-15-第四章精甲醇生产工艺计算工艺计算作为化工工艺设计,工艺管道,设备的选择及生产管理,工艺条件选择的主要依据,对平衡原料,产品质量,选择最佳工艺条件,确定操作控制指标,合理利用生产的废料,废气,废热都有重要作用。4.1甲醇合成塔的物料能量衡算4.1.1合成塔物料平衡计算已知:年产50000吨精甲醇,每年以300个工作日计算,损耗按0.3%计算。则年实际生产精甲醇50150吨。精甲醇中甲醇含量(wt):99.95%粗甲醇组成(wt):[Lurgi低压合成工艺]甲醇:93.89%轻组分[以二甲醚(CH3)2O计]:0.188%重组分[以异丁醇C4H9OH计]:0.026%水:5.896%所以:时产精甲醇:44.694424300100050150Kg/h时产粗甲醇:66.7392%89.93%95.9944.6944Kg/h根据粗甲醇组分,算得各组分的生成量为:甲醇:6944.44Kg/h216.74kmol/h4855.0Nm3/h二甲醚:13.90Kg/h0.302kmol/h6.77Nm3/h异丁醇:1.92Kg/h0.026kmol/h0.58Nm3/h水:432.4Kg/h24.02kmol/h538.1Nm3/h合成甲醇的化学反应为:、主反应:CO+2H2CH3OH+102.37KJ/mol……①副反应:2CO+4H2(CH3)2O+H2O+200.39KJ/mol……②CO+3H2CH4+H2O+115.69KJ/mol……③4CO+8H2C4H9OH+3H2O+49.62KJ/mol……④CO2+H2CO+H2O-42.92KJ/mol……⑤-16-生产中,测得每生产1吨粗甲醇生成甲烷7.56Nm3,即0.34kmol,故CH4每小时生成量为:7.567.39266=55.889Nm3,即2.495kmol/h,39.920Kg/h。忽略原料气带入份,根据②、③、④得反应⑤生成的水的量为:24.02-0.302-0.00783-2.495=21.145kmol/h,即在CO逆变换中生成的H2O为21.145kmol/h,即473.648Nm3/h。5.06Mpa,40℃时各组分在甲醇中的溶解度列表于表4-1表4-15.06Mpa,40℃时气体在甲醇中的溶解度组分H2COCO2N2CH4溶解度Nm3/t甲醇00.6823.4160.3410.682Nm3/h01.0085.5010.5041.008《甲醇生产技术及进展》华东工学院出版社.1990据测定:35℃时液态甲醇中释放CO、CO2、H2等混合气中每m3含37.14g甲醇,假定溶解气全部释放,则甲醇扩散损失为:(1.008+5.501+0.504+1.008)100014.37=0.298kg/h即0.0093kmol/h,0.208Nm3/h。根据以上计算,则粗甲醇生产消耗物料列表4-2及生成物料列表4-3。表4-2甲醇生产消耗物料和生成物量及组成消耗方式单位反应①生Kmol/h成甲醇Nm3/h反应②生Kmol/h成二甲醚Nm3/h反应③生Kmol/h成甲烷Nm3/h反应④生Kmol/h成异丁醇Nm3/h反应⑤CO2Kmol/h逆变换Nm3/h气体溶解Nm3/h扩散损失Nm3/h合计Nm3/h消耗组成%(v)消耗物料合计COH2CO2N2消耗216.74433.484855.09710145650.6041.20813.5427.0840.622.4954.9955.889111.778167.6680.1040.2082.334.666.99(21.145)21.14521.145(473.648)473.648473.648473.6481.00805.0510.5046.5630.20800.4160.6245401.610327.2479.1150.50416208.433.363.712.960.031-17-消耗方式单位反应①生Kmol/h成甲醇Nm3/h反应②生Kmol/h成二甲醚Nm3/h反应③生Kmol/h成甲烷Nm3/h反应④生Kmol/h成异丁醇Nm3/h反应⑤CO2Kmol/h逆变换Nm3/h气体溶解Nm3/h扩散损失Nm3/h合计Nm3/h生成质量Kg/h生成组成%(wt)生成物料合计CH4CH3OHC4H9OH(CH3)2OH2O生成216.744855.04855.00.3020.3026.776.7713.542.4952.49555.88955.889111.7780.0780.581.7472.32921.145473.648473.6481.008(0.208)0.20854.8814855.2080.586.77538.15455.56944.71.9213.90432.4739393.890.0260.1885.896100设新鲜气量为G新鲜气,驰放气为新鲜气的9%[1],驰放气组成与循环气相同。见表4-3。表4-3驰放气组成组分H2COCO2CH4N2CH3OHH2OMol%79.316.293.504.795.490.610.01《甲醇生产技术及进展》华东工学院出版社.1990G新鲜气=G消耗气+G驰放气所以:G新鲜气=G消耗气+0.09G新鲜气=15261.11+0.09G新鲜气则G新鲜气=16770.5Nm3/h新鲜气组成见表4-4表4-4甲醇合成新鲜气组成-18-组分H2COCO2CH4N2总计Nm3/h11558.235560.38556.7821.8050.9817748.17组成mol%65.1231.333.120.120.29100测得:甲醇合成塔出塔气中含甲醇7.12%。根椐表4-2、表4-4,设出塔气量为G出塔。又知醇后气中含醇0.61%。所以有:出塔醇后GG%61.00.4855=7.12%G醇后=G出塔-(G醇+G副+G扩)+GCH4=G出塔-5400.61所以:G出塔=74071.6Nm3/hG循环气=G出塔-(G醇+G副+G扩)+GCH4-G驰放气=74071.6-5456.5+55.89-16770.50.09=67161.6Nm3/h甲醇生产循环气量及组成见表4-5表4-5甲醇生产循环气量及组成组分COCO2H2N2CH4CH3OHH2O合计流量:Nm3/h4224.52350.753265.73687.23217388.616.7167140.4组成%(V)6.293.5079.315.494.790.610.01100G入塔=G循环气+G新鲜气=67161.6+16770.5=83932.1Nm3/h由表4-4及表4-5得到表4-6。表4-6甲醇生产入塔气流量及组成单位:Nm3/h组分COCO2H2N2CH4CH3OHH2O合计流量:Nm3/h9794.882904.1644683738.23238.8388.615.8883932.1组成(V)%11.673.4676.814.1173.860.4630.007100又由G出塔=G循环气-G消耗+G生成据表4-2、4-6、得表4-7。组分COCO2H2N2CH4入塔9794.882904.164468.253738.23238.8-19-消耗5401.6478.710327.20.5041.008生成55.89出塔4392.32425.454141.13737.73293.7组成(V)%7.23.2772.235.044.44组分CH3OHH2OC4H9OH(CH3)2O合计入塔388.615.8883932.1消耗16209生成4855.21538.10.586.775456.5出塔5243.82543.980.586.7773785.4组成(V)%7.080.7340.00080.009100甲醇分离器出口气体和液体产品的流量、组成见表4-8。表4-8甲醇分离器出口气体组成、流量:单位:Nm3/h组分COCO2H2N2CH4损失1.0085.05100.5041.008出气4391.22420.354141.13737.23292.6组成(V)%6.43.5479.195.474.82出液组成Mol%重量Kg组成(wt)%组分CH3OHC4H9OH(CH3)2OH2O合计损失0.2087.679出气388.368371.7组成(V)%0.567100出液4855.2080.586.77538.15400.66组成Mol%89.90.0110.1259.96100重量Kg6944.71.9213.9432.47392.92组成(wt)%93.940.0260.1885.58100甲醇驰放气流量及组成见表4-9。表4-9甲醇驰放气流量及组成组成COCO2H2CH4CH3OHN2合计-20-流量Nm3/h166.669.6875.475.63.04501209.4组成(V)%13.785.7572.46.250.254.13100粗甲醇贮罐气流量及组成见表4-10。表4-10贮罐气组成、流量组成COCO2H2CH4CH3OHN2合计流量Nm3/h1.0085.05101.0080.2080.5047.679组成(V)%13.1365.77013.132.716.56100由表4-2、表4-10、可得表4-11。表4-11甲醇生产物料平衡汇总表组分新鲜气入塔气循环气流量组成流量组成流量组成Nm3/h(V)%Nm3/h(V)%Nm3/h(V)%CO5560.3831.339794.8811.674224.56.29CO2556.783.122904.13.462350.73.5H211558.2365.1264468.2576.8153265.779.31N250.980.293738.24.1173687.25.49CH421.800.123238.83.863217.04.79CH3OH388.610.463388.610.61C4H9OH(CH3)2OH2O5.880.0076.710.01合计17748.1710083932.110067140.4100组分出塔气醇后气流量组成流量组成Nm3/h(V)%Nm3/h(V)%CO4392.27.24391.17.7CO22425.43.272420.33.5H254141.172.2354141.178.10N23737.75.043737.25.385CH43293.74.443292.64.75-21-CH3OH5243.827.08391.650.565C4H9OH0.580.0008(CH3)2O6.770.009H2O543.980.734很少合计73785.410068374100根椐计算结果,可画出甲醇生产物流图,如:图4-1甲醇生产物流图新鲜气循环气入塔气驰放气醇后气储罐气出塔气粗甲醇图4-1甲醇生产物流图4.1.2合成工段能量计算1.合成能量计算已知:合成塔入塔气为220℃,出塔气为250℃,热损失以5%计,壳层走4MPa的沸水。查《化工工艺设计手册》得,4MPa下水的气化潜热为409.7kmol/kg,即1715.00kJ/kg,密度799.0kg/m3,水蒸气密度为19.18kg/m3,温度为250℃。入塔气热容见4-12。表4-125MPa,220℃下入塔气除(CH3OH)热容组分COCO2H2N2CH4合计流量:Nm3/h9794.882904.164468.255174.413238.885580.44比热:kJ/kmol℃30.1545.9529.3430.3547.05/热量:kJ/℃13183.75957.384441.97010.96802.9117396.7查得220℃时甲醇的焓值为42248.46kJ/kmol,流量为388.61Nm3。所以:Q入=42248.464.2261.388+117396.7220甲醇合成塔分离塔冷凝器粗甲醇储罐-22-=732954.4+25827274=26560228.2kJ出塔气热容除(CH3OH)见表4-13。表4-135MPa,250℃下出塔气除(CH3OH