Shanghai Daoqin Plastics Co., Ltd.

摘 need: China polyolefin industry positive product structure rise grade key/critical stage/phase, Domestic polyolefin product toward in high development accelerated, production high add value polyolefin product for/regarding enterprise is key/critical. main/primary introduction for USA Univation Unipol versus 流化床 process use metallocene catalytic agent XCAT-EZ production high 附 add value metallocene polyethylene (PE) research.  

1, Unipol process metallocene polyethylene (PE) process process/workflow  

USA Univation Unipol gas versus 流化床 process, ethylene as is mono can use Ziegler -Natta catalytic agent, Cr catalytic agent, metallocene catalytic agent, PRODIGY series di catalytic agent. ethylene, copolymer mono 体(丁烯-1 and 己烯-1) in 流化床 reaction device inner anionic 离子配位 polymerization, formed polymer.  

载体 type titanium, metallocene, di or catalytic agent add to reaction device in, reaction hot ring gas belt/tape 出, product powder material 不断 撤出, 经 脱 gas rear 就 can pelletizing. plant/unit currently most large mono production can force 600 kt/a, year as 时数 8000 h, as elastic property 60%～110%(pelletizing system 70%～120%) can production density is 0.915～0.965kg/m3 high, in, low density resin product.  

该 process product main/primary used for injection molding, rotational molding, film, wire drawing, pipe/tube and other. process tool has has simple, 经济, tool has high can property, as elastic property large, safety property high and ring good property and other features, its process/workflow 如图1 示.  

2, metallocene polyethylene (PE) production key points  

in in recent years newly built Unipol polyethylene (PE) plant/unit, can basic 不改变 production process process/workflow, use will Acclaim series catalytic agent add reaction device Mark V catalytic agent add material device will metallocene catalytic agent add reaction device, and PRODIGY series catalytic agent similar, need add 入CA-200 as is catalytic agent. if in patent let in 未包含 metallocene polyethylene (PE) product, production metallocene polyethylene (PE) need attention/notes lower:  

(1) made system: due to metallocene catalytic agent for 杂质 敏感 property more high, therefore for plant/unit made system requirements more high, plant/unit made system can force is 否 meet/satisfy metallocene catalytic agent production requirements need 进一步 assessment.  

(2) pelletizing system: due to metallocene catalytic agent production product molecular weight distribution more narrow, its force large, mixing/compounding machine screw 扭拒会 increase, 导致原 pelletizing system can negative 荷运行; meanwhile due to metallocene catalytic agent active property large, combined ultra- cold production, copolymer mono decrease/reduce 20%, decrease light powder material viscous 现 象, from can has improve/increase plant/unit production can force.  

(3) recycling system: and plant/unit production can force improve/increase versus 匹配, recycling system can force 也需进一步 improve/increase.  

(4) polymerization reaction system: generally polymerization system production can force has 一定余 amount, can meet/satisfy metallocene catalytic agent production need, 尚需进一步 assessment.  

(5) catalytic agent system: metallocene catalytic agent and Acclaim series catalytic agent use sleeve/set Mark V catalytic agent add material system, due to types catalytic agent series 不 兼容, in production XCAT EZ catalytic agent product 时, must for Acclaim series catalytic agent 进行充 separation active and 清理. design used for production Acclaim series catalytic agent product Mark V catalytic agent add material device, due to catalytic agent and add material amount 改变, amount is need heavy new design need 进一步 assessment.  

3, Unipol metallocene polyethylene (PE) production control  

(1), XCAT EZ metallocene polyethylene (PE) for raw materials requirements for/regarding raw materials in requirements, metallocene catalytic agent and Acclaim series catalytic agent versus 似, ratio titanium catalytic agent more is 苛刻. table/sheet 1 示, requirements has raw materials in water, oxygen content small 于1.0ppm, made rear requirements oxygen content small 于0.1ppm, water content small 于0.2ppm, CO2 content small 于0.1ppmw, therefore in production 茂 metal polyethylene (PE) product need according to requirements for made 床层进行定期 recycled, for raw materials indicators 进行监控.  

(2), XCAT EZ metallocene polyethylene (PE) reaction device as process amount effect/influence similar 于UCAT J, increase hydrogen gas micro reduce rate, increase copolymer mono increase rate, for/regarding XCAT EZ catalytic agent, increase 共 poly mono increase rate large copolymer mono for UCAT J effect/influence (table/sheet 1). due to XCAT EZ catalytic agent selection property high 于UCAT J catalytic agent 5 倍, C6/C2 摩尔 ratio small use UCAT J ratio value.  

stability reaction device as  

table/sheet 2 is process amount 响应情况.  

(1) reaction device temperature degree control: catalytic agent rate temperature degree upper rise increase high, 但改变 temperature degree effect/influence MFR, increase reaction device temperature degree improve/increase MFR, temperature degree 并不 is used for control MFR as type as. for/regarding XCAT EZ catalytic agent grade, catalytic agent rate in 85˚C most excellent.  

(2) catalytic agent rate control: C2 separation pressure is for rate main/primary control 手段, meanwhile rate reaction device temperature degree, hydrogen gas concentrated degree effect/influence.  

(3) table/sheet gas speed (SGV) control: for/regarding table/sheet gas speed usually control in 0.61～0.82m/s between, target/goal value is 0.715m/s, relatively low table/sheet gas speed formed expand large 段冲刷不 good, formed sheet/slice, high table/sheet gas speed formed powder belt/tape, 堵塞流化回路.  

(4) ethylene separation pressure control: due to ethylene separation pressure is XCAT EZ metallocene catalytic agent rate main/primary control parameters, and UCAT J catalytic agent versus ratio, XCAT EZ catalytic agent as 时C2 separation pressure usually relatively high, increase ethylene separation pressure, formed MFR reduce.

(5) material control: construction start control good material is important, XCAT EZ construction start 期间, in reaction device above 1m, 3 次BTO rear material 位 target/goal value is above 0.75m.  

(6) distribution (APS) control: distribution (APS) and catalytic agent rate related, relatively high catalytic agent rate, relatively large pellets dimensions, usually control in 648～901μm, 同样 粒径 distribution (APS) 会受杂质 effect/influence.  

(7) resin viscous property control: XCAT EZ in 建议 操 as parameters scope/range inner, in and UCAT J same MI/ density lower, resin viscous property usually 不必担心.  

(8) melt flow index control: XCAT EZ catalytic agent requirements hydrogen gas amount ratio UCATJ catalytic agent less 数百倍. hydrogen gas for catalytic agent rate and UCAT J 催 化 agent product is same, hydrogen gas can polymer growth, reduce catalytic agent active property. in construction start 时, must use amount ratio control, stability production use concentrated degree ratio control.  

(9) density control: XCAT EZ catalytic agent product for 己烯 进 material control and UCAT-J same, due to in reaction device in time short (约 15min), amount ratio rate control non important, generally utilizing C6/C2流 amount ratio control, concentrated degree ratio as is 参考. in same density lower, XCAT EZ catalytic agent 产 product need new copolymer mono amount is UCAT-J product 75%, XCAT EZ polymer in copolymer mono distribution more uniform, copolymer mono utilizing more has 效, micro small 变化都 for density has very large effect/influence.  

(10) additives (CA-200) control: and BMC-200 catalytic agent product same, in production XCAT EZ catalytic agent product 时, need add 入CA-200 additives, 以 decrease/reduce reaction device sheet/slice. in reaction device or heavy new construction start 时, need add 入约15ppmw CA-200 for types 子床进行预处理, catalytic agent 注入时, 开始注入CA-200. production control process in, control CA-200 concentrated degree target/goal value is 30ppmw.  

(11) cold 凝模式操 as: and UCAT-J catalytic agent same, in production XCAT EZ catalytic agent product 时同样 need in cold 凝模式 lower as, cold rate maintain in 8%～10% between. value attention/notes is, and UCAT-J catalytic agent product versus ratio, due to copolymer mono concentrated degree relatively low, production XCAT EZ catalytic agent product ring gas hot can force has reduce. in cold 凝时, need fast 远离露点 temperature degree +/-3℃ left right amount decrease/reduce cold 凝 次数, anti ring 回路结 垢, 堵塞. and UCAT-J catalytic agent different, cold rear reaction device electrical 不会完 full 消失, 但振幅会 reduce, has 偏移, for/regarding XCAT EZ 催 化 agent product, electrical effect/influence relatively small.  

(12) electrical control: and UCAT-J catalytic agent different, for/regarding production XCAT EZ catalytic agent product, use anti-static system for reaction device 进行静 electrical control is 无 效, versus also can can formed sheet/slice, catalytic agent add material device and other.  

(13) product material system as: resin in product material in time can ultra- 35S(G 阀关闭 rear), anti resin in material in reaction 并结 block, its as and UCAT-J catalytic agent product same.  

4, 结语 

currently world upper has metallocene polyethylene (PE) product patent production technology company has Switzerland Ineos company, USA ExxonMobil company, Netherlands Lyondell Basell company, Japan Mitsui Chemicals 株式会社, France Total company, Korea large company, USA Chevron Phillips company, USA Dow chemical 公 司, 奥 利 Borealis company and other.  

国 inner tool 备Unipol metallocene polyethylene (PE) production can force enterprise has 齐鲁石化, 独山子石化, 兰州石化, large 庆石化, cationic wax and other.  

due to Domestic metallocene production amount less, production 厂连续 stability production time versus for relatively short, market upper 流通货源不 more, currently lower factory more procurement 进 口 metallocene polyethylene (PE) is 主. year, related 部门, 科研院 and high 校, 各石化 enterprise for metallocene polyethylene (PE) development heavy 视, versus in 不 久 will high polyethylene (PE) product to rate large degree improves, for Imported product 依赖.