CN100471876C - 互连环管反应器 - Google Patents
互连环管反应器 Download PDFInfo
- Publication number
- CN100471876C CN100471876C CNB2005800046625A CN200580004662A CN100471876C CN 100471876 C CN100471876 C CN 100471876C CN B2005800046625 A CNB2005800046625 A CN B2005800046625A CN 200580004662 A CN200580004662 A CN 200580004662A CN 100471876 C CN100471876 C CN 100471876C
- Authority
- CN
- China
- Prior art keywords
- annular
- reactor
- pipe reactor
- polymkeric substance
- transferred
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 37
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 239000012968 metallocene catalyst Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- -1 polyethylene Polymers 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 230000002902 bimodal effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical class Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1837—Loop-type reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
- B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/007—Separating solid material from the gas/liquid stream by sedimentation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Executing Machine-Instructions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明描述了包括两个互连环管的反应器,其中生长的聚合物连续地在回路中从第一环管通过第一管线流向第二环管,和通过第二管线返回第一环管。本发明还公开了一种于两个互连环管反应器中聚合烯烃的方法。
Description
本发明涉及双环反应器(double loop reactor)中的乙烯聚合领域。
高分子量聚烯烃如聚乙烯通常较相应低分子量聚烯烃具有改善的机械性能。然而,高分子量聚烯烃难于加工且制备成本高。具有宽或双峰分子量分布(MWD)的聚烯烃是理想的,因为其组合了高分子量组分带来的有利的机械性能以及低分子量组分带来的改善的加工性能。
对于很多高密度聚乙烯(HDPE)应用而言,聚乙烯具有增强的韧性、强度和抗环境应力裂化(ESCR)是很重要的。高分子量的聚乙烯更易于具有这些增强的性能。然而,随聚合物分子量的增加,树脂的可加工性就会下降。通过提供具有宽或双峰MWD的聚合物,在可加工性,特别是挤压性能得以改善的同时保有高分子量树脂特性的理想性能。
一些制备具有双峰或宽分子量分布的树脂的方法有:溶体混合、串联结构反应器或带有双位催化剂体系的单反应器。
用于制备聚烯烃的铬催化剂趋向扩大分子量分布,且在某些情况下能够得到双峰分子量分布,但通常这些树脂的低分子部分含有大量的共聚单体。尽管宽分子量分布提供了可接受的加工性能,双峰分子量分布可提供更优良的性能。在某些情况下,后者甚至可调节高分子量和低分子量部分的份量从而调节机械性能。
已知使用两个串联反应器由Ziegler Natta催化剂可制得双峰聚乙烯。典型地,在第一反应器中,由氢气和乙烯在Ziegler Natta催化剂存在下反应形成低分子量均聚物。该方法中必需使用过量的氢,由此需在产物通入第二反应器之前从第一反应器中除去所有的氢气。在第二反应器中,得到乙烯和己烯的共聚物从而制得高分子量的聚乙烯。本领域还公开了相反结构(reverse configuration)。
金属茂催化剂也已知用于制备聚烯烃。例如,EP-A-0619325描述了制备具有多峰或至少双峰分子量分布的聚烯烃如聚乙烯的方法。在该方法中,使用包括至少两种金属茂组分的催化剂体系。金属茂组分可选自,例如双(环戊二烯基)二氯化锆和亚乙基-双(茚基)二氯化锆。通过在相同反应器中使用两种不同的金属茂催化剂组分,得到至少双峰的分子量分布。
某些如管材的应用需要聚乙烯树脂具有裂纹缓慢扩展(slow crackgrowth)的高耐受力以及快速裂纹扩展产生的冲击韧性(rapid crackpropagation yielding toughness)的耐受力。EP-A-0571987公开了例如使用多级聚合制备乙烯聚合物组合物的方法。作为主要组分的催化剂包括,过渡金属化合物,能够与过渡金属化合物反应形成离子络合物的化合物和有机铝化合物。
或者,宽或多峰分子量分布可通过如EP-A-0735090中所述的物理共混两种或多种树脂而获得,该文献中公开的聚乙烯树脂组合物由三种聚乙烯组分通过物理共混制得。
在另一种方法中,使用Ziegler-Natta催化剂体系在两个或多个互连聚合区内进行α-烯烃的气相催化聚合,其特征在于第二聚合区内引入的气体与第一聚合区内的气体组分不同:即多区循环反应器工艺。它由两个互连的聚合区组成:
1.“升液管”或快速流化区,其中气体速度大于转移速度;
2.“降液管”,其中聚合颗粒在重力作用下流下。
将单体和催化剂体系在聚合条件下加料入“升液管”。生长的聚合物(growing polymer)于快速流化条件下向上流动,然后离开“升液管”并进入“降液管”,其中聚合颗粒在重力作用下向下流动。然后颗粒离开“降液管”,并再次引入到“升液管”中。于是在两个聚合区内建立了循环。
该方法进一步需要:
1.完全或部分地阻止“升液管”中存在的气体混合物进入“降液管”;
2.引入到“降液管”中的气体和/或液体混合物不同于“升液管”中存在的气体混合物;
多区循环反应器工艺例如在WO-A-97/04015和WO-A-00/02929中所述。其主要应用Ziegler-Natta催化剂体系,并受限于难于完全除去“升液管”中存在的气体混合物并难于阻止其进入“降液管”缺陷。且该工艺难于控制两区中的气体组成。由此需要一个不存在上述缺陷的聚合体系。
本发明的一个目的在于提供一种制备非常均质聚合物的聚合工艺。
本发明的另一目的在于提供一种制备具有宽或多峰分子量分布的聚合物的聚合工艺。
本发明相应地公开了一种用于聚合烯烃的双环反应器,其包括:
a)双环反应器(1)和(11);
b)将生长的聚合物从第一环管反应器转移至第二环管反应器的连接装置(4);
c)将生长的聚合物从第二环管反应器返回至第一环管反应器的连接装置(14)。
本发明还公开了由两个互相连接的环管组成的聚合技术,其中生成的聚合物在回路中(in circuit)连续地从第一环管流向第二环管和返回第一环管。
聚合物环绕两环管流动优选平均不超过三次,更优选不超过两次。
在双环反应器正常操作条件下,单体、稀释剂、氢气和共聚单体在泵下游注入第一环管中,生长的聚合物以约8m/sec的速度环绕环管循环流动,相当于每30秒循环一次100m3的反应器。单体溶于稀释剂中,颗粒聚合物悬浮于液体中。在第一环管平均驻留时间的40分钟到1小时后,相当于环绕环管约100转后,颗粒聚合物转移至第二环管中。
转移通常难于进行,因为需要单独控制每一环管中的聚合混合物,从而从第一反应器存在的蒸汽中除去任何第二环管中不理想的组分。文献中公开了一些转移操作方法。例如,US-2001/0018499中描述了一种通过在将悬浮液送入第二反应器之前降低其压力而除去大部分第一反应器中的氢的方法。US-A-5,639,834描述了一种方法,其中第一反应器中形成的富含共聚单体的悬浮液通过沉降柱(settling leg)从该反应器中移除,浓缩的悬浮液送入第二反应器,其中共聚单体量减少。US-A-4,692,501描述了一种方法,其中第一反应器形成的悬浮液在送入第二反应器之前于交换区用逆流液体洗涤。US-A-2001/0018500描述了一种连续聚合方法,其中聚乙烯颗粒的悬浮液从第一反应器中移除,送入旋液分离器,在其中将其分离成的浓缩悬浮液送入第二反应器,分离成的含有稀释剂的液体部分循环回第一聚合区。
第二反应器中的操作条件通常与第一反应器不同,因为其需要制备具有宽分子量分布的聚烯烃。第二反应器的驻留时间短于第一反应器,典型地短少50%,压力通常较第一反应器低1bar以促进转移。
双环反应器可以直接模式(direct mode)进行操作,其中于第一反应器中制得高分子量组分的聚合物,并于第二反应器中制得低分子量组分,或以相反模式(reverse mode)进行。
最终聚合物优选通过沉降柱移出,可增加其固含量。
这些操作条件是本领域已知的。本发明进一步公开了将生长的聚合物从第二环管转移回第一环管中,于是生长的聚合物连续地从一个环管转移至另一个环管。
根据本发明的一个优选实施方式,从第一环管转移至第二环管并回到第一环管是通过沉降柱进行操作。
图1表示了根据本发明的互连环管反应器。单体、任选的共聚单体、氢气和稀释剂加料入在泵(2)下游的第一环管(1)中。生长的聚合物使用沉降柱(3)通过线路(4)转移至第二环管,将其供应到在泵(12)的上游处的第二环管(11)中。循环回第一环管的一部分生长聚合物在第二反应器泵下游处在沉降柱中收集,然后通过线路(14)加入在泵的上游处的第一反应器。该装置具有在第二反应器脱离点和第一反应器进入点之间的正压差,由此易于从第二环管向第一环管的转移。最终聚合物使用沉降柱(13)通过线路(15)从第二环管中取出。
根据本发明的另一个实施方式示于图2,脱离第一环管的物质通过传送线路24送入旋液分离器(25)。所有或部分聚合物颗粒悬浮液通过传送线26被送入第二环管,如果有任何残余物,可通过传送线27返回第一环管或取出。在第二环管驻留后,聚合物颗粒于沉降柱13中浓缩,然后通过传送线28返回第一环管或通过线29取出。
选择易于从一个环管向另一个环管转移的新聚合工艺的几何结构和操作条件。更特别地,必须选择各反应器的压力以使得接受部分的压力总是低于发送部分的压力。这将通过图1公开的结构达到,其利用了以下事实:泵下游的压力比泵上游的压力高约1bar。
或者,可使用离心泵以推动聚合物颗粒通过转移管线,脱离压差限制。
在另一个实施方式中,从第二反应器中排出的聚合物浆料于低压在搅拌器中脱气以除去所有痕量的氢气,并借助于多级离心泵注入第一反应器(图3)。
根据本发明的另一个实施方式中,从反应器中排出的浆料被送入闪蒸罐并完全脱除气体。气体返回循环部分。一部分聚合物被送入挤出机,一部分聚合物被异丁烷润湿并泵送回第一反应器(图4)。
可用于本发明聚合反应的催化剂体系没有特别限制,但优选选择对氢气和共聚单体均能表现良好响应的催化剂体系,因为该反应需要两个聚合区各自独立地操作。优选的催化剂体系包括金属茂组分,更优选如下通式的双茚基组分,
R”(Ind)2MQ2
其中R”是结构桥,Ind是取代或未取代的茚基或四氢茚基,M是周期表IV族金属,Q是具有1-20个碳原子的烃基或卤素,
或如下通式的环戊二烯基-芴基组分,
R”(Cp-Flu)MQ2
其中Cp是取代的或未取代的环戊二烯基,Flu是取代的或未取代的芴基。
用于本发明的催化剂体系除上述催化剂组分外,还包括一种或多种具有离子化作用和能够活化金属茂催化剂组分的活性剂。典型地,活化剂包括本领域公知的含铝或含硼化合物。
该方法当使用金属茂催化剂体系时特别有利,因为它们难以混合:不断地从一个环管向另一个环管转移物质增加了聚合物的均一性。均一性在聚合组合物的水平上增加,且在各颗粒内均一性在聚合物中高分子量和低分子量的百分比水平上增加。此外,由于金属茂消耗氢,因此在向第二环管转移前,无需除去脱离第一环管的聚合物中残余的氢。金属茂催化剂体系对氢和共聚单体均能产生优良的响应。
优选的聚合物是聚乙烯。
图列
图1表示根据本发明的一个实施方式,其中聚合物通过压差从一个环管反应器向另一个环管反应器转移。
图2表示根据本发明的一个实施方式,其中聚合物通过旋液分离器从一个环管反应器向另一个环管反应器转移。
图3表示根据本发明的一个实施方式,其中聚合物通过Moineau型泵从第二环管反应器向第一环管反应器转移。从第二反应器排出的聚合物浆料在低压在搅拌器中脱气以去除所有痕量氢,并借助多级离心泵注入第一反应器。
图4表示根据本发明的另一个实施方式,其中聚合物通过Moineau型泵从第二环管反应器向第一环管反应器转移。从反应器中排出的浆料送入闪蒸罐并完全脱除气体。部分聚合物送入挤出机,其它部分聚合物用异丁烷润湿并泵送回第一反应器。
实施例
在根据本发明的一个特别的操作实施例中,根据图1所示的结构,泵(2)下游处第一环管中的压力为约41bars。大约在第一环管中部约40.5bars压力处从第一环管取出聚合物。第二环管总是保持在比第一环管压力稍低的总压下,此处指泵(12)下游约40.5bars的压力。从第一环管取出的聚合物注入泵(12)上游约39.5bars压力处的第二环管中。在泵(12)下游约40.5bars压力处从第二环管取出聚合物,注入泵(2)上游约40bars压力处的第一环管中。该结构易于聚合物在两个反应器间的流动,但也可使用其它任何聚合物在两个环管间循环流动的方法。
根据本发明制得的聚合物非常均质,因为它们在各反应器中从一个到另一个地逐步生长,而先前的双环体系制得的聚合物是第一反应器继而第二反应器条件的叠加结果。
Claims (8)
1.一种用于聚合烯烃的双环反应器,其包括:
d)双环反应器(1)和(11),定义为第一环管反应器(1)和第二环管反应器(11);
e)将生长的聚合物从第一环管反应器转移至第二环管反应器的连接装置(4);
f)将生长的聚合物从第二环管反应器返回至第一环管反应器的连接装置(14)。
2.一种于两个互连环管反应器(1)和(11)中聚合烯烃的方法,其中生长的聚合物连续地在回路中从第一环管反应器通过管线(4)流向第二环管反应器,然后再通过管线(14)返回第一环管反应器。
3.权利要求2的方法,其中生长的聚合物通过沉降柱(3)从第一环管反应器转移至第二环管反应器和/或从第二环管反应器转移至第一环管反应器。
4.权利要求2的方法,其中生长的聚合物通过压差从第一环管反应器转移至第二环管反应器和/或从第二环管反应器转移至第一环管反应器。
5.权利要求4的方法,其中压差是由各反应器循环泵上游和下游压力的差异而产生的。
6.权利要求2的方法,其中生长的聚合物通过旋液分离器(25)从第一环管反应器转移至第二环管反应器和/或从第二环管反应器转移至第一环管反应器。
7.权利要求2的方法,其中生长的聚合物通过Moineau型泵从第一环管反应器转移至第二环管反应器和/或从第二环管反应器转移至第一环管反应器。
8.权利要求2-7任一项的方法,使用基于金属茂催化剂组分的催化剂体系。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04100588.5 | 2004-02-13 | ||
EP04100588A EP1564223A1 (en) | 2004-02-13 | 2004-02-13 | Interconnected loop reactors |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1926159A CN1926159A (zh) | 2007-03-07 |
CN100471876C true CN100471876C (zh) | 2009-03-25 |
Family
ID=34684754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005800046625A Expired - Fee Related CN100471876C (zh) | 2004-02-13 | 2005-02-08 | 互连环管反应器 |
Country Status (12)
Country | Link |
---|---|
US (1) | US7851566B2 (zh) |
EP (2) | EP1564223A1 (zh) |
JP (1) | JP5006052B2 (zh) |
KR (1) | KR101174524B1 (zh) |
CN (1) | CN100471876C (zh) |
AT (1) | ATE326485T1 (zh) |
DE (1) | DE602005000008T2 (zh) |
DK (1) | DK1603955T3 (zh) |
EA (1) | EA010065B1 (zh) |
ES (1) | ES2264120T3 (zh) |
PT (1) | PT1603955E (zh) |
WO (1) | WO2005080442A1 (zh) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101110800B1 (ko) | 2003-05-28 | 2012-07-06 | 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 | 히드록실기 함유 화합물의 제조 방법 |
EP1803498A1 (en) * | 2005-12-30 | 2007-07-04 | Total Petrochemicals Research Feluy | Dynamic pressure control in double loop reactor |
EP1825909A1 (en) * | 2006-02-23 | 2007-08-29 | Total Petrochemicals Research Feluy | Transfer pipe between loop reactors |
EP1825911A1 (en) * | 2006-02-27 | 2007-08-29 | Total Petrochemicals Research Feluy | Transfer pipe between loop reactors |
EP1839742A1 (en) * | 2006-03-30 | 2007-10-03 | Total Petrochemicals Research Feluy | Flushing in a multiple loop reactor |
EP1842861A1 (en) | 2006-04-03 | 2007-10-10 | Total Petrochemicals Research Feluy | Process for improving the polymerization of ethylene and one or more optional comonomer(s) in a polymerization loop reactor. |
JP2010537021A (ja) * | 2007-08-27 | 2010-12-02 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | 複数のループ反応器を用いるオレフィン重合方法 |
US9556283B2 (en) | 2010-05-21 | 2017-01-31 | Chevron Phillips Chemical Company, Lp | Polyethylene production with multiple polymerization reactors |
US9108147B2 (en) | 2010-10-15 | 2015-08-18 | Chevron Phillips Chemical Company Lp | Component separations in polymerization |
US9180405B2 (en) * | 2010-10-15 | 2015-11-10 | Chevron Phillips Chemical Company Lp | Ethylene recovery by absorption |
US20150361191A1 (en) * | 2011-08-25 | 2015-12-17 | Hanwha Chemical Corporation | A process for the preparation of polyethylene wax using metallocene catalyst |
US8987390B2 (en) | 2012-12-18 | 2015-03-24 | Chevron Phillips Chemical Company, Lp | Chain transfer agent removal between polyolefin polymerization reactors |
US9295964B2 (en) | 2013-09-19 | 2016-03-29 | Chevron Phillips Chemical Company, Lp | Pressure relief for multiple polyolefin polymerization reactors |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7700412A (nl) * | 1977-01-15 | 1978-07-18 | Synres Internationaal Nv | Continu bereiding van polymeren in de massa. |
BE1013235A4 (fr) * | 2000-01-18 | 2001-11-06 | Solvay | Procede de fabrication d'une composition de polymeres d'olefines. |
EP1195388A1 (en) * | 2000-10-04 | 2002-04-10 | ATOFINA Research | Process for producing bimodal polyethylene resins |
US6916892B2 (en) * | 2001-12-03 | 2005-07-12 | Fina Technology, Inc. | Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropylene |
-
2004
- 2004-02-13 EP EP04100588A patent/EP1564223A1/en not_active Withdrawn
-
2005
- 2005-02-08 JP JP2006552608A patent/JP5006052B2/ja not_active Expired - Fee Related
- 2005-02-08 CN CNB2005800046625A patent/CN100471876C/zh not_active Expired - Fee Related
- 2005-02-08 DK DK05716636T patent/DK1603955T3/da active
- 2005-02-08 EP EP05716636A patent/EP1603955B1/en not_active Revoked
- 2005-02-08 AT AT05716636T patent/ATE326485T1/de active
- 2005-02-08 WO PCT/EP2005/050524 patent/WO2005080442A1/en active Application Filing
- 2005-02-08 EA EA200601485A patent/EA010065B1/ru not_active IP Right Cessation
- 2005-02-08 US US11/501,182 patent/US7851566B2/en not_active Expired - Fee Related
- 2005-02-08 PT PT05716636T patent/PT1603955E/pt unknown
- 2005-02-08 ES ES05716636T patent/ES2264120T3/es active Active
- 2005-02-08 DE DE602005000008T patent/DE602005000008T2/de active Active
-
2006
- 2006-09-05 KR KR1020067018025A patent/KR101174524B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
US20080242808A1 (en) | 2008-10-02 |
JP5006052B2 (ja) | 2012-08-22 |
EP1564223A1 (en) | 2005-08-17 |
EA010065B1 (ru) | 2008-06-30 |
CN1926159A (zh) | 2007-03-07 |
DK1603955T3 (da) | 2006-09-11 |
KR20070004688A (ko) | 2007-01-09 |
KR101174524B1 (ko) | 2012-08-16 |
EP1603955B1 (en) | 2006-05-17 |
EA200601485A1 (ru) | 2007-02-27 |
EP1603955A1 (en) | 2005-12-14 |
DE602005000008D1 (de) | 2006-06-22 |
WO2005080442A1 (en) | 2005-09-01 |
DE602005000008T2 (de) | 2006-11-23 |
PT1603955E (pt) | 2007-07-23 |
JP2007522307A (ja) | 2007-08-09 |
ATE326485T1 (de) | 2006-06-15 |
US7851566B2 (en) | 2010-12-14 |
ES2264120T3 (es) | 2006-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100471876C (zh) | 互连环管反应器 | |
CN100582125C (zh) | 用于乙烯聚合的方法和装置 | |
CN1093863C (zh) | 制备聚乙烯的方法 | |
JP5072637B2 (ja) | プロピレンポリマーの製造方法 | |
CN101084059B (zh) | 用于丙烯聚合的方法和装置 | |
CN101735349B (zh) | 用于聚合的环流型反应器 | |
CN102639571B (zh) | 生产聚烯烃的方法 | |
JP5074770B2 (ja) | ビモダルなオレフィン製造での触媒の展開 | |
CN104520338B (zh) | 烯烃的多级聚合方法 | |
CN1378561A (zh) | 生产聚烯烃的方法 | |
WO1997013790A1 (en) | Process for making propylene homo or copolymers | |
CN1922219A (zh) | 改进聚合环流反应器中乙烯和烯烃共聚单体共聚的方法 | |
KR20070057139A (ko) | 바이패스 라인을 구비한 중합 반응기 | |
CN100379490C (zh) | 淤浆环管聚烯烃反应器 | |
CN101942051A (zh) | 一种液相丙烯本体聚合反应连续聚合工艺 | |
CN102060943A (zh) | 一种烯烃聚合的多区循环反应装置和反应方法 | |
US9109058B2 (en) | Method for improving ethylene polymerization reactions | |
CN112745440A (zh) | 抗冲聚丙烯及其制备方法 | |
JP2023514429A (ja) | 多段階重合プロセスにおいてアルファ-オレフィンポリマーを製造するための方法 | |
CN101495224B (zh) | 用于聚合的环流型反应器 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C56 | Change in the name or address of the patentee |
Owner name: TOTAL PETROCHEMICALS RESEARCH FELUY Free format text: FORMER NAME: TOTAL PETROCHEMICALS RES FELUY |
|
CP03 | Change of name, title or address |
Address after: Senev Belgium Patentee after: Total Petrochemicals Res Feluy Address before: Belgium Senev (Eph) Patentee before: Total Petrochemicals Res Feluy |
|
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090325 Termination date: 20200208 |
|
CF01 | Termination of patent right due to non-payment of annual fee |