Shanghai Daoqin Plastics Co., Ltd.

乙丙橡胶（EPR） is 继Zieg1er一Natta catalytic agent 发明, polyethylene (PE) and polypropylene (PP) rear 问世 一 types ethylene. propylene is basic mono copolymer 橡胶, separation is binary 乙丙橡胶（EPM） and ternary 乙丙橡胶（EPDM）两 large type. front is ethylene and propylene copolymer; rear is ethylene, propylene and a small amount of non 共轭二烯烃 copolymer. EPR tool has many its it general purpose combined formed 橡胶 不 tool excellent property can, add mono 体价廉 easy, applications 广泛, is 80 year 代以 国 outer large combined formed product types in development most fast types, its output/production volume, production can force and amount in 发达国家 in 均居第三位, 仅次于丁苯橡胶, 顺丁橡胶. 1998 year world EPR总 production can force is 102吨, amount is 81．4 10,000 tons. statistics, 1999 year amount is 83．61 10,000 tons, expected 2003 year will to 98．0 10,000 tons. 1998～2003 year EPR demand growth rate is 3．8％, high 于丁苯橡胶 and 顺丁橡胶 demand amount growth speed rate. 　　 currently FPR industrial production process has solvent liquid polymerization method, polymerization method and gas versus polymerization method types. lower will separation detailed discussion its technology and 待点, 并进行 technology comparison. 　　1, solvent liquid polymerization process 　　1．1 technology 状况　　60 year achieve industrial 化, 经不断完善 and 改进, technology formed 熟, is many newly built plant/unit use, is industrial production technology, 约占FPR总 production can force 77．6％. 　　该 process is in can solvent understanding product, also can solvent understanding mono and catalytic agent system solvent agent in 进行 均 versus reaction, usually 以直链烷烃如 positive is solvent agent, using/adopting V一A1 catalytic agent system, polymerization temperature degree is 30～50C, polymerization pressure is 0．4～0．8 MPa, reaction material in polymer quality separation generally is 8％～10％. process process basic upper Raw Materials 准备, chemical product made, polymerization, catalytic agent remove, mono and solvent agent recycling made and poly, drying and 　　 packaging and other 工序组 formed, due to company in certain separation or control has patent technology, 因而各 tool process methods. table/sheet property company has DSM, Exxon, uniroya1, DuPont, Japan Mitsui and JSR company. its in most type table/sheet is DSM company, it not only is full most large EPR production 者, but also in Netherlands, USA, Japan, Brazil has sleeve/set plant/unit is using/adopting solvent liquid polymerization process, world solvent liquid polymerization process production EPR总 can force 1/4. lower will company is 例进行说明. 　　DSM company using/adopting is solvent agent, drop sheet/slice 烯（ENB） or di ring 戊二烯（DCPD） is mono 体, hydrogen gas is molecular weight adjustment agent, VOCL3一1／2AL2Et3CL3 is catalytic agent. in addition, is improve/increase catalytic agent active property and reduce its use amount, also add promote agent. catalytic agent ratio use amount, 预处理 methods, promote agent type type is DSM company has technology. reaction material material grade cold to 一500C, according to production grade, mono or 两釜串联操 as. poly 　　 combined 釜容积 large is 6m3. polymerization reaction conditions is: temperature degree low 于650C, pressure low 于2. 5 MPa, reaction hot used for reaction device hot rise temperature. in alkali property agent and hot water function lower, polymer liquid in 残留 钒 catalytic agent water versus, 经两次转 versus process by 彻底脱 remove. reaction mono 体经二次 decrease pressure recycling ring use. toward liquid in add stabilizer and other additives （ production grade add filling 油）. 汽提蒸出残存 ethylene, propylene and large separation solvent agent rear liquid 送至两台串联 凝 poly 釜进行凝 poly, 并进一步蒸出 recycling 残余己烷 solvent agent ring use, JC胶粒浆 liquid water rear drying system, rear pressure block or powder material packaging. 含ENB waste hot gas 送至焚烧炉焚烧, 含钒污 water 送至污 water mono 元, in agent in and function lower, 钒进入钒渣 in, 定期送堆埋场掩埋, 经脱钒 污 water 排至污 water 处理 injection molding parts processing 处理. 　　DSM company EPR solvent liquid polymerization process technology formed 熟, comparison 先进, has lower advantages: （1） investment low, process most 佳化. reaction device excellent ratio design can meet/satisfy reaction material material mixed combined requirements, can control polymerization reaction process parameters and product quality, polymer liquid concentrated degree high ring solvent agent amount less, polymerization 釜体积 small production strong/high degree high, raw materials and ring mono need made, catalytic agent efficiency high, waste in content low, production elastic property large. （2） production as use low, plant/unit year as time long, raw materials and ratio agent consumption low, using/adopting control system for production control. （3） product quality tool has strong/high competition force. product in catalytic agent content low, production in product less, product grade 切换灵 active, waste product amount less, product features can use requirements adjustment, product grade more, value can in 20～160 wide scope/range inner adjustment, quality stability, heavy property good, product specifications indicators 变化幅 degree narrow and product processing properties excellent. 　　1．2 technology features 　　 technology comparison formed 熟, as stability, is industrial production EPR main/primary methods; product product types grade relatively more, quality uniform, ash content content relatively less, application scope 广泛; product electrical insulation property can good. is due to polymerization is in solvent agent in 进行, 传质传 hot to made, polymer separation generally control in 6％～9％, most high 仅达11％～14％, polymerization efficiency low. meanwhile, due to solvent agent recycling made, production process/workflow long, equipment more, construction investment and as cost relatively high. 　　2 悬浮 polymerization process 　　2． technology 状况　　EPR悬浮 polymerization process product grade more, its applications has property, main/primary used as polyolefin modified, currently has Enichem company and Bayer company use, 占EPR总 production can force 13.4%. process is according to propylene in copolymer reaction in active property relatively low principle, will ethylene solvent understanding in liquid propylene in copolymer combined. propylene is mono also as reaction 介质, its 本身 蒸发致 cold as control reaction temperature degree, reaction pressure. formed copolymer solvent liquid propylene, 而呈悬浮于 its in fine 粒淤浆. also can separation is generally polymerization process and 简化悬浮 polymerization process. 　　2．1．1 generally polymerization process 　　Enichem company using/adopting process: 以乙酰丙 ketone and AlEt2Cl is catalytic agent, chlorine acid ester is active agent, HNB or DCPD is mono 体, 二乙基 zinc and hydrogen gas is molecular weight adjustment agent. production product grade different, will ethylene, propylene, mono and catalytic agent add tool has more 桨式搅拌 device sleeve/set polymerization in, reaction conditions is: temperature degree 一20～20oC, pressure 0．35～1．05MPa. reaction hot reaction versus mono 体蒸发移 remove. reaction versus in polymer quality separation control in 30％～35％, polymerization reaction in high degree control lower 进行, formed polymer propylene 淤浆间歇 （10～15次／h）送入洗涤 device, use poly alcohol make catalytic agent active, again use NaOH water solvent liquid 洗涤. liquid 送入汽提塔汽提, reaction ethylene, propylene and ENB separation recycling system made rear ring use. 胶粒一 water liquid 经振动筛脱 water, pressure drying, pressure block and packaging formed product 胶. process features is polymerization made use solvent agent, polymer concentrated degree high, strong/high equipment production can force, meanwhile solvent agent ring and recycling, can amount. 　2．1．2简化悬浮 polymerization process 　　该 process is in generally polymerization process upper development formed 功, main/primary is using/adopting high titanium catalytic system, 不必进行 catalytic agent remove, reaction mono 体不需处理即 can use. usually used for production EPM, this is is 闪蒸不 easy remove reaction mono 体. its process process/workflow is: reaction in belt/tape sleeve/set 搅拌釜 in 进行, using/adopting TiC1, 一MgC12一A1（i一Bu）, catalytic agent system, catalytic agent efficiency is 50kg polymer ／g titanium, reaction temperature degree 27C, pressure 1．3MPa, polymer quality separation is 33％. reaction 釜出 蒸汽 material material pressure shrink to 2．7 MPa并 cooling rear reaction 釜. polymer 淤浆经闪蒸脱 remove reaction mono 体, 不需精 made 处理, pressure shrink and cooling rear 直接循 ring to reaction use. remove mono polymer 不必净化处理即 can as is formed product. product can is powder 状, sheet/slice or pellets 状. in recent years, Enichem company using/adopting rear V一A1 catalytic system, catalytic agent efficiency improve/increase to 30～50kg polymer /g钒, 省 洗涤脱 remove catalytic agent 工序, 同样简化 process process/workflow. 　　2．2 technology features 　　EPR悬浮 polymerization process features is: polymerization material solvent reaction propylene, system viscosity relatively low, improve/increase rate, polymer quality separation high 达30％～35％, its production can force is solvent liquid method 4～5倍; solvent agent recycling made and poly and other 工序, process process/workflow 简化, investment less; can production very polymer/macromolecule amount product types; product cost ratio solvent liquid method low. its 不足之处 is: due to use solvent agent, from polymer in 脱离残留 catalytic agent comparison difficult; product 　　 product types grade less, quality uniform property 差, ash content content relatively high; polymer is solvent liquid propylene pellets, make maintain 悬浮状态 relatively difficult, especially polymer concentrated degree relatively high and a small amount of 凝胶时, reaction easy 于挂胶, 甚至发生 equipment pipeline phenomenon; product electrical insulation property can relatively 差. 　　3 gas versus polymerization process 　　3．1 technology 状况　　EPR gas versus polymerization process is 由Himont company rate 先于20世纪80 year rear 期实施 industrial 化. UCC company 则于90 year 代初宣布 gas versus method EPR in plant/unit 投入试 production, its 9．1 10,000 tons / year gas versus method EPR industrial plant/unit 于1999 year positive start production. currently, process 占EPR总 production can force 9％. UCC company EPR gas versus polymerization process most tool table/sheet property, it separation is polymerization, separation 离净化 and packaging 三 工序. quality separation is 60％ ethylene, 35．5％ propylene, 4．5％ ENB同 catalytic agent, hydrogen gas, nitrogen gas and 炭黑一起 add ratio reaction device, in 50～65C and for pressure 2．07 kPa lower gas versus polymerization reaction. ethylene, propylene and ENB mono 程转化 rate separation is 5．2％. 0.58％ and 0.4％. reaction device reaction mono 体经循 ring gas pressure shrink machine pressure shrink rear 进入循 ring gas cooling device remove reaction hot, and new raw materials gas 一起循 ring reaction device. from reaction device EPR powder 未经脱 gas drop pressure rear 进入净化塔, use nitrogen gas remove 残留烃 type. 自净化塔顶部 gas cold recycling ENB rear use 泵送回流 ratio reaction device. formed micro product packaging 工序. 3．2 technology features 　　 and front types process versus ratio, gas versus polymerization process has its advantages: process process/workflow short, 仅三道工序, 而传统 process has 七道工序; need solvent agent or dilute agent, solvent agent recycling and made 工序; 几乎无三暖排放, has 利于生态 ring 境保护. its product general purpose property relatively 差, has product is black. this is due to is 　　避免 polymer viscous, using/adopting as is 流态化 additives 之故. although development formed use silicon viscous and 云母代替炭黑 production white and has color product, 但第一 sleeve/set industrial production plant/unit still can production black FPR. 　　4 various production process technology comparison 　　FPR various production process technology comparison table/sheet: 示. 　　由 table/sheet 1 can 看出, in FPR various production process in, solvent liquid polymerization process investment and cost most high. investment high is is process/workflow long, high viscosity dispersion hot difficult, equipment production strong/high degree low, reaction rear polymer concentrated degree dilute （仅 is 6％～14％, polymerization process is 33%）, mono 体, solvent agent recycling relatively high use; cost high main/primary is is use engineering 费, 折旧费, solid cost use high. this is due to production process in consumption relatively high electrical and 蒸汽 致. 　　悬浮 polymerization process investment and cost process separation versus same solvent liquid polymerization process 77％ and 88％, tool has investment less, raw materials consumption and can consumption low, production cost low, waste 处理费 use less and other features. 　　 gas versus polymerization process investment and product cost most low, separation versus 当于同 and other solvent liquid polymerization process 42％ and 68％. 　　 table/sheet: EPR various production process technology comparison 　　 project solvent liquid polymerization polymerization gas versus polymerization 　　 production can force ／（万t/a） 4．5 4．5 9．1 　　 investment, ／百 10,000 USD 　　界区 inner 6900 5250 6000 　　界区 outer 2510 2020 1900 　　总 investment 9410 7270 7900 　　 versus for mono investment ／％ 100 77 42 　　 production cost ／（美元／t） 　　 raw materials 691 688 686 　　公 use engineering 178 103 34 　　 its it 35 35 13 　　 can cost /(美元／t) 904 826 733 　　 solid cost /(美元／t) 200 168 83 　　总现金 cost /(美元／t) 1104 994 816 　　折 day 费／(美元／t) 261 201 109 　　总 cost (美元／t) 1365 1195 925 　　 versus for cost ／％ 100 88 68 　　5结论　　综 upper 述, although EPR solvent liquid polymerization process investment and cost most high, its product comprehensive property can good, speed degree fast, product application scope 广, is currently outer most use methods. polymerization process production process/workflow short, investment and cost relatively low, however product property can has advantages, application scope relatively narrow, currently and solvent liquid polymerization process use 广泛. gas versus polymerization process product in has a large amount of 炭黑, general purpose property relatively 差, made it use scope/range, its process process/workflow short. production high and 清洁, has reduce production cost and 保护生态 ring 境, for long use solvent liquid polymerization process tool has 根本变革 property 意义, is combined formed industrial technology in the future development trend, already formed is outer large company versus development and excellent development project. process although currently has 不尽如人意之处, has company for it 甚至持谨慎态 degree, also large can can very fast long industrial application solvent liquid polymerization technology, from long 远 看, its development outlook/prospects is 乐观. but also, technology positive in toward poly butadiene gas versus combined formed technology direction expand 展, will for combined formed production technology future development generate heavy large toward property function.