年产4200吨环氧氯丙烷车间合成工艺设计

SHAPE\*MERGEFORMAT内容摘要设计对年产4200吨环氧氯丙烷车间氯丙烯合成工段进行了工艺设计。并对环氧氯丙烯的生产方法、生产原理、流程路线，物料衡算，能量衡算以及主要设备等进行了论述和计算。关键词：环氧氯丙烯AbstractThisdesignsynthesizestheproductionmethodoftheworksegmentandproduceto42,00tonEC/yearprinciple,processrouteandmainequipmentsetc.proceededthetreatise.Keywords:3-chloro-1-propene、3-chloropropene、引言环氧氯丙烯是一种重要的有机化工原料和精细化工产品，用途十分广泛。以它为原料制得的环氧树脂具有粘结性强，耐化学介质腐蚀、收缩率低、化学稳定性好、抗冲击强度高以及介电性能优异等特点，在涂料、胶粘剂、增强 材料 关于××同志的政审材料调查表环保先进个人材料国家普通话测试材料农民专业合作社注销四查四问剖析材料 、浇铸材料和电子层压制品等行业具有广泛的应用。此外，环氧氯丙烷还可用于合成甘油、硝化甘油炸药、玻璃钢、电绝缘品、表面活性剂、医药、农药、涂料、胶料、离子交换树脂、增塑剂、（缩）水甘油衍生物、氯醇橡胶等多种产品，用作纤维素酯、树脂、纤维素醚的溶剂，用于生产化学稳定剂、化工染料和水处理剂等。目录i内容摘要i引言i目录11文献综述11.1环氧氯丙烯在国民经济中的重要作用11.2环氧氯丙烯的生产原料及主要产品11.3环氧氯丙烯的工业生产方法及选择1.4环氧氯丙烯的用途1.5环氧氯丙烯的物理化学性质12生产流程和设备12.1理论生产流程简述12.2设备生产流程建树12.3设备论述及其选择2.3.1氯化反应器12.3.2冷蒸塔12.4小结13计算13.1反应器的物料衡算13.1.1管式反应器13.1.2塔前换热器13.1.3冷蒸塔13.1.4精馏塔13.1.5水洗塔13.1.6碱洗塔13.2反应器热量计算13.2.1反应焓的计算13.2.2部分产物由355k～773k焓值的变化13.2.31,2-Da,1,3-De由355k～773k焓值的变化13.2.4计算丙烯预热温度13.3设备衡算13.3.1反应器3.3.21氯精二塔14附录1参考文献1文献综述1.1环氧氯丙烯在国民经济中的重要作用环氧氯丙烯是一种重要的有机化工原料和精细化工产品，用途十分广泛。以它为原料制得的环氧树脂具有粘结性强，耐化学介质腐蚀、收缩率低、化学稳定性好、抗冲击强度高以及介电性能优异等特点，在涂料、胶粘剂、增强材料、浇铸材料和电子层压制品等行业具有广泛的应用。此外，环氧氯丙烷还可用于合成甘油、硝化甘油炸药、玻璃钢、电绝缘品、表面活性剂、医药、农药、涂料、胶料、离子交换树脂、增塑剂、（缩）水甘油衍生物、氯醇橡胶等多种产品，用作纤维素酯、树脂、纤维素醚的溶剂，用于生产化学稳定剂、化工染料和水处理剂等。1.2环氧氯丙烯的生产原料及主要产品环氧氯丙烯是一种重要的有机化工原料和精细化工产品，用途十分广泛。以它为原料制得的环氧树脂具有粘结性强，耐化学介质腐蚀、收缩率低、化学稳定性好、抗冲击强度高以及介电性能优异等特点，在涂料、胶粘剂、增强材料、浇铸材料和电子层压制品等行业具有广泛的应用。此外，环氧氯丙烷还可用于合成甘油、硝化甘油炸药、玻璃钢、电绝缘品、表面活性剂、医药、农药、涂料、胶料、离子交换树脂、增塑剂、（缩）水甘油衍生物、氯醇橡胶等多种产品，用作纤维素酯、树脂、纤维素醚的溶剂，用于生产化学稳定剂、化工染料和水处理剂等。1.3环氧氯丙烯的工业生产方法及选择目前，工业上环氧氯丙烯的生产方法主要有丙烯高温氯化法和乙酸丙烯酯法两种。丙烯高温氯化法是工业上生产环氧氯丙烷的经典方法，由美国Shell公司于1948年首次开发成功并应用于工业化生产。目前，世界上90%以上的环氧氯丙烷采用此法进行生产。其工艺过程主要包括丙烯高温氯化制氯丙烯，氯丙烯与次氯酸化合成二氯丙醇，二氯丙醇皂化合成环氧氯丙烷3个反应单元。1.4环氧氯丙烯的用途氯丙烯作为一种重要的石油化工中间产品，一般不直接作为商品出售，主要是用于生产环氧氯丙烷、丙烯醇、甘油、烯丙胺、烯丙酯等下游产品。由于氯丙烯是含氯的烯烃化合物,具有氯有机化合物和烯烃的重要特征。能与乙醇、氯仿、乙醚、丙酮、苯、甲苯、四氯化碳和石油醚混溶。可发生氧化、加成、取代、烷基化等多种反应,使其在医药、农药、香料、塑料阻燃、有机合成等方面具有广泛的应用。二战期间得到迅速发展,成为有机合成的重要中间体,其消耗量逐年增加。氯丙烯一般不直接作市场商品出售,而是广泛用于合成树脂、医药、香料、农药和有机合成原料。其主要用途是生产环氧氯丙烷;用作合成甘油和合成树脂的原料,其余用来生产丙烯醇、丙烯胺和药物等1.5环氧氯丙烯的物理化学性质氯丙烯中文名称有3-氯-1-丙烯、3-氯丙烯、烯丙基氯；英文名称有3-chloro-1-propene、3-chloropropene、chloride、。化学式：CH2=CHCH2Cl；分子质量：76.50；性状：常温下为无色液体，有辛辣味，易挥发。性活泼，能发生加合反应及聚合反应，水解成丙烯醇，易燃。沸点：44.6℃；熔点：-136.4℃；相对密度：液态0.9382g/c（20/4℃）蒸气压：49.05KPa(25)℃；溶解度：水中：20℃时0.36g/100ml闪点：-31.67℃自然温度：390℃爆炸极限：下限2.9%，上限11.2%；油水分配系数：辛醇/水分配系数的对数值：-0.24；遇热或明火有着火危险，遇明火可爆炸，危险程度中等，能与HNO3、H2SO4、哌嗪、乙二胺、氯磺酸，NaOH发生激烈反应。2生产流程和设备2.1理论生产流程简述1.丙烯高温氯化制氯丙烯丙烯与氯气经干燥、预热后以摩尔比4～5:1混合进入高温氯化反应器，短时间(约3s)内进行反应，生成氯丙烯和氯化氢气体。精制后得氯丙烯产品，同时副产D-D混剂(1,2-二氯丙烷和1,3-二氯丙烯)，氯化氢气体经水吸收后得到工业盐酸。CH2=CHCH2+Cl2→CH2=CHCH2Cl+HCl2.氯丙烯次氯酸化合成二氯丙醇氯气在水中生成次氯酸(或采用介质叔丁醇和氯气在NaOH溶液中反应生成叔丁基次氯酸盐，该盐水解生成次氯酸，叔丁醇循环使用)，次氯酸与氯丙烯反应生成二氯丙醇(过程中二氯丙醇浓度一般控制在4%左右)。2CH2=CHCH2Cl+2HOCl→ClCH2CHClCH2OH+ClCH2CHOHCH2Cl(2,3-二氯丙醇，70%)(1,3-二氯丙醇，30%)3.二氯丙醇皂化合成环氧氯丙烷二氯丙醇水溶液与Ca(OH)2或NaOH反应生成环氧氯丙烷。ClCH2CHClCH2OH+ClCH2CHOHCH2Cl+1/2Ca（OH）2→ClCH2CHClCH2OH+ClCH2CHOHCH2Cl+1/2Ca（OH）2→丙烯高温氯化法的特点是生产过程灵活，工艺成熟，操作稳定，除了生产环氧氯丙烷外，还可生产甘油、氯丙烯等重要的有机合成中间体，副产D-D混剂（1，3-二氯丙烯和1，2-二氯丙烷）也是合成农药的重要中间体。缺点是原料氯气引起的设备腐蚀严重，对丙烯纯度和反应器的材质要求高，能耗大，氯耗量高，副产物多，产品收率低。生产过程产生的含氯化钙和有机氯化物污水量大，处理费用高，清焦周期短。2.2数据生产流程简述1.丙烯：经各部热交换后与反应器的氯化物逆向进行热交换，使丙烯预热至360—380℃，进入氯化反应器，与氯气按配比为5：1的比例在反应器中反应，生成氯丙烯的的混合物，反应温度控制在500℃，但不能超过510℃。氯化物进入换热器与丙烯间直接进行热交换后进入冷蒸塔，以丙烯液体进入喷淋；丙烯液体汽化吸收热量进入冷却器除去高氯化物；从塔顶蒸出丙烯与氯化氢；然后经过水洗塔，碱洗塔，除去HCl气体后进入压缩机，除水，除油，干燥，再压缩，全凝器后进入丙烯贮罐。从塔釜出来的高氯化物进入粗氯化物贮罐，再抽入精馏一塔进行精馏除去轻组分，从塔釜的高沸物进入精馏尔塔，除1,2—Da，1,3—De。从塔顶得到99.5%的氯丙烯。2.氯化氢（HCl）：从反应出来的气体中，与氯丙烯有相当量的HCl气体，在冷蒸塔塔顶和丙烯一同蒸出；在水洗塔中，通入不同浓度的盐酸溶液在水洗塔的不同位置进行喷淋，使得在塔釜出来的盐酸质量浓度达到25%，进入盐酸贮罐，作为氯丙烯的副产物而销售。其余的少量HCl气体在碱洗塔中除去，用质量百分比浓度为13—15%的NaOH溶液进行喷淋，在塔底时的碱浓度不能超过6%，并且直接进行排放，除HCl气体。3.少量的氮气：在Cl2中有少量的N2，N2是不活泼的气体，不与原料或生成的产物进行反应，所以N2的量没有变，也没有给反应带来危险和造成分离上的困难。N2由于K平衡很大，也同样从冷蒸塔顶出来，并且随丙烯进入一段压缩，在水冷却器河沿冷却器上直接排空出去。4.其他的高沸物在精馏二塔塔釜直接进入“DD混合剂”贮罐。2.3设备论述及其选择2.3.1氯化反应器因反应温度控制在500℃，反应物和生成物绝大部分属于易燃，易爆物品，要求设备能耐高温，密封好。结构上要求能使氯气和进料丙烯快速的混合；不能存死角，清碳方便。现有设备采用绝热反应的型式，必须严格控制反应温度，又要求反应完全，则在反应器的长度上有严格的计算要求。按照化工厂的型式选择长管式反应器，这里有反应的生产能力和快速混合所决定，采用喷射式混合器；在喉管与混合器连接的角度为32o，在椎体与反应器连接的椎角度为300。具有的计算在设备计算中。2.3.2冷蒸塔据物料平衡计算塔顶要求的工艺温度为-40℃，塔釜要求的工艺温度为56℃。由于反应的生成物中有大量的HCl气体，对各种金属设备的腐蚀性很大，所以在冷蒸塔内壁采用石墨砖防腐。并且该塔分为蒸出和冷凝两部分，在冷凝部分用丙烯蒸化气体吸收热来冷却，温度很低。而塔釜温度要求为50℃，则用列管加热器。并且用高压的热水进行加热。2.4小结要对工业装置进行设计，必须要对工业流程中各种设备及单元操作进行分析，了解物料衡算，能量衡算以及设备衡算的方法。3计算设计任务：年产量4200吨环氧氯丙烷/年设计依据：1.年工作日按300天计，每天24小时连续生产，即7200小时/年2.消耗定额：1.6吨液氯/1吨环氧氯丙烷3.各段收率： 氯化 氯精 环化 总收率 75% 98% 64% 47%4.原料纯度：新鲜丙烯：丙烯98%，丙烷2%；循环丙烯100%（mol%）液氯：氯气99.5%，氮气2%5.中间产品规格：3-氯丙烯（AC）≥98%(CH2=CHCH3mol)6.原料配比：氯气：丙烯=1：4.57.氯化反应方程式及粗氯化物（反应产物中除C3=，HCl,N2外）组成Xi(mol)CH2=CHCH3+Cl2—CH3CCl=CH2+HCl4.1%CH2=CHCH3+HCl—CH3CHCl–CH30.6%CH3CH2CH3+Cl2—CH3CHCl–CH3+HCl2.0%CH2=CHCH3+Cl2—CH2=CHCH2Cl+HCl79.9%CH2=CHCH3+Cl2—CH3CHClCH2Cl7.6%CH2=CHCH3+2Cl2—CH2ClCH=CHCl+2HCl5.8%忽略C3=在氯气中的燃烧8．进料Cl2和C3=全部反应掉（α=100%）3.1物料衡算3.1.1管式反应器1.液氯进料量：W液氯=4200ⅹ103ⅹ1.6÷7200=933.3333kg/h液氯的平均分子量：M平=71ⅹ0.995=28ⅹ0.005=70.8kg/hG液氯=W液率÷M=933.3333÷70.8=13.1827kmol/h其中氯气量：g氯气=G液氯×0.995=13.1827×0.995=13.1168kmol/hg氮气=G液氯×0.005=13.1827×0.005=0.0392kmol/h2.丙烯总进料量：G丙烯=4.5×g氯气=4.5×13.1168=59.0255kmol/h3.粗氯化物的生成量g氯气=G粗×（4.1+2.0+79.9+7.6+5.8×2）%=1.052×G粗G粗=g氯气÷1.052=13.1168÷1.052=12.4684kmol/h其中各组分：g粗I=G粗×4Ig粗2-e=12.4684×4.1%=0.5112kmol/hg粗2-a=12.4684×2.%=0.2494kmol/hg粗AC=12.4684×79.9%=9.9622kmol/hg粗1，2-dc=12.4684×7.6%=0.9468kmol/hg粗1，3-de=12.4684×5.8%=0.7232kmol/h4.HCl生成量：gHCl=G粗×（4.1-0.6+2.0+79.9+0+5.8×2）=0.97G粗=0.97×12.4684=12.0943kmol/h5.新鲜丙烯进料量：G新鲜C3==G粗=12.4684kmol/h其中g新鲜中的纯C3==G新鲜C3=×98%=12.4684×0.98=7.2733kmol/hG新鲜C3=×2%=12.4684×2%=0.2492kmol/hG循还C3==G总C3=-g新鲜C3==59.0255-12.3170=46.7085kmol/h表3.1反应器物料衡算表 序号 组分 分子量 进料 出料 Kmol/h Mol% Kg/h Wt% Kmol% Mol% Kg/h Wt% 12345678910∑ N2HClC3=b丙烯C30丙烷Cl22-e2-aAC1,3-Da1,3-De/ 2836.4642.0174470.90676.52978.54176.526112.98110.97/ 0.701060.200.28113.91000O075.90 0.094081.460.3418.10000O0/ 1.880102899.9011,9987987.09000O0/ 0.00049072.45720.3227.17000O01.0 0.071067.109949.4409000.5010.35911.90871.10981.1474.8 0.000916.9365.52000.720.4513.941.331.011.0 1.90227.10992109.980041.901729.0989897.94120.6787.353594.80 0.063614.0164.94001.200.8125.973.592.493.1.2塔前换热器反应气体气（A）+液（B）混合物F,Zit=-10℃,P=150KPa安托因 公式 小学单位换算公式大全免费下载公式下载行测公式大全下载excel公式下载逻辑回归公式下载 :InPSi=A-B/(T+C)式中:PSi——饱和蒸气压A,B,C——常数根据上式计算结果见下表表3.2塔前换热器物料计算1 组分i An公式中 lnPiS=A–B/(T+C) PiS(mmHg) Ki=PiS/P=PiS/750.1×1.5 A B C DC2-e2-a3-De12-Da13-De 15.702715.929816.038415.977216.038518.0753 1807.532395.1492490.482531.922985.074311.962 -26.15–38.15–43.15-47.15-52.16-0.1455 8.07125.27764.71034.24721.88051.6997 3200.9407–38.15111.088569.90946.55685.3088 2.84490.17410.09870.0620.00580.004718由式:∑xi=∑Zi/[Ki+(1-Ki)e]通过试差法得e=0.19计算结果见下表表3.3塔前换热器物料计算2 组分i 组成Zi Ki xi=Zi/[Ki+(1-Ki)e] Kmol/h yi=ai/∑ai fi=FZi bi=Fexi ai=fi-bi N2HClC3=2-e2-aAC12-Da13-De∑ 0.092316.9365.520.720.4513.941.331.01100.0 ∞∞2.84500.19840.09910.68980.005890.004718/ 000.26290.2170.1660.57050.06790.05411.0 0.07412.98748.98470.5190.34710.4090.9810.70275.9474 002.9873.1080.2398.2090.9210.69916.163 0.07413.98753.0980.2490.0811.8020.0180.01168.198 0.0011840.20110.78940.0034980.0032980.039080.003310.002211.0表3.4塔前换热器物料平衡表 组分i 进料Kmol/h 出料 气体A 液体B Kmol/h Mol% Kg/h Wt% Kmol/h Mol% Kg/h Wt% NHClC3=2-e2-aAC12Da13De∑ 0.07412.98748.98470.5190.34710.4090.9810.70275.9474 0.07412.98750.12090.2280.0981.8810.180.01265.6889 0.12220.1079.910,3180.1013.1010.0370.021100.0 1.9801460.21091980.9814.900929.9807169.09892.90871,90892719.9083 0.082418.1272.010.7111.0987.1090.00990.0701100 003.8980.3100.2408.3010.9910.70114.311 0028.22.911.88156.015.914.901100.0 00189.0925.09818.908608.09109.9087.0981028.094 0016.402.3551.72962.66510.716.082100.03.1.3冷蒸塔Pi气PD=140Kpa,tD=-40℃液态C3=回收段，Cu,i---回收度Fi=(ai+bi)P=150Kpa,t=-10℃蒸出段，Si=VKi/L蒸汽Pw=160KpaTw残液（粗氯化物）计算结果见下图表3.5冷蒸汽塔换热器物料计算1 组分i 进料F(Kmol） tD,PD,下KD,i 进料下Ki T冷，均P冷，均K冷,i T蒸，均P蒸，均K蒸,i TW,PW,下的KW,i Cu,i C0,i xi=Cu,i×C0,i 1/(1-xi) 气相ai 液相bi NHClC3=2-e2-aAC12Da13De∑ 0.07413.98753.0980.2490.0811.8020.0180.01168.198 003.8980.3100.2408.3010.9910.70114.311 ∞∞1.01510.03690.01810.01120.0070.007/ ∞∞2.9091.8210.1080.0710.0060.004/ ∞∞1.89020.9710.6010.02820.00220.021/ ∞∞8.0210.7810.4600.3310.0440.022/ ∞∞15.012.0310.6910.9810.1840.143/ 000.01590.32290.64540.98111.01.0/ 1.01.00.960.0970.0650.0440.0060.005/ 000.1510.2990.03930.01620.00620.0046/ 1.01.01.0241.1381.0411.0061.00661.004/由公式得上升气体量υ总i=(ai+biC0,i)×回收液体l总,i,=V总.iCu,I(Kmol/h)残余气体VD.i=Vi-Vl(Kmol/h)YD.i=VD,i/∑VD,iXD,i=YD,i/KD,i根据上面的程序计算结果见下表表3.6冷蒸汽塔换热器物料计算2 组分i ai+bi×C0,i(Kmol/h)i(i V总 L总 VD,i yD,,i xD,,i NHClC3=2-e2-aAC12Da13De∑ 0.07413.98753.0980.26810.12092.60910.031920.0188868.2830 0.07413.98754.10980.27210.12512.80910.021990.0189770.8911 000.068690.079810.070112.69010.028190.019043.4091 0.07413.98753.0980.17010.048010.056710069.9801 0.0011150.20500.79970.0030120.006970.000901oo1.0 000.77880.080820.44670.09580001.0由公式总和液体量：υ总i=(ai+biCU,i)×蒸出气体：l总,i,=(bi+aiCU,i)×残余液体：LW.i=l总,i－υ总iYD.i=VD,i/∑VD,iXD,i=YD,i/KD,i根据上面的程序计算结果见下表表3.7冷蒸汽塔换热器物料计算3 组分i ai+bi×C0,i(Kmol/h)i(i V总 L总 VD,i yD,,i xD,,i NHClC3=2-e2-aAC12-Da13-De∑ 004.09120.38710.27999.49800.90880.709116.1009 004.01190.37210.22519.30910.90810.699815.7891 003.88690.049810.018110.38910.0050910.0029894.0190 000.78780.37010.28018.89010.92010.699015.2097 000.0072970.027990.022620.79800.81900.062511.0 000.10670.060820.034670.79900.14980.009311.03.1.4精馏塔1.氯精一塔（低沸塔）(1)按清晰分割计算(2)由工艺要求给出两个关键组分选l为2-a，xW,2-a≤1%(mol%)选h为Ac，xD,AC≤5%(mol%)(3)泡点进料根据以上条件计算结算结果见下图表3.8氯精一塔物料衡算表 组分i 进料F(kmol/h) 塔顶di 塔釜wi C3=2-e2-aAC12-Da13-De∑ 0.080910.33010.26019.89010.90910.709811.9981 0.80910.33010.2459-0.01W0.05D00 000.01W9.8901-0.05D0.89900.6843由上表得,D=0.4460W=117844于是计算结果如下表3.9氯精一塔物料平衡表 组分i 相对挥发度a(mol) 进料Fi(mol) 进料组成xiF(mol%) 塔顶di(mol) 塔釜wi(mol) 塔顶组成Xi,d(mol%) C3=2-e2-aAC12-Da13-De∑ 45.78702.82211.601310.094740.07594/ 0.080910.33010.26019.89010.90910.709811.9981 0.0072720.027900.022490.79790.081880.62681.0 0.080910.30010.15010.02866000.4460 000.10489.99810.91080.701011.7488 0.14350.55040.25630.0500001.0回流比的计算:其中:ai－组分i的相对挥发度　XiF－进料组分的摩尔组成q－进料的液相分率;此处q=1;Rm　－最小回流比(XiD)－最小回流比流出液体组分I的摩尔分率;θ　－方程的根;对于有c个组分的系数有c个根,只取aLK›θ›aHK于是．解　得　θ　＝１５.７４２取R=1.3得R=1.3×15.742=20.4646理论塔板数计算最小理论板数公式:于是查吉兰特图得Y=0.40解得N=22.1373取塔板效率η=0.75得N实际=N/0.75=29.5164所以取N实际=30(块)进料位置的计算精流段的最小理论塔板数为NR=11.4901/0.40=28.7252NR实际=28.7272/0.75=38.30(块)所以取NR实际=39(块)2.氯精二塔（高沸塔）选l为Ac,xW,AC≤3%(mol%)h为1,2-Da,xD,1,2-Da≤0.5%(mol%)最终xD,AC≥98%(1)按照清晰分割计算(2)按照非清晰分割根据上述条件计算计算结果见下图表3.10氯精二塔物料衡算表 组分i 进料Fi(mol) 塔顶di(mol) 塔釜wi(mol) 2-aAC12-Da13-De∑ 0.26019.89010.90910.709810.6902 0.26019.8901-0.05D0.004D0 00.03W0.9091-0.005D0.7098由以上表3.10得D=11.7490W=1.84于是计算计算结果见下表表3.11氯精二塔物料衡算结果表 组分i 相对挥发度a(mol) 进料Fi(mol) 进料组成xiF(mol%) 塔顶di(mol) 塔釜wi(mol) 塔顶组成Xi.d(mol) 2-aAC12-Da13-De∑ 16.902410.555210.8016/ 0.26019.89010.90910.709810.6902 0.01010.83900.86890.66511.0 0.26019.40810.0043708.7490 00.00440.89010.70981.53 0.11810.98230.004901.0回流比的计算EMBEDEquation.3因为‹2根据要求取=2取R=1.3R=1.3×2=2.63.1.5水洗塔依据：1.冷蒸塔顶喷淋丙烯量（为进料丙烯的1/2）。2.采用15℃井水吸收剂。3.设HCl的吸收率为95-99%（粗氯化物全部溶解在盐酸中）。4.忽略丙烯，氮气溶解水中，塔顶蒸汽中水蒸汽饱和。计算：(1）塔底进口气体量及组成：VD=VD(冷蒸塔)+1/2×G总C3=48.17198+1/2×48.1342=99.7908kmol/h；(2）塔顶出口干气量：VN,干=VD-0.95VD，HCL-VD，粗氯=99.7908-0.95×7.199-0.201877=78.749873kmol/hkmol/h(3)塔顶出气带水量：yN,H2O=vN,H2O/vN=vN,H2O/(vN,干+vN,H2O)=78.749873×0.018171/(1.3-0.018171)=0.67851kmol/hPH2Os/PN,总经推：vN,H2O=VN,干×[PH2Os/（PN,总-PN，H2Os）](4）15%盐酸量：W盐酸=0.95vD,HCl×MHCl/0.15=2296.9876kg/h(5）进塔吸收剂（井水）量：W井水=WH2O+vN,H2O×18=1747.9081kg/h根据以上计算塔顶出口气体组成表3.12水洗塔塔底出口气体组成 组分 摩尔流量(kmol/h) 摩尔含量(%) 摩尔流量(kg/h) N2HClC2=H2OAC 0.092313.98765.520.66240.55 0.0916.8498.160.2550.72 1.799023.87693209.98094.01014.890计算得塔顶出口干气量25℃下水的饱和蒸汽压:塔顶出气带水量15%的盐酸量:进塔吸收剂量:根据以上公式,计算塔顶出口气体组成表3.13水洗塔塔顶出口气体组成 组分 摩尔流量(kmol/h) 摩尔含量(%) 摩尔流量(kg/h) N2HClC2=H2O 0.09230.609365.520.6624 0.090.8498.160.95 1.799023.87693209.980912.01013.1.6碱洗塔1.设HCl全部被NaOH液中和掉。2.新碱液浓度为15%（wt%），降至5%排出。3.忽略C3=,N2的溶解损失，出塔尾气中水蒸汽达到饱和。计算：(1)塔顶出口干气量:VN，干,=vD-vD,粗氯-vD,HCl=99.7908-0.201877-7.199=79.389923kmol/h塔顶出气带水量塔顶出气带水量25℃水PH2O2.45atm3)耗碱量：根据以上公式计算物料衡算表表3.14碱洗塔的物料衡算表 组分 入塔尾气(kmol/h) 喷淋液体(kmol/h) 塔顶排气(kmol/h) 塔釜排气(kmol/h) N2C3=HClH2ONaOHNaCl 0.092365.520.60930.662400 000399.9232.90870 0.092365.5201.399800 000.5989399.9232.97090.59893.2反应器热量计算C3=+Cl2→2-e+HCl-29.0C3=+Cl2→2-a-16.7=C3=+Cl2→2-a+HCl-16.7C3=+Cl2→AC+HCl-26.7C3=+Cl2→1,2Da-44.07C3=+Cl2→1,3De-51.0Cl2293.15KCp=6.432+8.082x10-3x293.15-9.241x10-6x293.15+3.695x10-9x293.15=8.09966355KCP=6.432+8.082x10-3x355-90241x10-6x3552=8.30172CP-=(8.09966+8.30172)/2=8.20C=3355KCP=0.886+5.602x10-3x355-2.771x10-5x3552+5.266x10-9x3553=17.514542-e355KCP=5.12x39.81x10-3x355-9.44x10-6x3552=18.0627773KCP=5.12x39.81x10-3x773-9.44x10-6x773=30.25246CP-=（18.06287+30.25246）/2=24.157672-a355KCP=0.2885426+8.338043x10-2x355-54.24319x10-6x3552+14.22245x10-9x3553=23.68889773KCP=38.89794CP-=（23.68889+38.89794）/2=31.293415AC355KCP=5.27+49.46x10-3x355-17.61x10-6x3552=20.60899773KCP=32.98009CP-=（20.60899+32.98009）/2=26.794051，2-Da355KCP=34.49+0.07724x355=41.27368（液体）773KCP=34.94+0.07724x97.37=42.46186CP液-=（41.27368+42.46186）/2=41.86727（气体）370.37KCP=7.55+64.96x10-3x370.37-24.8x10-6x370.372=28.20732773K，CP=42.94636CP-=（28.20732+42.94636）/2=35.576341，3-De355KCP=7.41+45.08x10-3x355-13.87x10-6x3552=21.66443773KCP=33.96911CP-=（21.66443+33.96911）/2=27.81727C3O355KCP=-1.009+7.315x10-2x355-3.789x10-5x3552+7.6878x10-9x3553=20.52667HCl355KCP=6.7+0.000847x355=7.000785773KCP=5.7+0.000847x773=7.354831CP-=（7.000785+7.354831）/2=7.177308：(25+273.15)～355k=56.85K=326.575℃EMBEDEquation.DSMT4=9.3691x8.20x62=4763.25kcal:（25+273.15）k～773k=474.85K=535.575KEMBEDEquation.DSMT4=0.056495×7.112×474.85=190.79kal/h:设预热温度为==(355-T)K=0.886+5.602×EMBEDEquation.DSMT4-2.771×EMBEDEquation.DSMT4+5.266×EMBEDEquation.DSMT4EMBEDEquation.DSMT4=50.594××(355-T)3.2.1反应焓的计算3-e:+→+HCL(-26.7kcal/h)6.9924×(-26.7)×=-199950.09kcal/h2-a:--+→+HCl(-16.7kcal/h)0.2275×(-16.7)×=-3089.3kcal/h2-e:+→+HCL(-29.0kcal/h)0.3501×(-29.0)×=-10643.0kcal/h1,2-Da:=CH-+→(-44.0kcal/h)0.6651×(-44.0)×=-29933.2kcal/h1,3-De:=CH-+2→+2HCl(-51.0kcal/h)0.5076×(-51.0)×=-26474.1kcal/h综上所得之和=-260989.99kcal/h3.2.2部分产物由355k～773k焓值的变化=418K=564KHCL:=7.235-0.172×T+2.976×EMBEDEquation.DSMT4-0.931×EMBEDEquation.DSMT4=7.1773kcal/kmol•k=10.366×8.7515×418=37620.3kcal/kmol•k:=0.886+5.602×T-2.771×EMBEDEquation.DSMT4+5.266×EMBEDEquation.DSMT4=17.5145kcal/kmol•k=17.5145×32.8532×418=82805.9kcal/kmol•k2-e:=3.2574+6.2412×T-1.1431×EMBEDEquation.DSMT4+0.008775×EMBEDEquation.DSMT4=24.1577kcal/kmol•k=24.1577×0.3501×418=3705.9kcal/kmol.k2-a:=0.440+8.330×T-5.539×EMBEDEquation.DSMT4+1.4×EMBEDEquation.DSMT4=31.2934kcal/kmol•k=0.2275×31.2934×418=2341.4kcal/kmol•k3-e:=0.604+7.277×T-5.442×EMBEDEquation.DSMT4+1.742×EMBEDEquation.DSMT4=30.2941kcal/kmol•k=6.9924×20.2941×418=100098.6kcal/kmol•k=296572.13.2.31,2-Da,1,3-De由355k～773k焓值的变化1,2-Da：沸点为369.5K,355k～369.5k～773k变化过程是由液体（）变气体(g)的变化。气体(g)：1,2-Da:=2.496+8.729×T-6.219×EMBEDEquation.DSMT4+1.849×EMBEDEquation.DSMT4=35.57634kcal/kmol.k=0.24=577k在355k～369.5k的变化过程中：=14.5K=362.25KR=1.987==0.6278=2.56+0.436+w[2.91+4.28×+0.296]=5.7963代入数据后得出=45.08405kcal/kmol.k=45.08405×0.6651×14.5=444.7248kcal/h=0.6651×403.5×33.5668=9214.1218kcal/h=0.6651×7500=5102.25kcal/h=++=14761.0966kcal/h1,3-De：沸点377.5K,355k～369.5k～773k变化过程是由液体（）变气体(g)的变化气体:=3.4055+6.3667×T-0.3812×EMBEDEquation.DSMT4+0.008652×EMBEDEquation.DSMT4=27.8173kcal/kmol.k==0.648625=0.294=0.829296=2.56+0.436+w[2.91+4.28×+0.296]代入数据后得出=6.262844×1.987+29.0954=41.4958=0.5076×41.4958×22.5=484.6606kcal/h=0.5076×29.0954×395.5=6800.7733kcal/h=0.5076×(8.1×1.10962)×=4665.6303kcal/h=++=19951.0642kcal/h3.2.4计算和丙烯预热温度+++EMBEDEquation.DSMT4×0.95++EMBEDEquation.DSMT4+EMBEDEquation.DSMT4=04763.25+159.06+35.57634××(355-T)+（-260989.99）×0.95+206572.1+14761.0966+11951.0642=0试差法：得T=606-273.15=336℃热损失为20℃所以T=360℃3.3设备衡算3.3.1反应器1．选型：管式绝热反应器2.选材：ICr-I8Ni-9Ti3.操作条件:(1)反应器操作压力0.4~0.8atm(2)丙烯入口压力大于反应器压力0.3~0.6atm表压(3）氯气入口芽率大于丙烯入口压力0.3~0.6atm表压4.混合器的计算(1)喷嘴气速WL={2gP1v2γ[1-(P2/P1)(γ-1)/γ]/(γ-1)}0.5其中γ─绝热指数γ=CP/CV，γCl2=1.36,V─进料比容m3/kg,g─m/s2P1─进口压力kg/cm2,P1─反应器压力kg/cm2,W─m/s(2)喷嘴截面积G进口气体流量kg/s,p1----入口压力，P2----反应器压力F2=554.3396/3600/{2×9.81×1.36/0.36×2.5×1.033×104/0.13544(1.4/2.5)2/1.36-(1.4/2.5)2.36/1.36}0.5=1.9317×10-4m2(3)喷嘴直径d内=（4F2/∏）0。5=（4×1。96317×10-4/3.14）0。5=16.5557mm经园整大约15mm,不锈钢耐酸无缝钢管（YB804-70）内径17mm外径20mm壁厚3mm5.喉管尺寸的计算(1)环隙处丙烯线速度计算：CP=0.866+5.602×607-2.771×10-5×6072+5.266×10-9×3553=24.943932CV=CP-R=24。943932-1。987=22.956932γ=CP/CV=24.943932/22.956932=1.087v=RT/MP=8.314×607/(42.078×1.01325×1.6×105)=0.739788m3/kgWL={2gP1v2γ[1-(P2/P1)(γ-1)/γ]/(γ-1)}0.5={2×9.81×1.6×1.033×0.739788×1.087×[1-(1.4/1.6)(0.087/1.087)]/0.087}0.5=228.50305m/s(2)丙烯进料环隙线速度的计算F2=∏（d丙内2-d氯外2）/4d丙内=（4F2/∏+d氯外2）0。5=（4×1.66317/∏+182）0.5=28.248内径29mm外径36mm壁厚3.5mm6.氯气丙烯进料口管径的计算：v=nRT/Pd=18.8(v/ω)0.5=18.8×(75.082/80)0.5=57.5946mm公称直径65mm外径76mm壁厚4mmv=35.3142×8.314×607×1000/1.6/101325=136.7106d丙=18.8×(136.7106/0.054)0.5=219.81582mm公称直径225mm外径245mm壁厚7mm7.反应器尺寸的确定：v=τQ/3600,τ=2s,Q----总体积流量（ 标准 excel标准偏差excel标准偏差函数exl标准差函数国标检验抽样标准表免费下载红头文件格式标准下载 态下）m3/h,Q总=N总RT/P=8。314×298×42。9418×1000/101325=1050。00149V=2×1050.00149/3600=0.5833342v=∏d2/4=5∏d3,d=0.333687ml=6.67337396m公称直径350mm外径377mm壁厚9mm8.实际安装尺寸的计算(1)喉管长度：l=2D丙烯外=2×31=84mm(2)混合器与反应器连接椎体角300故反应器椎体高度=[（反应器内径-后管内径）/2]tg150=（359-25）/2/tg15=823.2525mm(3)喷嘴椎体角度为320故喷嘴椎体高度=[（d进外径-d喷外经）]=(76-18)/2/tg18=101.2528mm(4)丙烯环隙入口椎体角度为320，故反应丙烯环隙入口椎体高度=[（丙烯入口管内径-后管内径）/2]/tg16=(231-25)/2/tg16=499.2037mm3.3.2氯精二塔：塔计算有前物料得进料F=12.9189kmol/h=865.0496kg/h塔顶出料：D=8.9518kmol/h=456.7165kg/h,塔釜出料：W=0.96764kmol/h=188.36799kg/h回流比R=20，进料状态q=1.、则塔径计算：V=L+D，V=26.8554kmol/h=19701495kg/hL=11.9036kmol/h=1313.433kg/h,液气比：0.667，则有精流段的温度：T=上升的气体体积流量：V=nRT/P==501.45194m3/h上升的气体重度：=下降液体以AC居多，其物参数：62度，rL=887.7kg/m3选外径为25mm的陶瓷拉西环为填料，填料因子为450m-1,得到wf=0.9536m/s则操作气速为0.4768m/s,D=0.6339m,加防腐层0.1m,则公称直径为800mm,外径820mm，壁后10mm提流段：平均温度：T=（438.080139+493.776001）/2=465.93K上升的气体量：V提=V精=21.8554kmol/h=1970.1495kg/h下降的液体量:1978.51749kg/h1液气比=上升的气体重度：rG=8.41395下降液体以12-Da为主rL=1059kg/m3,uc=0.405cp,rG/rL=0.00417,则：液泛速度：wf=0.9115m/s,操作气速=0.4558m/s,D=0.4909m加防腐层0.1m公称直径800mm外径820mm壁厚10mm则：精馏塔的塔径800mm外径820mm壁厚10mm4附录106-89-8英文文献及翻译AirToxicsSite106-89-8Epichlorohydrin(1-Chloro-2,3-Epoxypropane)106-89-8 HazardSummary-CreatedinApril1992;RevisedinJanuary2000Epichlorohydrinismainlyusedintheproductionofepoxyresins. Acute(short-term)inhalationexposuretoepichlorohydrinintheworkplacehascausedirritationtotheeyes,respiratorytract,andskinofworkers. Athighlevelsofexposure,nausea,vomiting,cough,laboredbreathing,inflammationofthelung,pulmonaryedema,andrenallesionsmaybeobservedinhumans. Chronic(long-term)occupationalexposureofhumanstoepichlorohydrininairisassociatedwithhighlevelsofrespiratorytractillnessandhematologicaleffects. Damagetothenasalpassages,respiratorytractandkidneyshavebeenobservedinrodentsexposedtoepichlorohydrinbyinhalationforacuteorchronicduration. Anincreasedincidenceoftumorsofthenasalcavityhasbeenobservedinratsexposedbyinhalation. EPAhasclassifiedepichlorohydrinasaGroupB2,probablehumancarcinogen.PleaseNote:ThemainsourcesofinformationforthisfactsheetareEPA'sIRIS,whichcontainsinformationoninhalationchronictoxicityandcarcinogeniceffectsofepichlorohydrinandtheRfC,andunitcancerriskestimateforinhalationexposure,andtheHealthandEnvironmentalEffectsProfileforEpichlorohydrin.UsesTheprimaryuseofepichlorohydrinisintheproductionofepoxyresinsusedincoatings,adhesives,andplastics.(1,5)Epichlorohydrinisalsousedinthemanufactureofsyntheticglycerine,textiles,paper,inksanddyes,solvents,surfactants,andpharmaceuticals.(1)Epichlorohydrinisalsolistedasaninertingredientincommercialpesticides.(1)SourcesandPotentialExposureIndividualsaremostlikelytobeexposedtoepichlorohydrinintheworkplace.(1)Epichlorohydrinmaybereleasedtotheambientairduringitsproductionanduse.(1)Accidentalreleasestowaterwaysmayexposethegeneralpublictoepichlorohydrin.(1)AssessingPersonalExposureNoinformationwaslocatedconcerningthemeasurementofpersonalexposuretoepichlorohydrin.HealthHazardInformationAcuteEffects:Acuteinhalationexposuretoepichlorohydrinintheworkplacehascausedirritationtotheeyes,respiratorytract,andskinofworkers. Athighlevelsofexposure,nausea,vomiting,cough,laboredbreathing,chemicalpneumonitis(inflammationofthelung),pulmonaryedema,andrenallesionsmaybeobservedinhumans.(1,2)Dermalcontactwithepichlorohydrinmayresultinirritationandburnsoftheskininhumansandanimals.(1)Inratsandmiceacutelyexposedtoepichlorohydrinbyinhalation,nasalandlowerrespiratorytractirritationandlesions,hemorrhage,andsevereedemahavebeenobserved. RenaldegenerationandCNSdepressionwithparalysisofrespirationandcardiacarresthavealsoresultedfromacuteinhalationexposureinanimals.(1-3)Testsinvolvingacuteexposureofrats,miceandrabbitshavedemonstratedepichlorohydrintohavehighacutetoxicityfrominhalation,oral,anddermalexposure.(4)ChronicEffects(Noncancer):Chronicoccupationalexposureofhumanstoepichlorohydrininairisassociatedwithhighlevelsofrespiratorytractillnessandhematologicaleffects(decreasedhemoglobinconcentrationanddecreasederythrocyteandleukocytecounts).(1,5)Chronicinhalationexposurehasbeenobservedtocausepulmonaryeffectsincludinginflammationanddegenerativechangesinthenasalepithelia,severelungcongestion,andpneumoniainratsandmice. Effectstothekidneyswerealsoobserved.(1,2)Hepaticdamage,hematologicaleffects,myocardialchanges,anddamagetotheCNShavebeenreportedinchronicallyexposedrats.(1,5)TheReferenceConcentration(RfC)forepichlorohydrinis0.001milligramspercubicmeter(mg/m3)basedonchangesinthenasalturbinatesinratsandmice.TheRfCisanestimate(withuncertaintyspanningperhapsanorderofmagnitude)ofacontinuousinhalationexposuretothehumanpopulation(includingsensitivesubgroups),thatislikelytobewithoutappreciableriskofdeleteriousnoncancereffectsduringalifetime.Itisnotadirectestimatorofriskbutratherareferencepointtogaugethepotentialeffects.AtexposuresincreasinglygreaterthantheRfC,thepotentialforadversehealtheffectsincreases.LifetimeexposureabovetheRfCdoesnotimplythatanadversehealtheffectwouldnecessarilyoccur.(2)EPAhasmediumconfidenceinthestudyonwhichtheRfCwasbasedbecauseoftheinflammationintherespiratorytractofcontrolandexposedanimalsalthoughitwaswellconductedandcontaineddetailedhistopathologicalexaminationsofnumeroustissuesincludingtherespiratorytract;mediumconfidenceinthedatabasebecausechronicstudiesthatadequatelyaddresstherespiratorysystemandatwo-generationreproductivestudyarelackingandtheonlychronicinhalationstudyisconfoundedbyseverenasalinflammationinthecontrols;and,consequently,mediumconfidenceintheRfC.(2)TheprovisionalReferenceDose(RfD)forepichlorohydrinis0.002milligramsperkilogrambodyweightperday(mg/kg/d)basedonkidneyeffectsinrats.TheprovisionalRfDisavaluethathashadsomeformofAgencyreview,butitdoesnotappearonIRIS(6)Reproductive/DevelopmentalEffects:Inhumansoccupationallyexposedtoepichlorohydrin,effectsonspermcounts,hormonelevels,andfertilityhavebeennotdetected.(1,2)Epichlorohydrinhasbeendemonstratedtoreducefertilityinmaleratswheninhaledoradministeredorally.(1-3)Teratogeniceffects(birthdefects)havenotbeenobservedinstudiesofrodentsexposedbyinhalationoringestion.(1,2,5)CancerRisk:Anincreasedincidenceoflungcancermortality(notstatisticallysignificant)wasreportedinonestudyofworkersexposedtoepichlorohydrin.(1,2)Anincreasedincidenceoftumorsofthenasalcavityhasbeenobservedinratsexposedtoepichlorohydrinbyinhalation.(1,2,5)Anincreasedincidenceofforestomachtumorshasbeenreportedinratsexposedviagavage(experimentallyplacingthechemicalinthestomach)andindrinkingwater. Micehaveexhibitedlocaltumorswhenexposedbysubcutaneousinjection.(1-3,5)EPAhasclassifiedepichlorohydrinasaGroupB2,probablehumancarcinogen.(2)EPAusesmathematicalmodels,basedonhumanandanimalstudies,toestimatetheprobabilityofapersondevelopingcancerfrombreathingaircontainingaspecifiedconcentrationofachemical.EPAcalculatedaninhalationunitriskestimateof1.2×10-6(µg/m3)-1.EPAestimatesthat,ifanindividualweretocontinuouslybreatheaircontainingepichlorohydrinatanaverageof0.8µg/m3(0.0008mg/m3)overhisorherentirelifetime,thatpersonwouldtheoreticallyhavenomorethanaone-in-a-millionincreasedchanceofdevelopingcancerasadirectresultofbreathingaircontainingthischemical.Similarly,EPAestimatesthatbreathingaircontaining8.0µg/m3(0.008mg/m3)wouldresultinnotgreaterthanaone-in-a-hundredthousandincreasedchanceofdevelopingcancer,andaircontaining80.0µg/m3(0.08mg/m3)wouldresultinnotgreaterthanaone-in-tenthousandincreasedchanceofdevelopingcancer.Foradetaileddiscussionofconfidenceinthepotencyestimates,pleaseseeIRIS.(2)EPAhascalculatedanoralcancerslopefactorof9.9x10-3(mg/kg/d)-1.(2)PhysicalPropertiesThechemicalformulaforepichlorohydrinisC3H5OCl,anditsmolecularweightis92.53g/mol.(1,7)Epichlorohydrinisavolatileandflammableclearliquidatroomtemperatureandisinsolubleinwater.(1,2,7)Thethresholdforodorperceptionofepichlorohydrinis0.93partspermillion(ppm).Epichlorohydrinhasapungent,garlicky,sweetodor.(2,8)Thevaporpressureforepichlorohydrinis22mmHgat30°C.(1)ConversionFactors:Toconvertconcentrationsinair(at25°C)fromppmtomg/m3:mg/m3=(ppm)×(molecularweightofthecompound)/(24.45).Forepichlorohydrin:1ppm=3.78mg/m3.HealthDatafromInhalationExposureACGIHTLV--AmericanConferenceofGovernmentalandIndustrialHygienists'thresholdlimitvalueexpressedasatime-weightedaverage;theconcentrationofasubstancetowhichmostworkerscanbeexposedwithoutadverseeffects.AIHAERPG--AmericanIndustrialHygieneAssociation'semergencyresponseplanningguidelines.ERPG1isthemaximumairborneconcentrationbelowwhichitisbelievednearlyallindividualscouldbeexposeduptoonehourwithoutexperiencingotherthanmildtransientadversehealtheffectsorperceivingaclearlydefinedobjectionableodor;ERPG2isthemaximumairborneconcentrationbelowwhichitisbelievednearlyallindividualscouldbeexposeduptoonehourwithoutexperiencingordevelopingirreversibleorotherserioushealtheffectsthatcouldimpairtheirabilitiestotakeprotectiveaction.LC50(LethalConcentration50)--Acalculatedconcentrationofachemicalinairtowhichexposureforaspecificlengthoftimeisexpectedtocausedeathin50%ofadefinedexperimentalanimalpopulation.LOAEL--Lowest-observed-adverse-effectlevel.NIOSHIDLH--NationalInstituteofOccupationalSafetyandHealth'simmediatelydangeroustolifeorhealthlimit;NIOSHrecommendedexposurelimittoensurethataworkercanescapefromanexposureconditionthatislikelytocausedeathorimmediateordelayedpermanentadversehealtheffectsorpreventescapefromtheenvironment.NOAEL--No-observed-adverse-effectlevel.OSHAPEL--OccupationalSafetyandHealthAdministration'spermissibleexposurelimitexpressedasatime-weightedaverage;theconcentrationofasubstancetowhichmostworkerscanbeexposedwithoutadverseeffectaveragedoveranormal8-hworkdayora40-hworkweek.ThehealthandregulatoryvaluescitedinthisfactsheetwereobtainedinDecember1999.aHealthnumbersaretoxicologicalnumbersfromanimaltestingorriskassessmentvaluesdevelopedbyEPA.bRegulatorynumbersarevaluesthathavebeenincorporatedinGovernmentregulations,whileadvisorynumbersarenonregulatoryvaluesprovidedbytheGovernmentorothergroupsasadvice. OSHAnumbersareregulatory,whereasNIOSH,ACGIH,andAIHAnumbersareadvisory.cThisNOAELandLOAELarefromthecriticalstudyusedasthebasisfortheRfC.ReferencesU.S.EnvironmentalProtectionAgency.HealthandEnvironmentalEffectsProfileforEpichlorohydrin.EPA/600/x-85/400.EnvironmentalCriteriaandAssessmentOffice,OfficeofHealthandEnvironmentalAssessment,OfficeofResearchandDevelopment,Cincinnati,OH.1985.U.S.EnvironmentalProtectionAgency.IntegratedRiskInformationSystem(IRIS)onEpichlorohydrin.NationalCenterforEnvironmentalAssessment,OfficeofResearchandDevelopment,Washington,DC.1999.InternationalAgencyforResearchonCancer(IARC).IARCMonographsontheEvaluationoftheCarcinogenicRiskofChemicalstoMan:Cadmium,Nickel,SomeEpoxides,MiscellaneousIndustrialChemicalsandGeneralConsiderationsonVolatileAnaesthetics.Volume11.WorldHealthOrganization,Lyon.1976.U.S.DepartmentofHealthandHumanServices.RegistryofToxicEffectsofChemicalSubstances(RTECS,onlinedatabase).NationalToxicologyInformationProgram,NationalLibraryofMedicine,Bethesda,MD.1993.U.S.EnvironmentalProtectionAgency.EpichlorohydrinHealthAdvisory.OfficeofDrinkingWater,Washington,DC.1987.U.S.EnvironmentalProtectionAgency.HealthEffectsAssessmentSummaryTables. FY1997Update. SolidWasteandEmergencyResponse,OfficeofEmergencyandRemedialResponse,Cincinnati,OH. EPA/540/R-97-036. 1997.TheMerckIndex.AnEncyclopediaofChemicals,Drugs,andBiologicals.11thed.Ed.S.Budavari.MerckandCo.Inc.,Rahway,NJ.1989.J.E.AmooreandE.Hautala.Odorasanaidtochemicalsafety:Odorthresholdscomparedwiththresholdlimitvaluesandvolatilitiesfor214industrialchemicalsinairandwaterdilution.JournalofAppliedToxicology,3(6):272-290.1983.AmericanConferenceofGovernmentalIndustrialHygienists(ACGIH). 1999TLVsandBEIs. ThresholdLimitValuesforChemicalSubstancesandPhysicalAgents. BiologicalExposureIndices. Cincinnati,OH. 1999.NationalInstituteforOccupationalSafetyandHealth(NIOSH). PocketGuidetoChemicalHazards.U.S.DepartmentofHealthandHumanServices,PublicHealthService,CentersforDiseaseControlandPrevention. Cincinnati,OH. 1997.OccupationalSafetyandHealthAdministration(OSHA). OccupationalSafetyandHealthStandards,ToxicandHazardousSubstances. CodeofFederalRegulations.29CFR1910.1000. 1998.AmericanIndustrialHygieneAssociation(AIHA).TheAIHA1998EmergencyResponsePlanningGuidelinesandWorkplaceEnvironmentalExposureLevelGuidesHandbook.1998.空气中的有毒物质环氧氯丙烷（1-氯-2,3-环氧丙烷）106-89ChronicEffects(NoncancHazardSummary-CreatedinApril1992;RevisedinJanuary2000危险的主要信息创建于1992年4月;调整是在2000年1月Epichlorohydrinismainlyusedintheproductionofepoxyresins. Acute(short-term)inhalationexposuretoepichlorohydrinintheworkplacehascausedirritationtotheeyes,respiratorytract,andskinofworkers. Athighlevelsofexposure,nausea,vomiting,cough,laboredbreathing,inflammationofthelung,pulmonaryedema,andrenallesionsmaybeobservedinhumans. Chronic(long-term)occupationalexposureofhumanstoepichlorohydrininairisassociatedwithhighlevelsofrespiratorytractillnessandhematologicaleffects. Damagetothenasalpassages,respiratorytractandkidneyshavebeenobservedinrodentsexposedtoepichlorohydrinbyinhalationforacuteorchronicduration. Anincreasedincidenceoftumorsofthenasalcavityhasbeenobservedinratsexposedbyinhalation. EPAhasclassifiedepichlorohydrinasaGroupB2,probablehumancarcinogen.环氧氯丙烷，主要用于生产环氧树脂。急性（短期）吸入接触环氧氯丙烷在工作场所已引起刺激眼睛，呼吸道及皮肤的工人。在高层次的接触，恶心，呕吐，咳嗽，labored呼吸，发炎，肺癌，肺水肿，肾脏病变，可观察到人类。慢性（长期）职业暴露人类环氧氯丙烷在空气中是相关的高水平的呼吸道的疾病和血液的效果。损害鼻腔通道，呼吸道和肾脏已经观察到，在啮齿动物暴露于环氧氯丙烷吸入急性或慢性期。1发病率增加肿瘤的鼻腔一直在观察大鼠暴露出来的吸入。环保局已列为环氧氯丙烷作为一个群体，B2的，可能的人类致癌物质。PleaseNote:ThemainsourcesofinformationforthisfactsheetareEPA'sIRIS,whichcontainsinformationoninhalationchronictoxicityandcarcinogeniceffectsofepichlorohydrinandtheRfC,andunitcancerriskestimateforinhalationexposure,andtheHealthandEnvironmentalEffectsProfileforEpichlorohydrin.说明：主要的信息来源，这一事实表是EPA的虹膜，其中包含的信息吸入慢性毒性和致癌作用和环氧氯丙烷的RFC，本单位的患癌症的风险估计为吸入性接触，以及健康及环境的影响概况为环氧氯丙烷。Uses用途Theprimaryuseofepichlorohydrinisintheproductionofepoxyresinsusedincoatings,adhesives,andplastics.主要使用环氧氯丙烷是在生产环氧树脂的使用在涂料，粘合剂，和塑料工业。(1,5)Epichlorohydrinisalsousedinthemanufactureofsyntheticglycerine,textiles,paper,inksanddyes,solvents,surfactants,andpharmaceuticals.环氧氯丙烷也被用于制造合成甘油，纺织品，纸张，油墨和料，溶剂，表面活性剂和药品。(1)Epichlorohydrinisalsolistedasaninertingredientincommercialpesticides.环氧氯丙烷也被列为一种惰性成分，在商业农药领域。SourcesandPotentialExposure来源和潜在风险Individualsaremostlikelytobeexposedtoepichlorohydrinintheworkplace.个人最有可能接触到环氧氯丙烷的地区,接触到的环氧氯丙烷在工作场所。(1)Epichlorohydrinmaybereleasedtotheambientairduringitsproductionanduse.环氧氯丙烷可能会释放到空气中在其生产和使用。(1)Accidentalreleasestowaterwaysmayexposethegeneralpublictoepichlorohydrin.偶然的气体排放，水路可能使人们接触环氧氯丙烷。(1)AssessingPersonalExposure评估个人曝光Noinformationwaslocatedconcerningthemeasurementofpersonalexposuretoepichlorohydrin.没有资料被寻回有关测量个人接触到环氧氯丙烷。HealthHazardInformationAcuteEffects:急性效应：Acuteinhalationexposuretoepichlorohydrinintheworkplacehascausedirritationtotheeyes,respiratorytract,andskinofworkers. Athighlevelsofexposure,nausea,vomiting,cough,laboredbreathing,chemicalpneumonitis(inflammationofthelung),pulmonaryedema,andrenallesionsmaybeobservedinhumans.急性吸入暴露环氧氯丙烷在工作场所已引起刺激眼睛，呼吸道及皮肤的工人。在高层次的接触，恶心，呕吐，咳嗽，呼吸困难，化学性肺炎（炎症，肺），肺水肿，和肾脏病变，可观察到人类。(1,2)Dermalcontactwithepichlorohydrinmayresultinirritationandburnsoftheskininhumansandanimals.皮肤接触与环氧氯丙烷可能会导致刺激和灼伤的皮肤在人类和动物。(1)Inratsandmiceacutelyexposedtoepichlorohydrinbyinhalation,nasalandlowerrespiratorytractirritationandlesions,hemorrhage,andsevereedemahavebeenobserved. RenaldegenerationandCNSdepressionwithparalysisofrespirationandcardiacarresthavealsoresultedfromacuteinhalationexposureinanimals.在大鼠和小鼠敏锐地接触到环氧氯丙烷的吸入，鼻和下呼吸道的刺激和损伤，出血，水肿，严重的已被观察到。肾豆状核变性和中枢神经系统抑郁症的瘫痪，呼吸和心脏骤停，也造成急性吸入暴露于动物。(1-3)Testsinvolvingacuteexposureofrats,miceandrabbitshavedemonstratedepichlorohydrintohavehighacutetoxicityfrominhalation,oral,anddermalexposure.测试涉及急性暴露大鼠，小鼠和家兔表明，环氧氯丙烷有高的急性毒性吸入，口服，皮肤接触。(4)ChronicEffects(Noncancer):慢性效应（noncancer）：Chronicoccupationalexposureofhumanstoepichlorohydrininairisassociatedwithhighlevelsofrespiratorytractillnessandhematologicaleffects(decreasedhemoglobinconcentrationanddecreasederythrocyteandleukocytecounts).慢性职业暴露人类环氧氯丙烷在空气中是相关的高水平的呼吸道的疾病和血液的影响（减少血红蛋白浓度下降，红细胞和白细胞计数）。(1,5)Chronicinhalationexposurehasbeenobservedtocausepulmonaryeffectsincludinginflammationanddegenerativechangesinthenasalepithelia,severelungcongestion,andpneumoniainratsandmice. Effectstothekidneyswerealsoobserved.慢性吸入性接触已观察到引起肺的影响，包括炎症和退行性变化，在鼻上皮细胞，严重肺部的挤塞情况，和肺炎在大鼠和小鼠。影响到肾脏还观察到。(1,2)Hepaticdamage,hematologicaleffects,myocardialchanges,anddamagetotheCNShavebeenreportedinchronicallyexposedrats.肝损伤，血液的影响，心肌的变化，损害中枢神经系统已报道，在长期暴露的影响。(1,5)TheReferenceConcentration(RfC)forepichlorohydrinis0.001milligramspercubicmeter(mg/m3)basedonchangesinthenasalturbinatesinratsandmice.参考浓度（RFC）的为环氧氯丙烷是0.001毫克每立方米（毫克/米3）的基础上的变化，在鼻腔下鼻甲在大鼠和小鼠。TheRfCisanestimate(withuncertaintyspanningperhapsanorderofmagnitude)ofacontinuousinhalationexposuretothehumanpopulation(includingsensitivesubgroups),thatislikelytobewithoutappreciableriskofdeleteriousnoncancereffectsduringalifetime.的RFC是一个估计数（具有不确定性的跨越，或许一个量级）连续吸入暴露给人类的人口（包括敏感亚群），这很可能是没有称道的危险有害noncancer的影响，在一生。Itisnotadirectestimatorofriskbutratherareferencepointtogaugethepotentialeffects.它不是一个直接估算的风险，而是一个参考点来衡量的潜在影响。AtexposuresincreasinglygreaterthantheRfC,thepotentialforadversehealtheffectsincreases.在风险越来越大，比的RFC，健康构成的潜在危险增加。LifetimeexposureabovetheRfCdoesnotimplythatanadversehealtheffectwouldnecessarilyoccur.一生中暴露以上的RFC并不意味着不良的健康效应一定会发生。(2)EPAhasmediumconfidenceinthestudyonwhichtheRfCwasbasedbecauseoftheinflammationintherespiratorytractofcontrolandexposedanimalsalthoughitwaswellconductedandcontaineddetailedhistopathologicalexaminationsofnumeroustissuesincludingtherespiratorytract;mediumconfidenceinthedatabasebecausechronicstudiesthatadequatelyaddresstherespiratorysystemandatwo-generationreproductivestudyarelackingandtheonlychronicinhalationstudyisconfoundedbyseverenasalinflammationinthecontrols;and,consequently,mediumconfidenceintheRfC.环保局已在中等可信度的研究，其中的RFC是基于因为炎症在呼吸道的控制和动物暴露，虽然这是顺利进行，并载有详细的病理组织学检查，多次组织包括呼吸道;中等信心，在数据库中，因为慢性研究，充分解决呼吸系统和一个2代生殖研究的缺乏和唯一的慢性吸入研究是混淆了严重的鼻腔炎症的管制;和，因此，中等的信心的RFC。(2)TheprovisionalReferenceDose(RfD)forepichlorohydrinis0.002milligramsperkilogrambodyweightperday(mg/kg/d)basedonkidneyeffectsinrats.临时参考剂量（日基准剂量），环氧氯丙烷是0.002毫克每公斤体重每天（毫克/千克/d）根据对肾脏的作用的影响。TheprovisionalRfDisavaluethathashadsomeformofAgencyreview,butitdoesnotappearonIRIS(6)临时日基准剂量是一种价值，已某种形式的机构审查，但这并不出现在虹膜Reproductive/DevelopmentalEffec生殖/发育的影响：Inhumansoccupationallyexposedtoepichlorohydrin,effectsonspermcounts,hormonelevels,andfertilityhavebeennotdetected.在人类职业暴露环氧氯丙烷，影响对精子计数，激素水平，和生育率已未检出。(1,2)Epichlorohydrinhasbeendemonstratedtoreducefertilityinmaleratswheninhaledoradministeredorally.环氧氯丙烷已经证明，以减少生育率在雄性大鼠时，吸入或口服。(1-3)Teratogeniceffects(birthdefects)havenotbeenobservedinstudiesofrodentsexposedbyinhalationoringestion.致畸作用（出生缺陷）没有得到遵守，在研究啮齿动物所暴露出来的吸入或吞食。(1,2,5)CancerRisk:患癌症的风险：Anincreasedincidenceoflungcancermortality(notstatisticallysignificant)wasreportedinonestudyofworkersexposedtoepichlorohydrin.1增加肺癌发病率，死亡率（无统计学意义）据报道，在一项研究中的工人暴露于环氧氯丙烷。(1,2)Anincreasedincidenceoftumorsofthenasalcavityhasbeenobservedinratsexposedtoepichlorohydrinbyinhalation.一发病率增加肿瘤的鼻腔一直在观察大鼠暴露环氧氯丙烷吸入。(1,2,5)（Anincreasedincidenceofforestomachtumorshasbeenreportedinratsexposedviagavage(experimentallyplacingthechemicalinthestomach)andindrinkingwater. Micehaveexhibitedlocaltumorswhenexposedbysubcutaneousinjection.一发病率增加forestomach肿瘤已报道在大鼠暴露经灌胃（实验）和在饮水。小鼠呈现出本地肿瘤时，所暴露出来的皮下注射。(1-3,5)EPAhasclassifiedepichlorohydrinasaGroupB2,probablehumancarcinogen.环保局已列为环氧氯丙烷作为一个群体，B2的，可能的人类致癌物质。(2)EPAusesmathematicalmodels,basedonhumanandanimalstudies,toestimatetheprobabilityofapersondevelopingcancerfrombreathingaircontainingaspecifiedconcentrationofachemical.环保局利用数学模型的基础上，人类和动物的研究，估计概率一个人的发展，癌症，呼吸的空气含有指定浓度的化学品。EPAcalculatedaninhalationunitriskestimateof1.2×10-6(µg/m3)-1.EPA的计算，一吸入单位风险的估计为1.2×10-6（μ克/米3）-1。EPAestimatesthat,ifanindividualweretocontinuouslybreatheaircontainingepichlorohydrinatanaverageof0.8µg/m3(0.0008mg/m3)overhisorherentirelifetime,thatpersonwouldtheoreticallyhavenomorethanaone-in-a-millionincreasedchanceofdevelopingcancerasadirectresultofbreathingaircontainingthischemical.环保局估计，如果个别人不断呼吸的空气含有环氧氯丙烷在平均0.8μ克/米3（0.0008毫克/米3），超过他或她的整个一生中，这个人会在理论上有不超过一个在-1万增加的机会，发展中国家的癌症作为一个直接结果，呼吸空气中含有这种化学物。Similarly,EPAestimatesthatbreathingaircontaining8.0µg/m3(0.008mg/m3)wouldresultinnotgreaterthanaone-in-a-hundredthousandincreasedchanceofdevelopingcancer,andaircontaining80.0µg/m3(0.08mg/m3)wouldresultinnotgreaterthanaone-in-tenthousandincreasedchanceofdevelopingcancer.同样地，美国环保局估计，呼吸空气中含有8.0μ克/米3（0.008毫克/米3），会导致不大于一个在一100000的机会，增加发展中国家的癌症，和空中载有80.0μ克/米3（0.08毫克/米3），会导致不大于一个在-万增加的机会，发展中国家的癌症。Foradetaileddiscussionofconfidenceinthepotencyestimates,pleaseseeIRIS.为详细讨论了信心，在效估计，请参阅虹膜。(2)EPAhascalculatedanoralcancerslopefactorof9.9x10-3(mg/kg/d)-1.环保部门已计算出一个口腔癌的斜坡因素9.9×10-3（毫克/公斤）。(2)PhysicalProperties物理性质ThechemicalformulaforepichlorohydrinisC3H5OCl,anditsmolecularweightis92.53g/mol.化学公式环氧氯丙烷是C3小时5八达通卡公司，其分子量是92.53克/mol的。(1,7)Epichlorohydrinisavolatileandflammableclearliquidatroomtemperatureandisinsolubleinwater.环氧氯丙烷是一种挥发性和易燃液体清晰的在室温下是不溶于水。(1,2,7)Thethresholdforodorperceptionofepichlorohydrinis0.93partspermillion(ppm).气味的看法环氧氯丙烷是0.93百万分之（百万分之一）。Epichlorohydrinhasapungent,garlicky,sweetodor.环氧氯丙烷有辣，大蒜，甜气味。在30°C时,(2,8)Thevaporpressureforepichlorohydrinis22mmHgat30°C.汽压力为环氧氯丙烷的是22毫米汞柱(1)ConversionFactors:转换的因素包括：Toconvertconcentrationsinair(at25°C)fromppmtomg/m3:mg/m3=(ppm)×(molecularweightofthecompound)/(24.45).转换浓度在空气中（在25°C）由百万分之，以毫克/米3：毫克/米3=（百万分之一）×（分子量化合物）/（24.45）。Forepichlorohydrin:1ppm=3.78mg/m3.为环氧氯丙烷：1ppm的=3.78毫克/米3。HealthDatafromInhalationExposuAIHAERPG--AmericanIndustrialHygieneAssociation'semergencyresponseplanningguidelines.acgihTLV公司-美洲会议的政府和工业卫生值表示为一个时间加权平均;浓度的物质，其中大部分工人可以暴露无不良影响。AIHAERPG--AmericanIndustrialHygieneAssociation'semergencyresponseplanningguidelines.aihaerpg-美国工业卫生协会的紧急应变的规划指引。ERPG1isthemaximumairborneconcentrationbelowwhichitisbelievednearlyallindividualscouldbeexposeduptoonehourwithoutexperiencingotherthanmildtransientadversehealtheffectsorperceivingaclearlydefinedobjectionableodor;ERPG2isthemaximumairborneconcentrationbelowwhichitisbelievednearlyallindividualscouldbeexposeduptoonehourwithoutexperiencingordevelopingirreversibleorotherserioushealtheffectsthatcouldimpairtheirabilitiestotakeprotectiveaction.erpg1是最高的机载浓度低于它，相信几乎所有的个人可以暴露了长达一小时没有经历或发展不可逆转的或其他严重的健康影响，可能损害自己的能力，采取保护行动。LC50(LethalConcentration50)--Acalculatedconcentrationofachemicalinairtowhichexposureforaspecificlengthoftimeisexpectedtocausedeathin50%ofadefinedexperimentalanimalpopulation.立法会50（致死浓度50）-一计算浓度的化学品在空气中暴露，其中为一个特定的时间长度，预计造成死亡在50％的界定实验动物的人口。LOAEL--Lowest-observed-adverse-effectlevel.loael-最低观察-不良效应的水平。NIOSHIDLH--NationalInstituteofOccupationalSafetyandHealth'simmediatelydangeroustolifeorhealthlimit;NIOSHrecommendedexposurelimittoensurethataworkercanescapefromanexposureconditionthatislikelytocausedeathorimmediateordelayedpermanentadversehealtheffectsorpreventescapefromtheenvironment.nioshidlh-国家研究所，职业安全及健康的立即危险的生命或健康的极限;niosh建议暴露限值，以确保工人能够摆脱一曝光条件，是可能造成死亡或即时或延迟永久的不利健康影响或阻止脱离环境。NOAEL--No-observed-adverse-effectlevel.noael-没有观察-不良效应的水平。OSHAPEL--OccupationalSafetyandHealthAdministration'spermissibleexposurelimitexpressedasatime-weightedaverage;theconcentrationofasubstancetowhichmostworkerscanbeexposedwithoutadverseeffectaveragedoveranormal8-hworkdayora40-hworkweek.职业安全与卫生署，规划环境地政局-职业安全与卫生当局的允许暴露限值表示，作为一个时间加权平均;浓度的物质，其中大部分工人可以暴露无不良影响，平均超过正常的8小时工作日或40小时工作制。ThehealthandregulatoryvaluescitedinthisfactsheetwereobtainedinDecember1999.健康的价值观和规管中提到的这factsheet，上面这个是在获得了在1999年12月通过的。aHealthnumbersaretoxicologicalnumbersfromanimaltestingorriskassessmentvaluesdevelopedbyEPA健康的数字是毒理学的人数从动物试验或风险评估的价值开发的环保局。bRegulatorynumbersarevaluesthathavebeenincorporatedinGovernmentregulations,whileadvisorynumbersarenonregulatoryvaluesprovidedbytheGovernmentorothergroupsasadvice. OSHAnumbersareregulatory,whereasNIOSH,ACGIH,andAIHAnumbersareadvisory.b监管号码的价值观已被纳入政府规例，而咨询的人数nonregulatory价值观所提供的政府或其他团体的意见。奥沙号码的规管，而niosh，acgih，aiha号码咨询。cThisNOAELandLOAELarefromthecriticalstudyusedasthebasisfortheRfC.C本noael和loael是从批判性研究作为基础的RFC。参考文献.参考文献[1]张君,高灿柱．环氧氯丙烷生产中的绿色化学1山东化工[2]崔吉宏,尹琦岭,杨泉,等.我国环氧氯丙烷生产和消费及发展[3]雷崧僧．沈阳化工．１９９１；８３（４）：７[4]张爱华,袁令斌．齐鲁石化公司规划院,山东淄博255400[5]魏文德.有机化工原料大全上卷M.2版.北京:化学工业出版社,1999.[6]王新龙.环氧氯丙烷生产技术进展及发展建议J.化学工业与 工程 路基工程安全技术交底工程项目施工成本控制工程量增项单年度零星工程技术标正投影法基本原理 技[3]术,2006,27(1):46-48.[7]叶由忠,等发展环氧氯丙烷生产迫在眉睫中国化工信息北京:2005-06-27A6[8]环氧氯丙烷工艺装置试车 总结 初级经济法重点总结下载党员个人总结TXt高中句型全总结.doc高中句型全总结.doc理论力学知识点总结pdf 中国氯2.4t/a碱,():2000832-34[9]李明环氧氯丙烷的消费现状及发展前景化工文摘．２００６４[10]《化工设备手册》编写组。金属设备（2）[M]。上海：上海人民出版社，1975[11]《化工设备设计全书》编辑委员会，路秀林，王者相等编著。塔设备[M]。北京：化学工业出版社，2004。[12]美国环境保护署。健康及环境的影响概况为环氧氯丙烷。EPA/600/x-85/400.epa/600/x-85/400。EnvironmentalCriteriaandAssessmentOffice,OfficeofHealthandEnvironmentalAssessment,OfficeofResearchandDevelopment,Cincinnati,OH.环境标准和评估办公室，办公室的卫生和环境评估，办公室的研究和发展，辛辛那提。1985.1985。[13]有机化工原料大全[M].第一卷.北京:化学工业出版社.1989.[14]张廷深.氯丙烯的深加工与应用.中国氯碱.1998（6）：19-23[15]王海勇,李爱霞.利用氯丙烯生产装置的反应热提高丙烯的预热温度.氯碱工业.2000：27-293沈阳化工学院��本科毕业论文��题目：�年产4200吨环氧氯丙烷车间氯丙烯合成工���段工艺设计��院系：�科亚学院���专业：�化学工程与工艺���班级：�科华工0401���学生姓名：�夏之光���指导教师：�刘东斌���论文提交日期：�2008�年�6�月��日��论文答辩日期：��年��月��日��科亚学院专业班学生夏之光毕业设计（论文）任务书化学工程与工艺0401毕业设计（论文）题目：年产4200吨环氧氯丙烷车间氯丙烯合成工段工艺设计毕业设计（论文）内容：毕业设计（论文）专题部分：指导教师：教研室主任：院长：签字签字签字年年年月月月日日日塔前换热器氯化物500℃25℃氯气丙烯�EMBEDEquation.DSMT4����EMBEDEquation.DSMT4���产物355K原料355K�EMBEDEquation.DSMT4���_1234567890.unknown_1234567891.unknown_1234567892.unknown_1234567893.unknown_1234567894.unknown_1234567895.unknown_1234567896.unknown_1234567897.unknown_1234567898.unknown_1234567899.unknown_1234567900.unknown_1234567901.unknown_1234567902.unknown_1234567903.unknown_1234567904.unknown_1234567905.unknown_1234567906.unknown_1234567907.unknown_1234567908.unknown_1234567909.unknown_1234567910.unknown_1234567911.unknown_1234567912.unknown_1234567913.unknown_1234567914.unknown_1234567915.unknown_1234567916.unknown_1234567917.unknown_1234567918.unknown_1234567919.unknown_1234567920.unknown_1234567921.unknown_1234567922.unknown_1234567923.unknown_1234567924.unknown_1234567925.unknown_1234567926.unknown_1234567927.unknown_1234567928.unknown_1234567929.unknown_1234567930.unknown_1234567931.unknown_1234567932.unknown_1234567933.unknown_1234567934.unknown_1234567935.unknown_1234567936.unknown_1234567937.unknown_1234567938.unknown_1234567939.unknown_1234567940.unknown_1234567941.unknown_1234567942.unknown_1234567943.unknown_1234567944.unknown_1234567945.unknown_1234567946.unknown_1234567947.unknown_1234567948.unknown_1234567949.unknown_1234567950.unknown_1234567951.unknown_1234567952.unknown_1234567953.unknown_1234567954.unknown_1234567955.unknown_1234567956.unknown_1234567957.unknown_1234567958.unknown_1234567959.unknown_1234567960.unknown_1234567961.unknown_1234567962.unknown_1234567963.unknown_1234567964.unknown_1234567965.unknown_1234567966.unknown_1234567967.unknown_1234567968.unknown_1234567969.unknown_1234567970.unknown_1234567971.unknown_1234567972.unknown_1234567973.unknown_1234567974.unknown_1234567975.unknown_1234567976.unknown_1234567977.unknown_1234567978.unknown_1234567979.unknown_1234567980.unknown_1234567981.unknown_1234567982.unknown_1234567983.unknown_1234567984.unknown_1234567985.unknown_1234567986.unknown_1234567987.unknown_1234567988.unknown_1234567989.unknown_1234567990.unknown_1234567991.unknown_1234567992.unknown_1234567993.unknown_1234567994.unknown_1234567995.unknown_1234567996.unknown_1234567997.unknown_1234567998.unknown_1234567999.unknown_1234568000.unknown_1234568001.unknown_1234568002.unknown_1234568003.unknown_1234568004.unknown_1234568005.unknown_1234568006.unknown_1234568007.unknown_1234568008.unknown_1234568009.unknown_1234568010.unknown_1234568011.unknown_1234568012.unknown_1234568013.unknown_1234568014.unknown_1234568015.unknown_1234568016.unknown_1234568017.unknown_1234568018.unknown_1234568019.unknown_1234568020.unknown_1234568021.unknown_1234568022.unknown_1234568023.unknown_1234568024.unknown_1234568025.unknown_1234568026.unknown_1234568027.unknown_1234568028.unknown_1234568029.unknown_1234568030.unknown_1234568031.unknown_1234568032.unknown_1234568033.unknown_1234568034.unknown_1234568035.unknown_1234568036.unknown_1234568037.unknown_1234568038.unknown_1234568039.unknown_1234568040.unknown_1234568041.unknown_1234568042.unknown_1234568043.unknown_1234568044.unknown_1234568045.unknown_1234568046.unknown_1234568047.unknown_1234568048.unknown_1234568049.unknown_1234568050.unknown_1234568051.unknown_1234568052.unknown_1234568053.unknown_1234568054.unknown_1234568055.unknown_1234568056.unknown_1234568057.unknown_1234568058.unknown_1234568059.unknown_1234568060.unknown_1234568061.unknown_1234568062.unknown_1234568063.unknown_1234568064.unknown_1234568065.unknown_1234568066.unknown_1234568067.unknown_1234568068.unknown_1234568069.unknown_1234568070.unknown_1234568071.unknown_1234568072.unknown_1234568073.unknown_1234568074.unknown_1234568075.unknown_1234568076.unknown_1234568077.unknown_1234568078.unknown_1234568079.unknown_1234568080.unknown