煤焦油分離模擬與精制

用PRO/Ⅱ?qū)γ航褂偷姆蛛x模擬與精制報告人：王立成指導(dǎo)老師：孫津生日期：2006年12月8號

報告內(nèi)容一煤焦油組分分析二模擬熱力學(xué)方法的選擇及改進(jìn)三煤焦油分離模擬的簡單嘗試四煤焦油兩塔式分離的模擬與改進(jìn)五模擬結(jié)果與現(xiàn)場數(shù)據(jù)的比較六今后的工作安排

一煤焦油組分分析

煤焦油是復(fù)雜的多元組分混合物，由于其大多數(shù)單體化合物相互溶解而形成低共溶混合物，給蒸餾分離造成很大的困難。煤焦油的組分可以分為兩部分，一部分是有確定組分的輕組分，另一部分是無法具體定義其組成的虛擬組分——瀝青。1煤焦油的確定組分物質(zhì)名稱沸點（oC）摩爾質(zhì)量（g/mol）1水100.00018.0152苯80.10078.1153甲苯110.63092.1424鄰二甲苯144.410106.1695間二甲苯139.100106.1696對二甲苯138.350106.1697乙苯136.190106.1698苯乙烯145.140104.1539茚181.570116.16310四氫化萘207.550132.20611萘217.960128.17512α—甲基萘244.685142.20213β—甲基萘241.052142.202142，6—甲基萘262.000156.227152，7—甲基萘263.000156.22716聯(lián)苯255.000154.21117苊277.390154.21018芴297.290166.22219氧芴284.710168.19520蒽341.200178.23421菲338.370178.23422咔唑354.715167.21023芘393.000202.26024螢蒽382.800202.25525屈441.000228.29326吲哚253.000117.15027苯甲晴190.660103.12328苯酚181.84094.114292，4，6—三甲酚222.430136.194302，3—二甲酚216.950122.167312，4—二甲酚210.850122.167322，5—二甲酚211.150122.16733硫雜芴331.459184.26234吡啶115.30079.10235喹啉237.690129.1612煤焦油模擬的虛擬組分

瀝青的組成極為復(fù)雜，大多數(shù)為三環(huán)以上的芳香族烴類，還有含氮、氧、硫等元素的雜環(huán)化合物。為了便于模擬，我們用煉油廠煉油塔底的減壓渣油來代替煤焦油中的瀝青進(jìn)行模擬，在101.33kPa下，定義蒸餾的實沸點TBP(TrueBoilingPoint).這樣就解決了虛擬組分的定義問題。

瀝青實沸點的定義

蒸餾分率溫度/(oC)0.00360.001.00443.455.00489.4710.00517.2130.00597.3650.00650.0770.00729.1890.00989.0995.00989.0998.00989.09

瀝青的化驗處理圖3精制組分特性（1）萘萘是工業(yè)上最重要的稠環(huán)烴，主要用于生產(chǎn)苯酐、各種萘酚、萘胺等，是生產(chǎn)合成樹脂、增塑劑、染料的中間體、表面活性劑、合成纖維、涂料、農(nóng)藥、醫(yī)藥、香料、橡膠助劑和殺蟲劑的原料。（2）α-甲基萘可用于聚氯乙烯纖維和滌綸的印染載體，六六六的乳化劑，還可作熱載體和溶劑，表面活性劑，硫磺的提取劑，也可用作生產(chǎn)增塑劑，纖維助染劑的原料。（3）β-甲基萘用作生產(chǎn)維生素K3的中間體、植物生長調(diào)節(jié)劑，紡織助染劑、表面活性劑、DDT乳化劑；磺化后可作去垢劑。（4）苯酚是重要的有機化工原料，用它可制取酚醛樹脂、己內(nèi)酰胺、雙酚A、水楊酸、苦味酸、五氯酚、2,4-D、己二酸、酚酞N-乙酰乙氧基苯胺等化工產(chǎn)品及中間體，在化工原料、烷基酚、合成纖維、塑料、合成橡膠、醫(yī)藥、農(nóng)藥、香料、染料、涂料和煉油等工業(yè)中有著重要用途。此外，苯酚還可用作溶劑、實驗試劑和消毒劑。1997-2002年，美國、西歐、日本等主要地區(qū)苯酚需求量保持年均4.2%的速度增長。(5)芴用作有機合成原料?？芍瞥扇趸掏糜陟o電復(fù)??；合成芳基透明尼龍；可代替蒽醌合成陰丹士林染料；用于制造抗痙攣藥、鎮(zhèn)靜藥，鎮(zhèn)痛藥，降血壓藥；合成殺蟲劑，除草劑；制備抗沖擊有機玻璃和芴醛樹脂；亦可用作濕潤劑，洗滌劑，液體閃光劑，消毒劑等。(6)苊是有機合成原料，經(jīng)硝化可制硝基苊；進(jìn)一步氧化可制1,8-萘二甲酸酐和苊醌，可用于合成染料、聚酯樹脂、聚酯纖維；還可用于制熒光顏料，藥品，殺蟲劑等。苊脫氫得苊烯，可制苊烯樹脂。

二模擬熱力學(xué)方法的選擇及改進(jìn)模擬所采用的熱力學(xué)方法是Grayson—Streed（簡稱GS）法，它對于從輕到中等范圍的精煉廠的烴類通常是有用的。在模擬中發(fā)現(xiàn)用GS法計算的汽液平衡常數(shù)K在一些情況下與實際有些偏差，所以在模擬中進(jìn)行了一些修正。三煤焦油分離模擬的簡單嘗試兩塔式連續(xù)蒸餾用PRO/Ⅱ模擬與現(xiàn)場主要操作參數(shù)表

操作參數(shù)PRO/Ⅱ模擬現(xiàn)場數(shù)據(jù)閃蒸器1出口溫度/(oC)105120—130餾分塔1頂部溫度/(oC)110.495—115三混餾分側(cè)線溫度/(oC)210.806200—220一蒽油餾分溫度/(oC)319.341280—295餾分塔2頂部溫度/(oC)322.6370—374二蒽油餾分側(cè)線溫度/(oC)345.856330—355酚油塔酚油餾分側(cè)線溫度/(oC)170.557160—170萘油塔萘油餾分側(cè)線溫度/(oC)104198—200洗油塔洗油餾分側(cè)線溫度/(oC)266.815225—235餾分塔1底部壓力/(kpa)175.18≤150餾分塔2底部壓力/(kpa)153.28≤150酚油塔底部壓力/(kpa)201.75≤150萘油塔底部壓力/(kpa)139.83≤150組分祖墳瀝青一蒽油輕油二蒽油酚油萘油洗油煤焦油WATER0.00000.00010.00070.00000.00120.00000.00000.0212BENZENE0.00000.00000.30550.00000.00190.00000.00000.0017TOLUENE0.00000.00000.39480.00000.05000.00000.00000.0031OXYLENE0.00000.00000.00010.00000.02050.00000.00000.0004MXYLENE0.00000.00000.00020.00000.02050.00000.00000.0004PXYLENE0.00000.00000.00020.00000.02050.00000.00000.0004STYRENE0.00000.00000.00000.00000.00050.00000.00000.0000INDENE0.00010.00020.00030.00010.17130.00000.00000.0034BNZPHENO0.00010.00020.00000.00250.00000.00000.00000.00051234HNAP0.00010.00020.00010.00020.15300.00020.00000.0031NAPHTHLN0.00490.01050.00250.00980.24870.99970.09280.09971MNAPHTH0.00090.00180.00010.00390.00000.00000.15290.01252MNAPHTH0.00110.00220.00020.00460.00000.00000.21710.01751ENAPHTH0.00060.00100.00000.00370.00000.00000.07970.00692ENAPHTH0.00050.00090.00000.00350.00000.00000.08040.0069BIPH0.00030.00050.00000.00210.00000.00000.05180.0044ACENAP0.00310.00920.00010.04070.00000.00000.26220.0287FLUORENE0.00180.00800.00000.05770.00000.00000.02750.0137IBUPROFN0.00400.01140.00000.15990.00000.00000.00020.0312ANTHRCEN0.00440.03080.00000.07930.00000.00000.00000.0187PHNANTHR0.00820.02480.00000.15910.00000.00000.00010.0343DPM44DCN0.00670.03190.00000.16400.00000.00000.00000.0349PYRENE0.00760.12910.00000.05450.00000.00000.00000.0237CHRYSENE0.01100.08220.00000.00110.00000.00000.00000.0125INDOLE0.00010.00090.00000.00040.00000.00000.03120.0025BNZNITRL0.00000.00000.00000.00000.01240.00000.00000.0002PHENOL0.00000.00040.00100.00000.00000.00000.00000.0044DIBZTHIO0.00080.00300.00000.01740.00000.00000.00000.0037PYRIDINE0.00010.00020.29390.00000.29940.00000.00000.0075QUINOLIN0.00040.00130.00010.00140.00000.00000.00410.0062C18BENZ0.00810.00330.00000.22560.00000.00000.00000.0443NBP3370.00000.00000.00000.00000.00000.00000.00000.0000NBP3500.00000.00000.00000.00000.00000.00000.00000.0000NBP3590.00030.00130.00000.00480.00000.00000.00000.0011NBP5530.06850.51240.00000.00360.00000.00000.00000.0772NBP5790.14880.06100.00000.00000.00000.00000.00000.0843NBP6100.26090.04920.00000.00000.00000.00000.00000.1433NBP6320.15960.01650.00000.00000.00000.00000.00000.0866NBP6750.16590.00470.00000.00000.00000.00000.00000.0891NBP7250.13090.00070.00000.00000.00000.00000.00000.0700四煤焦油兩塔式分離的模擬與改進(jìn)STREAM組分酚油萘油洗油精制萘油萘塔底餾分1WATER0.04770.02930.02966.0380E-056.4754E-052BENZENE0.16630.04320.04166.3243E-046.2635E-043TOLUENE1.06790.11010.10492.6838E-032.6028E-034OXYLENE1.48800.02820.02631.3650E-031.2880E-035MXYLENE1.44890.02410.02269.7873E-049.2853E-046PXYLENE1.88230.03130.02951.2375E-031.1765E-037EBENZENE23.26610.38660.36400.01510.01438STYRENE24.09470.57890.53700.03570.03339INDENE9.89190.72090.61590.11570.1037101234HNAP2.19501.53200.90510.81630.508511NAPHTHLN7.279677.796060.684890.829866.5556121MNAPHTH5.0889E-042.13898.34168.1038E-055.2456132MNAPHTH2.0251E-034.752914.19658.5499E-0411.65561426DMNP1.1355E-060.06630.96787.0821E-090.16261527DMNP4.0073E-084.6416E-030.10689.8845E-110.011416BIPH7.3198E-070.03630.50184.8445E-090.089017ACENAP3.9883E-133.1820E-062.4841E-032.1390E-187.8040E-0618FLUORENE3.8068E-191.0301E-102.0217E-060.00002.5263E-1019DBZFURAN3.6280E-127.1449E-062.2046E-035.5163E-171.7523E-0520ANTHRCEN0.00000.00003.0309E-160.00000.000021PHNANTHR0.00000.00003.6048E-160.00000.000022CARBAZOL0.00000.00000.00000.00000.000023PYRENE0.00000.00000.00000.00000.000024FLUANTHE0.00000.00000.00000.00000.000025CHRYSENE0.00000.00000.00000.00000.000026INDOLE4.0606E-040.54931.28765.0352E-041.346727BNZNITRL0.59470.06720.05070.01370.011728PHENOL25.06600.38410.35020.01480.013629246TMPH0.08585.12164.74244.28077.11913023XYLNOL0.09041.34351.02061.64291.05903124XYLNOL0.33361.42110.86711.51870.65223225XYLNOL0.23360.69180.42650.69290.319633DIBZTHIO0.00000.00003.5021E-160.00000.000034PYRIDINE0.75920.05940.05611.5694E-031.5109E-0335QUINOLIN5.5459E-032.08253.71820.01375.090436NBP3660.00000.00000.00000.00000.000037NBP3790.00000.00000.00000.00000.000038NBP3940.00000.00000.00000.00000.000039NBP4080.00000.00000.00000.00000.000040NBP4220.00000.00000.00000.00000.000041NBP4420.00000.00000.00000.00000.000042NBP4690.00000.00000.00000.00000.000043NBP4950.00000.00000.00000.00000.000044NBP5240.00000.00000.00000.00000.000045NBP5530.00000.00000.00000.00000.000046NBP5820.00000.00000.00000.00000.000047NBP6050.00000.00000.00000.00000.0000

流程改進(jìn)熱力學(xué)方法的改進(jìn)

通過改變組分的塔板效率系數(shù)K，來改變組分在氣相及液相中分布，從而使某些餾分的組分要求與現(xiàn)場數(shù)據(jù)相符

1餾分塔熱力學(xué)方法的改進(jìn)

塔板數(shù)3233343536373839萘的K值14151617171818182甲基萘前處理塔熱力學(xué)方法的改進(jìn)3甲基萘塔的熱力學(xué)方法改進(jìn)塔板數(shù)

1918161211109萘的K10111213141516246-三甲酚的K10111213141516塔板數(shù)393837363330272625α-甲基萘K

60504037362535300.2β-甲基萘K

80706050454040350.24酚油預(yù)處理塔熱力學(xué)方法改進(jìn)5酚油塔熱力學(xué)方法改進(jìn)塔板數(shù)1918171615141312乙苯K15141312111098苯乙烯K15141312111098茚K0.010.020.030.040.050.050.050.01苯酚K2524232221200.20.1萘K2524232221200.20.1塔板數(shù)19181715萘K27262423苯酚K0.050.10.150.2五模擬結(jié)果與現(xiàn)場數(shù)據(jù)的比較1兩塔式連續(xù)蒸餾用PRO/Ⅱ模擬與現(xiàn)場主要操作參數(shù)表

操作參數(shù)PRO/Ⅱ模擬現(xiàn)場數(shù)據(jù)一段蒸發(fā)器出口溫度/(oC)105120—130餾分塔頂部溫度/(oC)11095—115一蒽油餾分溫度/(oC)282.55280—295二段蒸發(fā)器頂部溫度/(oC)322.6370—374酚油餾分側(cè)線溫度/(oC)150.34160—170萘油餾分側(cè)線溫度/(oC)225.34198—200洗油餾分側(cè)線溫度/(oC)178.23225—235一段蒸發(fā)器底部壓力/(kpa)105≤130二段蒸發(fā)器底部壓力/(kpa)110≤150蒽塔塔底部壓力/(kpa)130≤150餾分塔底部壓力/(kpa)130≤150

2模擬各餾分組分含量組分酚油萘油洗油甲基萘油苯酚油WATER0.03110.01890.02676.8627E-067.8078E-07BENZENE0.11000.02720.06289.6664E-054.3248E-05TOLUENE1.20250.06880.18755.7170E-048.9455E-04OXYLENE1.47880.01720.06275.3928E-040.0482MXYLENE1.48370.01480.05033.1869E-040.0147PXYLENE1.95460.01930.06423.9017E-040.0134EBENZENE24.29170.23810.78994.6709E-030.0189STYRENE23.37810.34761.44290.01930.1003INDENE7.79840.36532.42650.22050.44871234HNAP0.98240.52883.96362.01302.1208NAPHTHLN11.089397.205714.59360.81881.84541MNAPHTH1.4366E-064.4702E-0312.118928.80065.5368E-062MNAPHTH1.0042E-050.017123.899356.44963.8701E-0526DMNP3.7545E-101.3029E-050.67214.0307E-041.4470E-0927DMNP7.6567E-125.2662E-070.06281.2526E-052.9511E-11BIPH2.5326E-108.3006E-060.38251.4760E-049.7612E-10ACENAP7.3999E-183.6438E-119.5225E-041.3136E-100.0000FLUORENE0.00008.6925E-162.0398E-061.1990E-150.0000DBZFURAN1.2159E-161.5194E-107.3996E-040.00000.0000ANTHRCEN0.00000.00007.6879E-140.00000.0000PHNANTHR0.00000.00008.4142E-140.00000.0000CARBAZOL0.00000.00003.9289E-180.00000.0000PYRENE0.00000.00000.00000.00000.0000FLUANTHE0.00000.00000.00000.00000.0000CHRYSENE0.00000.00000.00000.06410.0000INDO