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夏克立(4043202,210015)[]磷肥;含氟废气;回收利用[]分析我国磷肥生产中氟回收利用现状:磷肥生产废气中的氟、硅资源每年分别达数十万t,但回收利用很差。介绍一种利用磷肥生产中的含氟废气生产氟化合物与白炭黑的清洁生产方法:用氟化铵或氨直接吸收含氟气体生成氟硅酸铵,然后氨化得氟化铵与白炭黑(SiO2),氟化铵可进一步加工为其它高价值氟化物产品。提出磷肥生产中的氟、硅资源化和接替战略资源——萤石的可能性。并介绍了该技术的开发现状,呼吁有关部门重视,促成该技术早日产业化。[]TQ442;X781[]A[]10076220(2005)05006005AbriefreviewonfluorinerecoveryinproductionofphosphatefertilizerXIAKeli(Room202,Unit3,No.404WusuoCun,XiaguanDistrict,Nanjing,Jiangsu210015,China)Keywords:phosphatefertilizer;fluorinecontaininggas;recoveryandutilizationAbstract:ThepresentstatusoffluorinerecoveryandutilizationinChinaisreviewed,includingtheabundantfluorineintailgas,siliconresourcewithseveralhundredkilotonsperyearbutpoorutilizationforproductionofphosphatefertilizer.Acleanproductiontechnologyforfluorineandsilicawhiteisintroduced,withfluorinecontaininggasrawmaterialdirectlyabsorbedbyammoniumfluoride,orammoniatoabtainammoniumfluorosilicate,andtogetammoniumfluorideandsilicawhitebyammonization,furthertomanufactureotherfluorideproductwithhighvalue.Theviewpointoffluorine,siliconasresourceandastrategicreplacementfluoriteintheproductionofphosphatefertilizer,andthedevelopmentstatusandtheindustrializationsuggestionofabovementionedtechnologyarepresented.,,,,,,,,;,,,;,,,,;,,,,,,;,3%4%,,,,,,,,,,,,,,,111过磷酸钙生产中氟回收利用技术现状,,,:[]20050418[](1942),,,,,2005年9月第20卷第5期磷肥与复肥Phosphate&CompoundFertilizer Sep.2005Vol.20No.53SiF4+3H2O2H2SiF6+H2SiO3(1),,,:H2SiF6+2NaClNa2SiF6+2HCl(2)(1),,5%SiO2,,1t100%SiO2,20tw(H2SiF6)8%10%(2),w(H2SiF6)8%10%,25%NaCl,130%,,Na2SiF6,1t100%H2SiF615t,12t,4%HCl,2%NaCl,100kg,(CaF2),;(CaCl2);,,12萃取磷酸浓缩中氟回收利用技术现状25%32%P2O5,,(SiF4)(HF),,:H2SiF6()2HF+SiF4(3),HFSiF421;,21;P2O550%,21;P2O556%,21,HFSiF421,SiF4,,SiF4,,P2O550%,;P2O556%,(HF),P2O533%35%,25%35%;P2O548%52%,60%;P2O555%57%,85%,P2O538%,,:,;,,H2SiF64%,P2O550%,,,H2SiF618%,,,,1t100%H2SiF6208.3kgSiO2,13存在问题,,(1),1tH2SiF6270.8kg(H2SiO3),208.3kg100%SiO2;(2),1t100%H2SiF6,506.9kg100%HCl,30%,243.7kg100%NaCl,15t,100kg(CaO),500kg100%CaO,(18%H2SiF6),(10t),,,,,,(10mgF/L),,,,800900/t,2;612005年第20卷第5期 夏克立 ,,,21氟化合物和二氧化硅的生产方法,3(1)/,,,,:SiF4+2NH4F(NH4)2SiF6(4)(SiF4),,,P2O550%,HFSiF421,,,:2HF+SiF4+2NH3(NH4)2SiF6(5)P2O550%,HFSiF42,(5)SiF4,SiF4NH4F,(4),,HFSiF42,SiF4,NH4F,NH3NH3NH4F,/,,,(2),,:(NH4)2SiF6+4NH3+2H2O6NH4F+SiO2(6),,w(NH4F)40%,,,,,(3),,,,:NH4F+KOHKF+NH3+H2O(7)NH4F+NaClNaF+NH4Cl(8)6NH4F+Na3A1O3Na3AlF6+3NH4OH+3NH3(9)(7)(9),(8),,,,,22以氟硅酸钠为原料制取氟化合物和二氧化硅的生产方法,NH4F40%,,,,,,,,3,,,,62磷肥与复肥2005年第20卷第5期31过磷酸钙生产中的氟、硅资源,,,2.4%F1%H2O40%,1t9.5kgFSiF4,9.5kgF7.5kgSiO2,m(F)/m(SiO2)1.26620t/a1.8,11.11t/a,1055.45t833.25t2000t,2000t10.55t8.33t,,,,32萃取磷酸中的氟、硅资源,65%70%,,1t30%P2O52.6%F,65%,16.9kgF8.89kgSiO2,m(F)/m(SiO2)1.90300tP2O5,30%P2O51000t,1000t,16.9t8.89t,50%P2O5,33磷肥生产中氟、硅资源利用的途径331,,332P2O550%;,,,,,,,,20,,98%99%,70%80%,,,4,20t/a1055.45t832.25t,,80%,90%,,1120t/a/(ta1)/(t1)/(a1)/(a1)11392.41100153.1648.783.522099.83200671.91085.6427.3749.93500262.4494.52750550151.332899.7100002899.73262.11049.33749.93500262.441849.955001017.41279.8840.5749.93500262.451424.85500783.71046.1739.8749.93500262.46!1749.84500787.41049.8558.19749.93500262.47!1399.85500769.91032.3442.35749.93500262.481111.05000555.5817.9544.7749.93500262.4:,150/t(100%NaCl);,350/t;,,;!Al(OH)3,2200/t632005年第20卷第5期 夏克立 1,,153.16/a,(262.4),,1000,400500,,,,,,,HFSiF421,,,1/31,1/3510t/a(,,40t/a),,3:1;2;3:13,1;,,800;,,,,3,70;10;23,,,,/40%,40%NH4F,,,(2),,ARL9800XP+X,32GB429394NaF%w(NaF)w(H2O)w(SiO2)w(Na2CO3)w(SO42)w()w(HF)1980.50.50.50.30.70.12951.01.01.00.530.13841.52.02.0100.13NaF/%/%/%w(Al)0.004w(S)0.125w(Zn)0.0005w(Ca)0.050w(P)0.006w()0.107w(Cl)0.259w(Si)0.023w(NaF)98.86w(K)0.0015w(Fe)0.005:320;3,ClS,,,,,:(1),,,1100m,(2),,,,1,,(3),,,,,,,(4),(5),,,(下转第67页)64磷肥与复肥2005年第20卷第5期75,,7525NaOH加入量100mg/kg,NaOH,33NaOHNaOH/mL/(mgkg1)NaOH/mL/(mgkg1)123645121715433933,4mLNaOH,,,,44w()/%/%S/%1515150.31,0.26,0.32,0.28,0.290.290.0248.27210100.40,0.38,0.36,0.41,0.390.390.0204.9723980.44,0.39,0.41,0.42,0.400.410.0184.39181660.32,0.34,0.29,0.30,0.280.310.0247.904,,4,90.8%3,;,[][1]GB/T244391,,1973[S].[2].[M].:,1976.137142.[3].[M].:,1976.3940.[4],,,.[M].:,1996.187212.[5],.()[M].:,1993.486524.(上接第64页)(6),,,,;,,,,7,,,,,;,,,,,,,,,,,,,,,[][1].[M].,1983.[2],.[M].,1997.672005年第20卷第5期 张永旺等