充分伸展的過程,通過溶脹作用,可使煤圖1 神府原煤與磺化神府煤的紅外光譜圖中的孔結(jié)構(gòu)發(fā)生改變,圓柱形孔增多,球形孔減Fig.1 FTIR of Shenfu coal and sulfonated Shenfu coal少60各種原煤與對(duì)應(yīng)的磺化煤在苯胺中的溶脹度側(cè)鏈烷基等脂肪基團(tuán)均被氧化成羧基.羥基等其他見表5.酸性基團(tuán),故一OH 與C- 0的吸收增強(qiáng),并且在磺表5原煤與對(duì)應(yīng)的磺化煤在苯胺的溶脹度化煤中出現(xiàn)S一0的吸收峰,而且酚、醉、酯的C- -0Table 5 Swelling capacity of sulfonated的吸收峰增強(qiáng),可見磺化作用對(duì)增加煤的酸性基有很coal in aniline solution好的作用,從1 602 cm~',1 450 cm-'與833 cm-'~LSDYHLDY779 cm~'的峰可知磺化煤中仍保持原煤所特有的分QRe1.5071.2111.217. 1 102子基本骨架. .1.7171.7311.9061. 940從表5可知,煤經(jīng)過磺化作用.各種煤的溶脹度4結(jié)論都有所增加,綠水洞原煤、綠水洞洗精煤和黃陵讓店頭煤這三種煤是含礦物質(zhì)較高,即其灰分較高,在它1)煤的磺化反應(yīng)能有效地增加煤的酸性基團(tuán)，們磺化時(shí),有一部分礦物質(zhì)被除掉,從而導(dǎo)致孔隙增并且煤的酸性基團(tuán)隨著磺化溫度的提高及磺化時(shí)間大,苯胺容易進(jìn)入,使得這四種煤磺化后其溶脹度變的廷長而增大.煤中灰分越低其磺化作用越強(qiáng),煤的化較大,對(duì)神府煤來講,其低灰.化學(xué)性質(zhì)好,表面含化學(xué)活性越強(qiáng),接上的磺酸基越多.氧官能團(tuán)較多等特點(diǎn)使得其原煤與磺化后的溶脹度2)磺化煤的紅外光譜圖及其在苯胺中的溶脹都較大.度表明,煤在適宜條件下磺化,只是改變煤鍘鏈基團(tuán)和一些取代基團(tuán),煤的基本骨架結(jié)構(gòu)并沒有發(fā)生本3.4紅外光譜分析質(zhì)上的變化,仍然保持煤的交聯(lián)大分子網(wǎng)絡(luò)結(jié)構(gòu)與由圖1可以看出,神府煤磺化后,煤中的甲基、豐富的孔隙結(jié)構(gòu)和分子篩結(jié)構(gòu).參爭文獻(xiàn)[] 虛曉蘭,周安寧，秦苯胺/責(zé)化煤復(fù)合導(dǎo)電材料的合成與表征[].天律城市建設(shè)學(xué)院學(xué)極22.-8-8.8[2] Giray ESV.Chen C,Takanohasbi T“al. Increase of the Extrecio Yield of Coale by the Addition of Aromaeic Amiene[J].Ful.2000.791533-1538.[3]倪獻(xiàn)智. 磺化煤制備的基礎(chǔ)研究[]煤類轉(zhuǎn)化.1997,201)66-69.[4]徐革聯(lián).鄂景景等. 磺化煤制備方法的研究[].煤炭加工與綜合利199951-24-2[5] 鐘蘊(yùn)英,關(guān)夢(mèng)嬪.崔開仁等媒化學(xué)DM].江蘇,中國礦量大學(xué)出版社。中國煤化工[6]劉勁松,馮杰.李 凡等溶脹作用在煤結(jié)構(gòu)與熱分解研究中的應(yīng)YHCNM HG28煤炭轉(zhuǎn)化2007年STUDY AND APPLIED ON PREPARING SULFONATEDCOAL WITH SHENFU COALLiao Xiaolan Wang Xiaoqin * and Zhou Anning' and Yao Tianguo'(Department of Materials Science and Engineering ,Tianjin Institute of Urban Construction,300384 Tianjin; # Department of Materials Engineering, Xi'an Universityof Science and Technology,710054 Xi"an; * * Department of EnergyTechnology and Mechnical Engineering ,Tianjin Insititue ofUrban Construction , 300384 Tianjin)ABSTRACT In the sulfonation reaction of coal, the effect of sulfonation temperature andtime on the sulfonation value and acid groups of coal were researched, the structure of thesulfonated coal were identified by FTIR, the swelling property of sulfonated coal in aniline werestudied by swelling. The result showed that the acidity of coal increased with the increase oftemperature and time, the swelling property of coal in aniline were improved by the sulfonationreaction.KEY WORDS Shenfu coal ,sulfonation reaction ,swelling(上接第21頁)COAL SURF ACE PHYSICAL ADSORPTION TO OXYGENMOLECULES MECHANISMWang Jiren Deng Cunbao Deng Hanzhong and Lu Weidong(College of Safety Science and Engineering, LiaoningTechmical University,123000 Fuxin ,Liaoning)ABSTRACT It had studied the non-crystal physical adsorption mechanism of coal by using the theoryof quantum chemistry , which reveals the adsorption mechanism and adsorption process in microscopic ，andquantitatively studies the relation of adsorption capacity and the heat gived out in the physical adsorptionprocess of coal to oxygen, thus it reveals the essence of coal oxidation spontaneous combustion initialreaction. It can show that from coal surface adsorption to multi- oxygen molecules optimized equilibriumgeometry, when the coal surface adsorbs oxygen molecule less than five, one is adsorbed in the coalsurface side chain including the nitrogen, the others are adsorbed by the benzene ring. When the coalsurface adsorbs oxygen molecule more than six, the adsorption of benzene ring to oxygen moleculeweakens, the adsorbed oxygen molecule partial to side chain, it has adsorbed massive oxygen molecule inthe coal surface side chain, this has also proved that in the process of coal oxidation spontaneouscombustion, the correctness of the conclusion that the side chain is firstly oxidized. It shows linearrelationship that the adsorption capacity and adsorption pow中國煤化Inolecule.KEY WORDS non-crystal material ,coal surface molecu:fYHCNMHG-ption mechanism