煤焦油分离模拟与精制

用PRO/Ⅱ对煤焦油的分离模拟与精制报告人：王立成

指导老师：孙津生日期：2006年12月8号报告内容一煤焦油组分分析二模拟热力学方法的选择及改进三煤焦油分离模拟的简单尝试四煤焦油两塔式分离的模拟与改进五模拟结果与现场数据的比较六今后的工作安排—煤焦油组分分析煤焦油是复杂的多元组分混合物，由于其大多数单体化合物相互溶解而形成低共溶混合物，给蒸馏分离造成很大的困难。煤焦油的组分可以分为两部分，一部分是有确定组分的轻组分，另一部分是无法具体定义其组成的虚拟组分——沥青。1

煤焦油的确定组分物质名称沸点（oC）摩尔质量（g/mol）1水100.00018.0152苯80.10078.1153甲苯110.63092.1424邻二甲苯144.410106.1695间二甲苯139.100106.1696对二甲苯138.350106.1697乙苯136.190106.1698苯乙烯145.140104.1539茚181.570116.16310四氢化萘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联苯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萤蒽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硫杂芴331.459184.26234吡啶115.30079.10235喹啉237.690129.1612煤焦油模拟的虚拟组分沥青的组成极为复杂，大多数为三环以上的芳香族烃类，还有含氮、氧、硫等元素的杂环化合物。为了便于模拟，我们用炼油厂炼油塔底的减压渣油来代替煤焦油中的沥青进行模拟，在101.33kPa下，定义蒸馏的实沸点TBP(True

Boiling

Point).这样就解决了虚拟组分的定义问题。沥青实沸点的定义蒸馏分率温度/(oC)0.00360.001.00443.455.00489.4710.00517.2130.00597.3650.00650.0770.00729.1890.00989.0995.00989.0998.00989.09沥青的化验处理图Perce

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Cuts3精制组分特性 萘萘是工业上最重要的稠环烃，主要用于生产苯酐、各种萘酚、萘胺等，是生产合成树脂、增塑剂、染料的中间体、表面活性剂、合成纤维、涂料、农药、医药、香料、橡胶助剂和杀虫剂的原料。 α-甲基萘可用于聚氯乙烯纤维和涤纶的印染载体，六六六的乳化剂，还可作热载体和溶剂，表面活性剂，硫磺的提取剂，也可用作生产增塑剂，纤维助染剂的原料。 β-甲基萘用作生产维生素K3的中间体、植物生长调节剂，纺织助染剂、表面活性剂、DDT乳化剂；磺化后可作去垢剂。 苯酚是重要的有机化工原料，用它可制取酚醛树脂、己内酰胺、双酚A、水杨酸、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产品及中间体，在化工原料、烷基酚、合成纤维、塑料、合成橡胶、医药、农药、香料、染料、涂料和炼油等工业中有着重要用途。此外，苯酚还可用作溶剂、实验试剂和消毒剂。1997-2002年，美国、西欧、日本等主要地区苯酚需求量保持年均4.2%的速度增长。(5)芴用作有机合成原料。可制成三硝基芴酮，用于静电复印；合成芳基透明尼龙；可代替蒽醌合成阴丹士林

染料；用于制造抗痉挛药、镇静药，镇痛药，降血压药；合成杀虫剂，除草剂；制备抗冲击有机玻璃和芴醛树脂；亦可用作湿润剂，洗涤剂，液体闪光剂，消毒剂等。(6)苊是有机合成原料，经硝化可制硝基苊；进一步氧化可制1,8-萘二甲酸酐和苊醌，可用于合成染料、聚酯树脂、聚酯纤维；还可用于制荧光颜料，药品，杀虫剂等。苊脱氢得苊烯，可制苊烯树脂。二模拟热力学方法的选择及改进模拟所采用的热力学方法是Grayson—Streed（简称GS）法，它对于从轻到中等范围的精炼厂的烃类通常是有用的。在模拟中发现用GS法计算的汽液平衡常数K在一些情况下与实际有些偏差，所以在模拟中进行了一些修正。三煤焦油分离模拟的简单尝试F1F3T2130T1SP1F2WASH144T3144T4CON7502E1M1PITCHCOMP101102R71022002012022032NOIL3013033023MIX1NOIL304500510511501503502521522523S1STEAM1STEAM2OIL两塔式连续蒸馏用PRO/Ⅱ模拟与现场主要操作参数表操作参数PRO/Ⅱ模拟现场数据闪蒸器1出口温度/(oC)105120—130馏分塔1顶部温度/(oC)110.495—115三混馏分侧线温度/(oC)210.806200—220一蒽油馏分温度/(oC)319.341280—295馏分塔2顶部温度/(oC)322.6370—374二蒽油馏分侧线温度/(oC)345.856330—355酚油塔酚油馏分侧线温度/(oC)170.557160—170萘油塔萘油馏分侧线温度/(oC)104198—200洗油塔洗油馏分侧线温度/(oC)266.815225—235馏分塔1底部压力/(kpa)175.18≤150馏分塔2底部压力/(kpa)153.28≤150酚油塔底部压力/(kpa)201.75≤150萘油塔底部压力/(kpa)139.83≤150组分祖坟沥青一蒽油轻油二蒽油酚油萘油洗油煤焦油WATER0.00000.00010.00070.00000.00120.00000.00000.0212BENZENE0.00000.00000.30550.00000.00190.00000.00000.0017TOLUENE0.00000.00000.39480.00000.05000.00000.00000.0031OXYLENE0.00000.00000.00010.00000.02050.00000.00000.0004MXYLENE0.00000.00000.00020.00000.02050.00000.00000.0004PXYLENE0.00000.00000.00020.00000.02050.00000.00000.0004STYRENE0.00000.00000.00000.00000.00050.00000.00000.0000INDENE0.00010.00020.00030.00010.17130.00000.00000.0034BNZPHENO0.00010.00020.00000.00250.00000.00000.00000.00051234HNAP0.00010.00020.00010.00020.15300.00020.00000.0031NAPHTHLN0.00490.01050.00250.00980.24870.99970.09280.09971MNAPHTH0.00090.00180.00010.00390.00000.00000.15290.01252MNAPHTH0.00110.00220.00020.00460.00000.00000.21710.01751ENAPHTH0.00060.00100.00000.00370.00000.00000.07970.00692ENAPHTH0.00050.00090.00000.00350.00000.00000.08040.0069BIPH0.00030.00050.00000.00210.00000.00000.05180.0044ACENAP0.00310.00920.00010.04070.00000.00000.26220.0287FLUORENE0.00180.00800.00000.05770.00000.00000.02750.0137IBUPROFN0.00400.01140.00000.15990.00000.00000.00020.0312ANTHRCEN0.00440.03080.00000.07930.00000.00000.00000.0187PHNANTHR0.00820.02480.00000.15910.00000.00000.00010.0343DPM44DCN0.00670.03190.00000.16400.00000.00000.00000.0349PYRENE0.00760.12910.00000.05450.00000.00000.00000.0237CHRYSENE0.01100.08220.00000.00110.00000.00000.00000.0125INDOLE0.00010.00090.00000.00040.00000.00000.03120.0025BNZNITRL0.00000.00000.00000.00000.01240.00000.00000.0002PHENOL0.00000.00040.00100.00000.00000.00000.00000.0044DIBZTHIO0.00080.00300.00000.01740.00000.00000.00000.0037PYRIDINE0.00010.00020.29390.00000.29940.00000.00000.0075QUINOLIN0.00040.00130.00010.00140.00000.00000.00410.0062C18BENZ0.00810.00330.00000.22560.00000.00000.00000.0443NBP

3370.00000.00000.00000.00000.00000.00000.00000.0000NBP

3500.00000.00000.00000.00000.00000.00000.00000.0000NBP

3590.00030.00130.00000.00480.00000.00000.00000.0011NBP

5530.06850.51240.00000.00360.00000.00000.00000.0772NBP

5790.14880.06100.00000.00000.00000.00000.00000.0843NBP

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6320.15960.01650.00000.00000.00000.00000.00000.0866NBP

6750.16590.00470.00000.00000.00000.00000.00000.0891NBP

7250.13090.00070.00000.00000.00000.00000.00000.0700四煤焦油两塔式分离的模拟与改进M1P1F1P2E1F3

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S24S25S29S26S27S14S15S28S30S31S34S35S32S37S38S36S33S39S40S41S42S43S44STREAM组分酚油萘油洗油精制萘油萘塔底馏分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流程改进M1P1F1P2E1F3

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120T6S1S2S3S4S5S6S10S11S12S17S18S20S21S22S16S19S23S24S25S29S26S27S14S15S28S30S31S43S44S7S8S9S13S32S33S34S35S36S37S38S39S40S41S42S45S46S47S48S49S50S51S52S53S54S55热力学方法的改进通过改变组分的塔板效率系数K，来改变组分在气相及液相中分布，从而使某些馏分的组分要求与现场数据相符1馏分塔热力学方法的改进塔板数3233343536373839萘的K值14151617171818182

甲基萘前处理塔热力学方法的改进3甲基萘塔的热力学方法改进塔板数1918161211109萘的K10111213141516246-三甲酚的K10111213141516塔板数393837363330272625α-甲基萘K60504037362535300.2β-甲基萘K80706050454040350.24酚油预处理塔热力学方法改进5酚油塔热力学方法改进塔板数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塔板数19181715萘K27262423苯酚K0.050.10.150.2五模拟结果与现场数据的比较1两塔式连续蒸馏用PRO/Ⅱ模拟与现场主要操作参数表操作参数PRO/Ⅱ模拟现场数据一段蒸发器出口温度/(oC)105120—130馏分塔顶部温度/(oC)11095—115一蒽油馏分温度/(oC)282.55280—295二段蒸发器顶部温度/(oC)322.6370—374酚油馏分侧线温度/(oC)150.34160—170萘油馏分侧线温度/(oC)225.34198—200洗油馏分侧线温度/(oC)178.23225—235一段蒸发器底部压力/(kpa)105≤130二段蒸发器底部压力/(kpa)110≤150蒽塔塔底部压力/(kpa)130≤150馏分塔底部压力/(kpa)130≤1502模拟各馏分组分含量组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-040.000