發(fā)布時間：2018-04-02 11:08

  本文選題：共液化殘渣　切入點：瀝青質　出處：《太原理工大學》2015年碩士論文

【摘要】：煤與油漿共液化處理，可以增加輕質油產(chǎn)量和降低循環(huán)溶劑用量，緩解我國石油資源短缺的現(xiàn)狀。煤油共液化殘渣是一種含碳量較高的副產(chǎn)物，主要用于氣化、燃燒、焦化、熱解和液化等方面，近年來煤炭產(chǎn)業(yè)趨向集約化發(fā)展，人們開始用殘渣來制備碳素材料。目前用于制備碳素材料的原料主要有價格昂貴的純芳烴（如萘瀝青等），還有組成變化較大的煤焦油瀝青、石油瀝青以及它們不同比例的混合料，相比之下，，用價格低廉、組成均勻的煤油共液化殘渣來制備碳素材料對資源的高效利用和環(huán)境保護具有重要意義。 本文以不同工藝下兗州煤和石家莊催化裂化甩出油漿共液化殘渣為原料，通過熱聚合法制備中間相瀝青。考察了共液化工藝對殘渣組成分布的影響；課題進一步通過殘渣中瀝青質（HI）的熱重分析（TG）和熱臺實驗探討了殘渣制備碳素材料的可能性，利用偏光顯微鏡和傅里葉紅外光譜分析儀（FT-IR）考察了熱聚合溫度、時間、添加劑、升溫速率等對聚合產(chǎn)物中間相瀝青性質的影響；本文最后對中間相瀝青進行碳化，通過掃描電子顯微鏡（SEM）和X射線衍射儀（XRD）等手段分析了碳化中間相瀝青的結構和微觀形貌，測試了碳化中間相的電化學性能。主要得出以下結論： （1）煤油共液化殘渣中含有約30%-40%的瀝青質（HI）、50%左右的重油（HS）和2%-10%的四氫呋喃不溶物（THFIS）。加氫液化使得殘渣中瀝青質含量增加，重油和THFIS含量減少，同時重質產(chǎn)物分子量減少；加氫促進了煤的熱解反應，生成的瀝青質聚合程度較高，相反氮氣下得到的瀝青質聚合程度較低，含有較多的烷基側鏈和環(huán)烷結構。 （2）瀝青質類物質生成中間相瀝青的熱聚合溫度宜選在350℃-500℃之間，其分子量大小要適宜，一般范圍為500-600。隨著熱聚合溫度的升高或聚合時間的延長，甲苯不溶物和喹啉不溶物的含量隨之增加，中間相瀝青從微球形態(tài)融并為流線型結構再轉化為焦炭，瀝青質HI1（H2下共液化所得）在440℃反應6h就可生成廣域流線型中間相，有可能用于制備碳纖維或針狀焦，瀝青質HI2（N2下共液化所得）在440℃反應12h就可生成體型中間相，HI1和HI2在380℃反應10h均可生成大量中間相微球。 （3）添加劑聚丙烯（PP）增加了HI1多核芳烴的烷基側鏈，降低了體系粘度，促進了球晶的形成和長大，而且隨著PP添加量的增多促進作用更明顯，而PP與HI2作用時部分烷基與其作用，部分自組裝成環(huán)烷烴或芳烴，促進微晶形核；添加劑炭黑在中間相形成初期促進形核，后期阻礙微球融并成體中間相。 （4）升溫速率太慢，不利于中間相的形成；升溫速率太快，揮發(fā)分逸出較快，粘度迅速變化，不利于光學各向異性組織的有序排列。因此只有在適宜的升溫速率下粘度變化適中，才能生成有序的各向異性中間相。 （5）由碳化后的中間相微球形貌可知其成核機理為“顆�；締卧獦嬛�，為均相形核，結構是“Brooks-Taylor”型結構；碳化后的針狀焦結晶度高，擇優(yōu)取向好。上述碳化中間相瀝青都有很好的循環(huán)伏安特性。
[Abstract]:Coal oil co - liquefaction residue is a byproduct of high carbon content , mainly used for gasification , combustion , coking , pyrolysis and liquefaction .

The effects of co - liquefaction process on the composition distribution of residues were investigated in this paper by using the catalytic cracking of Yanzhou coal and Shijiazhuang in different processes as raw materials , and preparing intermediate phase pitch by thermal polymerization .
In this paper , the possibility of preparing the carbonaceous material from the residue was investigated by TG and FT - IR , and the effects of thermal polymerization temperature , time , additive and temperature rise rate on the properties of the intermediate phase asphalt were investigated by means of polarization microscope and Fourier transform infrared spectrum analyzer ( FT - IR ) .
In this paper , the structure and microstructure of the intermediate phase asphalt were analyzed by scanning electron microscopy ( SEM ) and X - ray diffraction ( XRD ) . The electrochemical properties of the carbonized intermediate phase were tested . The results were as follows :

( 1 ) the coal oil co - liquefaction residue contains about 30 % -40 % of asphalt ( HI ) , 50 % of heavy oil ( HS ) and 2 % -10 % tetrahydrofuran insoluble matter ( THFIS ) . The hydrogenation liquefaction causes the content of asphaltene in the residue to increase , the heavy oil and THFIS content are reduced , and the molecular weight of the heavy product is reduced ;
the hydrogenation promotes the pyrolysis reaction of the coal , the generated pitch polymerization degree is high , and the degree of polymerization of the asphaltene obtained under the opposite nitrogen gas is lower , and contains more alkyl side chains and naphthene structures .

( 2 ) The thermal polymerization temperature of the asphaltene - producing intermediate phase asphalt is preferably between 350 and 500 DEG C . The molecular weight of the intermediate phase asphalt is preferably 500 - 600 . As the temperature of the thermal polymerization increases or the polymerization time is prolonged , the content of the toluene insoluble substance and the quinoline insoluble substance is increased , and the intermediate phase asphalt can be formed into a wide - area streamline intermediate phase at 440 DEG C for 6 hours , and a large amount of intermediate phase microspheres can be generated at the reaction time of HI1 and HI2 at 380 DEG C for 10h .

( 3 ) The additive polypropylene ( PP ) increased the alkyl side chain of HI1 , decreased the system viscosity , promoted the formation and growth of spherulites and promoted the formation and growth of spherulites .
The additive carbon black promotes nucleation at the initial stage of the intermediate phase , and the latter blocks the microspheres to melt and form an intermediate phase .

( 4 ) the heating rate is too slow to be beneficial to the formation of the intermediate phase ;
In order to produce an ordered anisotropic intermediate phase , the temperature rise rate is too fast , the volatile component escapes quickly and the viscosity changes rapidly , which is not good for the ordered arrangement of the optically anisotropic tissue .

( 5 ) It is known that the nucleation mechanism is " particle basic unit construction " , and the structure is " Brooks - Taylor " type structure .
The carbonized intermediate phase asphalt has good cyclic voltammogram characteristics .

【學位授予單位】：太原理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ529;TQ127.11

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本文編號：1700114