丙烯腈装置副产氢氰酸的工业利用Hydrocyanic acid of acrylonitrile plant industrial utilization.docx

丙烯腈装置副产氢氰酸的工业利用Hydrocyanic acid of acrylonitrile plant industrial utilization.docx

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丙烯腈装置副产氢氰酸的工业利用Hydrocyanicacidofacrylonitrileplantindustrialutilization

丙烯腈装置副产氢氰酸的工业利用（Hydrocyanicacidofacrylonitrileplantindustrialutilization）

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Reviewon

Chemicalscienceandtechnology,2003,11

（2）:

60~63SCIENCE&TECHNOLO,GY,IN,CHEMICAL,,INDUSTR,Y

Hydrocyanicacidofacrylonitrileplantindustrialutilization

ZhouChunyan1,ZhangWenwu2

（the1.ResearchInstituteofPetroChinaJilinPetrochemicalCo,JilinJilin132021;researchexperimentfactoryofJilinChemicalGroupCorporationJilin2.,Jilin132021）

022*******

Hydrocyanicacid（HCN）isacolorlessliquid,easytoflow,extremelyvolatile）,arehighlytoxic,theproportionof0.687620/（4-14degreesC,meltingpoint,boilingpointof26DEGC.Misciblewithwater,ethanol,orether.Isaweakacid,widelyusedinindustry,agricultureaspesticides,usedtofumigationwarehouses,fruittrees,seedlingsandsoon.Theindustrialproductionmethodsusinghydrocyanicacidsynthesisofotherchemicals,designedtoenableenterprisestolearnmoreaboutthecomprehensiveutilizationofhydrocyanicacid.

1.12isobutylenemethodhydrocyanicacid

Thegenerationofhydrocyanicacidandisobutene,tertbutylaminesulfate,thenTERTbutylamineandammonianeutralization,andby-productammoniumhydrogensulfate.Thechemicalreactionis:

（CH3）2CCH2+HCN+H2+SO42H2O（CH3）3CNH2?

2SO4+HCOOHH（CH3）3CNH2?

2SO4+NH3（CH3）3CNH2HNH4（TERTbutylamine）+HSO4theoperationprocessissimple,goodproductquality,productyieldwithISObutenemetercanreachmorethan83%,butthehighcorrosionresistancerequirementsonequipment,rawmaterialsofcyanidepollutesenvironment,highproductioncost.1.22MTBEmethodusinghydrocyanicacidhydrocyanicacidasrawmaterial,thesulfuricacidcatalyzedreactionwithmethyltertbutylether,acidreactionafteraddingmethanolandmethylformateproduction,by-productmethylformatebydistillationafterneutralizationwithNaOH,formationofTERTbutylamineandsodiumsulfate,thendistillationofTERTbutylamine.Thechemicalformulais:

CH3

CH3,CH3,O,CH3+HCN+H2,SO4+

1synthesisoftertiarybutylamine

Tertbutylamineasrawmaterialoforganicsynthesis[1,2],forthesynthesisofMedicine（antituberculosisdrugrifampin）,pesticides（pesticides,fungicides）,highefficiencyandsafetyofrubberaccelerator（NS,TBSI）,dyestain,alsocanbeusedasasolvent.ForeigncountriesaremainlyusedinsyntheticrubbervulcanizingacceleratorNS,insteadofNOBS[3].NOBSmoleculecontainssecondarystructure（fromrawmaterialmorpholine）,intherubberprocessing,production,storageanduseprocess,easytoformN2nitrosamines,carcinogeniceffect.NSissimilartoNOBSinmolecularstructure,butNSistheprimaryaminestructureanddoesnotproduceN2nitrosamines.AsarawmaterialforsynthesisofNS,tertiarybutylaminehasalargermarketcapacityanddevelopmentpotential.DomesticNSdemandisexpectedtoreach14thousandTin2010,about7000toftertbutylamine,inaddition,tertiarybutylamineinmedicine,pesticides,dyesandotherindustrieshaveawiderangeofapplications.Therefore,fromtheperspectiveofdevelopment,tertbutylmarketisverypromising.MethodsusinghydrocyanicacidasrawmaterialsinthesynthesisofTERTbutylaminewithisobutylenemethodandmethyltertbutylether（MTBE）method[4].

Date:

2002212210acceptedtheauthor:

ZhouChunyan（1971-）,female,SichuanLiangping,engineerResearchInstituteofJilinPetrochemicalCo,

Mainlyengagedinchemicalinformationresearchwork.

OH

methanol

H2O

（CH3）3,CN,H2,2,SO4+HCOOCH3,H

（CH3）3,CN,H2,2,SO4+2NaOH,H（CH3）3,CN,H2+Na2,SO4+2,H2,O

Themethodhastheadvantagesofsimpleprocess,highyield,goodproductquality,lowproductioncostandnopollutiontotheenvironment,andissuitableforthenationalconditionsofourcountry.Foreigncountrieshaveachievedindustrialproduction.China'sQiluPetrochemicalIndustriesCo,FushunPetrochemicalResearchInstitute,ChineseAcademyofSciences,DalianInstituteofphysicalchemistry,Nanjingchemicalindustry

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Secondissue

ZhouChunyan,etal.Hydrocyanicacidofacrylonitrileplantforindustrialuse

61?

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Factory,Liaoning,AnshanXindaChemicalPlant,etc.,havealsostudiedthelaw,andbuiltasmallproductionequipment.

2synthesisofmethylmethacrylate（MMA）

Methylmethacrylateisoneofthemostimportantorganicchemicalrawmaterials.Itisthemonomerofsyntheticacrylicresin.MainlyusedintheproductionoforganicglassandPVCimpactmodifieradditivesACRandMBS,aswellasthesecondmonomerofacrylicfiberproduction,ionexchangeresin,papercoatingagents,textileauxiliaries,leatherprocessingagent,lubricatingoiladditive,pourpointdepressant,woodandsoftwoodinfiltrationagent,penetrant,motorcoilinsulationfillingmaterialsandplasticemulsionplasticizeretc..Inrecentyears,withtherapiddevelopmentofnationaleconomyandtheimprovementofpeople'slivingstandards,theconsumptionofMMAisgrowingrapidly,isexpectedto2005thetotaldemandforMMAinChinawillreachabout168thousandT,thepotentialmarketisstillthemainorganicglass,water-basedpaintindustryandPVCmodifieretc..Atpresent,China'sMMAproductioncapacityandoutputcannotmeettheneedsofdomesticactualproduction,andalargenumberofimportsareneededeveryyear.In1995,theimportvolumewasabout11thousandT,andimportvolumereached65thousandTin2001.Acetonecyanohydrin（ACH）methodisthefirstindustrializedproductionofMMA,bythedirectadditionofacetoneandhydrocyanicacid,suchascausticinthepresenceofalkalinecatalystcanquantitativelygenerateacetonecyanohydrin.Thenatabout100DEGCtoacetonecyanohydrinwithconcentratedsulfuricacidtreatment,whichgeneratesmethylacrylamide.Itisreactedwithmethanolat80DEGCtoproducea[5,6]methylacrylate.Thereactionequationisasfollows:

CH3

CH3CCH3OCH3CH3CH3+HCNOHCH3CH2CCOOCH3H4HSO4CN+N+H2+SO4CH3OHCH3CH3OHCN（acetonecyanohydrin）

Themainrawmaterialofhexamethylenediaminealso,theproductionofadipicacid.In1972theUnitedStatesDuPontCodevelopedusinghydrocyanicacidasrawmaterials,"industrialproductionmethodofdirecthydrogencyanideproductionofadiponitrilebutadiene7].Atpresent,theDuPontCohasdevelopedthethirdgenerationofbutadieneforadiponitrilecatalyst[8],therealizationofindustrializationsetinFranceonthejointventureRhodiaInc.Synthesisofadiponitrilebutadienehydrocyanationmethodisdividedintothreesteps,thereactionisasfollows:

（1）pentenenitrilesreaction

CH2,CHCH,CH2+HCN,CH2

Ni[P（OR3）3]

Solvent,100DEGC

-NCCH2,CH2,CH-NCCH2,CH-NC-C,HCH

CH3CH2

CHCH3

（2）isomerizationreactionNC,C,H2,CH,CH3,CH2

10~200DEGC

ZnClNi[P（PoArCH3）3]4

-NCCH2CH

CHCH3CH2

-NCCH2,CH2,CH

（3）adiponitrileformationreactionsofHCCH2CH+2HCN

ZnC1Ni[,P（PoArCH3）3]4ZnCl22TiCl3CdIaromaticsolvent

CHCH3+NCCH2CH2CH

2nc（ch2）4cn（己二腈）（4）合成己二胺

（甲基丙烯酸甲酯）该法工艺流程短,技术成熟,产品收率高,既避开了剧毒的氰化钠又解决了丙烯腈的副产,减少了氢氰酸对环境的污染,是目前国内外生产mma的主要方法.用该法生产的mma其产量约占世界mma总产量的80%.

在骨架镍骨架钴催化剂存在下,己二腈催化加氢还原得己二胺[9].化学反应式为:

nc（ch2）4cn+4h2h2n（ch2）6nh2（己二胺）（5）合成己二酸己二腈在酸或碱的水溶液催化下,水解生成己二酸和氨[10].在浓硫酸中限制水量进行水解,则停留在己二酰胺阶段.化学反应式为:

nc（ch2）4cn+h2oh2noc（ch2）4conh2或hooc（ch2）4cooh+nh3（己二酸）

h+或oh

3合成己二腈

己二腈是生产尼龙丝的关键中间体,是生产

4合成亚氨基二乙酸

亚氨基二乙酸用于农药合成草甘膦,草甘膦

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1994-2010chinaacademicjournalelectronicpublishinghouse.allrightsreserved.

22甲基232丁烯ch2

顺、32戊烯反

42戊烯腈

62?

化工科技

第11卷

是一种重要的除草剂,用于农耕地和非农耕地除草;在电镀工业上用于化学镀金和配制三价铬电镀液;在水处理行业中,与其它螯合物配合,可螯合钙、镁离子;用其合成的表面活性物可作为盐水系统热交换器的阻垢剂;将其引入不同的聚合体系中,可得到用途各异的螯合型阳离子交换树脂,这些树脂用于处理化学镀废液,以及核工业和反应堆废液.亚氨基二乙酸在其它方面也有广泛的用途.氢氰酸法合成亚氨基二乙酸,是将氢氰酸、六（乌洛托品）和甲醛以酸性水溶液为反亚甲基四胺应介质,在管式反应器中连续反应生成亚氨基二乙腈,加入烧碱使之水解成亚氨基二乙酸钠,再以浓硫酸酸化和调节ph值,亚氨基二乙酸从溶液中结晶出来,经离心分离、、洗涤干燥得产品[11].反应实例:

在管式反应器中,反应温度120～170℃,停留时间1.5～5min,反应混合物ph值6.5～9.5,反应完成后产物进入水解釜,水解温度100～102℃,水解后得产品.化学反应式为:

n4（ch2）6（六亚甲基四胺）+8hcn+2ch2o

4nh（ch2cn）2+2h2onh（ch2cn）2+2naoh+4h2onh（ch2coona）2+2nh4ohnh（ch2coona）2+h2so4nh（ch2cooh）2（亚氨基二乙酸）+na2so4

6合成丙烯腈

乙烯和氢氰酸在钯催化剂作用下合成丙烯腈,可增加丙烯腈产量.该技术由日本旭化成公司开发[13].化学反应式为:

ch2ch2+hcn+1/2o2ch2chcn+h2o

（丙烯腈）

7合成羟基乙腈

羟基乙腈作为有机合成原料,可与苯胺缩合制取苯胺基乙腈,然后水解制取苯胺基乙酸,代替氯乙酸合成靛蓝染料[14].甲醛与氢氰酸在催化剂存在下制得羟基乙[15]腈.

Thechemicalreactionsare:

（HCHOH5+HCN,hoch2）C6（hoch2）+H2

H5,C6,hch2（Glycineaniline,acetonitrile）,C6,H5,N+,H2,H3,O,hch2,,H5,hch2,COOH,C6

8conclusion

（1）hydrocyanicacidisaby-productofacrylonitrile,comprehensiveutilizationofhydrogen

Themethodismatureandeasytobeindustrialized.Thequalityandproductioncostofthismethodareverycompetitive.Atpresent,allforeigncompanieshaveadoptedthismethodtoproduceiminodiaceticacidtwo.

5synthesisofcyanuricchloride

Cyanuricchlorideisanimportantfinechemicalintermediates,widelyusedinpesticides,dyesandauxiliariesandotherindustries,mainlyusedinthemanufactureofreactivedyes,fluorescentwhiteningagentBL.,pharmaceuticals,herbicides,shrink-resistagent,surfactantandexplosives.AstheEuropeanchemicalintermediateeastmove,Chinahasbecometheimportantsupplyofcyanuricchloridebase,coupledwiththec