FI89929C - Foerfarande foer homo- eller sampolymerisering av eten - Google Patents
Foerfarande foer homo- eller sampolymerisering av eten Download PDFInfo
- Publication number
- FI89929C FI89929C FI906427A FI906427A FI89929C FI 89929 C FI89929 C FI 89929C FI 906427 A FI906427 A FI 906427A FI 906427 A FI906427 A FI 906427A FI 89929 C FI89929 C FI 89929C
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- Prior art keywords
- ethylene
- propane
- hydrogen
- polymerization
- pressure
- Prior art date
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 22
- 239000005977 Ethylene Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 22
- 238000007334 copolymerization reaction Methods 0.000 title description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001294 propane Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- -1 Polyethylene Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000012429 reaction media Substances 0.000 description 11
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 235000013847 iso-butane Nutrition 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerisation Methods In General (AREA)
Description
ii 9 9 29
Menetelmä eteenin homo- tai kopolymeroimiseksi Förfarande för homo- eller sampolymerisering av eten 5
Keksintö koskee menetelmää eteenin homo- tai kopolymeroimiseksi kiinteiden polymee-ripartikkeleiden muodossa.
Eteenin polymerointi kiinteiden partikkelien muodossa nestefaasissa on tunneUua. 10 Tälläisissä prosesseissa polymerointi suoritetaan tyypillisesti reaktiovällaineessa tai laimentimessa, jonka muodostaa isobutaani, pentaani, heksaani tai muu tyydytetty alifaattinen hiilivety. Polymerointi suoritetaan usein Ziegler-Natta-katalyytin läsnäollessa korotetussa lämpötilassa. Monomeerien lisäksi polymeroinnissa käytetään usein modifiointiaineena vetyä, jolla voidaan vaikuttaa syntyvän polymeerin molekyylipainoon 15 ja muihin ominaisuuksiin.
Tunnetaan myös prosesseja, joissa reaktioväliaineena käytetään nestemäistä propaania. Esimerkiksi US-patentissa 4 754 007 on esitetty prosessi partikkelimuodossa olevan eteenikopolymeerin valmistamiseksi käyttäen nestefaasina nestemäistä propaania. Tällä 20 tavalla esitetään vältettävän eräitä edellämainittujen hiilivetyjen käyttöön liittyviä ongelmia. Näitä haittoja ovat mm. se, että käyttökelpoinen lämpötila on rajoitettu, koska korkeissa lämpötiloissa polyeteeniä liukenee reaktioväliaineeseen. Tästä johtuen komonomeerien ja reaktioväliaineen erottaminen toisistaan on vaikeaa. Lisäksi syntyvillä kopolymeereillä on suhteellisen leveä molekyylipainojakautuma.
25 US-patentin 4 754 007 mukaan reaktioväliaineena käytetään nestemäistä propaania. Tällä tavalla saavutettavia etuja ovat propaanin halpuuden lisäksi se, että propaanilla on alhaisempi höyrystymislämpö ja se on helpommin haihtuvaa kuin esimerkiksi isobutaani. Siten propaanin käyttö mahdollistaa tehokkaamman reaktioväliaineen 30 erottamisen polymeeristä. Lisäksi propaanin käyttö edesauttaa reaktorin pysymistä puhtaana polymeroitaessa eteeniä partikkelimuodossa.
2 . r> r~\ 1 y y t 9 US-patentissa todetaan erityisesti se, että polymerointi tulisi suorittaa propaanin kriittisen lämpötilan alapuolella, joka on 96,8 °C. Prosessi suoritetaan patentin mukaan panosreak-torissa, jossa nestefaasin yläpuolella on huomattava kaasutilavuus. Jos halutaan käyttää jatkuvatoimista loop-reaktoria, niin tilanne on tällöin kokonaan erilainen. Reaktorin on 5 tällöin oltava kokonaan nestefaasin täyttämä, koska reaktioväliaineessa olevat kaasukuplat aiheuttaisivat kavitointia ja siten kulumista reaktioväliaineen kierrätyspunipuissa. Tilanne pahenee, jos loop-reaktorissa halutaan valmistaa korkeamman sulaindek-sin omaavaa tuotetta lisäämällä reaktioväliaineeseen vetyä. Kriittisen pisteen alapuolella toimittaessa, kuten US-patentissa 4 754 007, tapahtuu faasien erottumista vedyn kupliessa 10 sekä paineiskuja, joten prosessi ei ole sovellettavissa loop-reaktoriin.
Voidaan osoittaa, että loop-reaktori n reaktioseoksen sisältäessä propaania 93 mol-% ja eteeniä 7 mol-%, seoksen kriittinen piste on Tc=92,9 °C, Pc=44,l bar. Jos reaktioväliaineessa on eteeniä 7 mol-% ja vetyä 2 mol-% (loput propaania), on reaktorin maksimi 15 operoitavissa oleva lämpötila 75 °C, mikä on aivan liian alhainen lämpötila polymeroin-nin kannalta. Seoksella, jossa on eteeniä 7 mol-% ja vetyä 2,5 mol-% (loput propaania) on maksimi operoitavissa oleva lämpötila enää vain 60 °C. Siten on selvää, että mainitun US-patentin mukainen prosessi ei ole toteutettavissa loop-reaktorissa.
20 Keksinnön mukaisesti on kuitenkin havaittu, että loop-reaktoria voidaan käyttää, jos polymerointi suoritetaan kriittisen pisteen yläpuolella. Tarkemmin sanottuna kysymyksessä on sen fluidiseoksen kriittinen piste, jonka muodostavat monomeerinä toimiva eteeni (+ mahdolliset komoneerit), propaani ja mahdollisesti modifiointiaineena toimiva vety. Eteeni ja vety laskevat mainittua kriittistä pistettä jonkin verran ja kriittinen piste on 25 kokeellisesti määritettävissä, kun tiedetään reaktioväliaineessa olevien komponenttien konsentraatiot.
Siten keksintö koskee menetelmää eteenin homo- tai kopolymeroimiseksi Ziegler-Natta-katalyytin ja mahdollisen komonomeerin ja vedyn läsnäollessa propaanissa partikkeli-30 muodossa olevan eteenin homo- tai kopolymeerin valmistamiseksi loop-reaktorissa. Keksinnön mukainen menetelmä on tunnettu siitä, että polymerointi suoritetaan loop-
II
j v v 2 > 3 reaktorissa sellaisissa olosuhteissa, joissa lämpötila on suurempi kuin eteenin, propaanin ja mahdollisen vedyn ja komonomeerin muodostaman fluidiseoksen kriittinen lämpötila, mutta alempi kuin polymeroinnissa muodostuvan eteenipolymeerin sulamislämpötila, ja paine on korkeampi kuin ko. seoksen kriittinen paine.
5
Ylikriittisessä tilassa olevan propaanifaasin käyttämisestä seuraa lukuisia tärkeitä etuja: 1) Reaktorin vetypitoisuutta voidaan säätää laajalla alueella, koska operointi tapahtuu kriittisen pisteen yläpuolella. Tällöin ei voida enää puhua neste- ja kaasufaaseista, vaan 10 kysymyksessä on yksi faasi. Faasien erottumista ei siten pääse tapahtumaan ennen kuin vetykonsentraatio kasvaa erittäin korkeaksi. Siitä johtuen reaktorissa voidaan valmistaa useamman laatuisia polymeerejä kuin esimerkiksi iso-butaania käytettäessä tai käytettäessä propaania kriittisen pisteen alapuolella toimittaessa. Vetyä voidaan lisätä riittävästi, koska vedyn tai kaasujen erottumista (kuplimista) ei tapahdu tarvittavilla 15 vetykonsentraatioilla.
2) Koska reaktoria operoidaan ylikriittissä olosuhteissa, reaktiofluidin kompressibilitcetti on hyvä ja reaktorin käynnistys ja operointi (paineen säätö) helpottuu, sillä paineisku-vaikutuksia ei esiinny. Tuotteen ulosotossa esiintyy aina nestetilavuuden muutoksia, 20 minkä seurauksena tapahtuu kuplimista. Toimittaessa ylikriittisessä tilassa kuplimisil-miötä ei esiinny.
3) Polyeteenin liukoisuus on huonompi propaaniin kuin isobutaaniin, jolloin erityisesti korkean sulaindeksin, kuten esim. 50-500, omaavat polymeeripartikkelit eivät liukene 25 väliaineeseen ja reaktori likaantuu vähemmän.
4) Koska propaanin kiehumispiste on alhainen, voidaan hiilivedyt erottaa polymeroinnin jälkeen polymeeripartikkeleista tehokkaammin.
4 • 5 9 9 2 9
Keksinnön mukainen menetelmä soveltuu eteenin homo- tai kopolymeroi mi seksi. Sopivia komonomeereja ovat mm. propeeni, 1-buteeni, 1-penteeni, 1-hekseeni, 4-metyyli-l-penteeni, 1-okteeni, 1-dekeeni, 1-dodekeeni ja 1-oktadekeeni.
5 Vedyn käyttö modifiointiaineena soveltuu erityisen hyvin keksinnön mukaiseen menetelmään käytettäessä Ziegler-Natta-tyyppisiä katalyyttejä ja haluttaessa korkeamman sulaindeksin omaavia polymeerejä. Vetyä voidaan edellämainituista syistä johtuen lisätä aina riittävä määrä.
10 Polymerointi suoritetaan siis olosuhteissa, joissa lämpötila on korkeampi kuin propaanin, eteenin ja mahdollisen komonomeerin sekä vedyn muodostaman seoksen kriitittinen piste ja alhaisempi kuin syntyvän eteenipolymeerin sulamispiste, ja paine on korkeampi kuin reaktioseoksen kriittinen paine. Tällöin muodostuva polymeeri on erillisinä hiukkasina, joilla on oleellisesti tasainen koko ja muoto.
15
Siten keksinnön mukainen polymerointi suoritetaan edullisesti lämpötila-alueella 90-110°C. Koska ylikriittisessä tilassa olevan fluidin tiheys on voimakkaasti riippuvainen paineesta kriitisen pisteen läheisyydessä, tulee operointipaine valita niin korkeaksi, että paineen vaikutus tiheyteen on vähäisempi. Riittävä painealue riippuu käytetystä 20 vetykonsentraatiosta, mutta yleensä sopiva paine polymerointireaktorissa on välillä 60-80 bar. Vetyä voidaan reaktorin operoitavuuden kärsimättä lisätä aina 4 mol %-iin asti. Yleisesti polymerointireaktio suoritetaan propaanissa, johon lisätään monomeerinä toimiva eteeni, mahdolliset komonomeerit sekä vety ja katalyytti. Polymeeriä poistetaan jaksottain reaktorista, polymeeri erotetaan propaanista ja monomeereistä tavanomaisella 25 tavalla. Edullisesti polymeeri erotetaan muista aineista flash-tekniikalla alentamalla painetta.
Polymerointikatalyyttinä voidaan käyttää mitä tahansa eteenin polymeroinnissa tavanomaisesti käytettäviä katalyyttejä. Ziegler-katalyytit ovat erittäin sopivia 30 käytettäviksi keksinön mukaisessa menetelmässä. Ne ovat katalyyttejä jotka sisältävät siirtymämetallikomponentteja Alkuaineiden jaksollisen jäijestelmän ryhmien IV, V ja
II
5 j ) 'y 2? VI metalleista. Titaania sisältävät katalyytit ovat erityisen sopivia ja keksinnön mukaisessa menetelmässä käytettävät katalyytit voivat sisältää myös kantajan, joka voi olla esimerkiksi silika, alumina ja silika-alumina.
5 Ziegler-katalyyttien lisäksi keksinnön mukaisessa menetelmässä voidaan käyttää edullisesti muita katalyyttityyppejä, kuten esimerkiksi kromikatalyyttejä. Katalyytin valinta riippuu oleellisesti siitä, minkä tyyppistä polyeteeniä on tarkoitus valmistaa.
Keksinnön mukainen menetelmä ei ole rajoitettu pelkästään yhteen loop-reaktori in. On 10 mahdollista ja joissakin tapauksissa jopa edullista käyttää sarjassa kahta loop-reaktoria, jolloin molemmissa reaktoreissa tai kummassa reaktorissa tahansa voidaan käyttää hyvin korkeita vetykonsentraatioita ja näinollen voidaan valmistaa leveän tai bimodaalisen molekyylipainojakautuman omaavia eteenipolymeerejä ja/tai kopolymeerejä.
15 Keksinnön selittämiseksi viitataan edelleen seuraaviin esimerkkeihin 1-3, joissa polymerointi suoritettiin pilot-mittakaavaisessa loop-reaktorissa, jossa reaktorin läpimitta oli 0,25 m ja pituus 12 m. Katalyyttinä esimerkeissä käytettiin silikakantajalla olevaa Ziegler-Natta tyyppistä katalyyttiä, jossa Ti-pitoisuus oli 4,30 p-%, Mg-pitoisuus 2,80 p-% ja Al-pitoisuus 1,20 p-%.
20
Loop-reaktorin ajo-olosuhteet ja tuotteen ominaisuudet on esitetty jäljempänä olevassa taulukossa.
6 ·, /*· ' r- y / β
Taulukko 1
Aio-olosuhteet Esimerkki 1 Esimerkki 2 Esimerkki 3
5 Lämpötila (°C) 98 °C 98 °C 98 °C
Paine (bar) 65 bar 65 bar 65 bar
Katalyytin syöttönopeus (g/h) 11 11 11
Propaanin syöttönopeus (kg/h) 32 30 30
Eteenin syöttönopeus (kg/h) 21 22 25 10 Eteenikonsentraatio (mol-%) 6,5 6,4 6,4
Vedyn syöttönopeus (g/h) 43 47 57
Vetykonsentraatio (mol-%) 1,44 1,48 1,67
Polymeerin tuotantonopeus (kg/h) 20 20 20
Tuoteominaisuudet 15 Tiheys (kg/m3) 980,6 982,0 983,0
Sulaindeksi MI2 (g/10 min) 67,0 86,0 104,0
Keskim. partikkelikoko (mm) 0,27 0,27 0,27
Bulkkitiheys (kg/m3) 425 422 420 20
Suoritettaessa esimerkkien mukaiset koeajot todettiin, että reaktorin operoitavuus oli erinomainen huolimatta siitä, että vetypitoisuutta nostettiin sulaindeksin korottamiseksi.
Claims (5)
1. Menetelmä eteenin homo- tai kopolymeroimiseksi Ziegler-Natta-katalyytin ja mahdollisen komonomeerin ja vedyn läsnäollessa propaanissa partikkelimuodossa olevan 5 eteenin homo- tai kopolymeerin valmistamiseksi loop-reaktorissa, tunnettu siitä, että polymerointi suoritetaan loop-reaktorissa sellaisissa olosuhteissa, joissa lämpötila on suurempi kuin eteenin, propaanin ja mahdollisen vedyn ja komonomeerin muodostaman seoksen kriittinen lämpötila, mutta alempi kuin polymeroinnissa muodostuvan eteenipolymeerin sulamislämpötila, ja paine on korkeampi kuin ko. seoksen kriittinen 10 paine.
2. Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, että polymeroin-tilämpötila on välillä 95-110 °C ja paine välillä 60-80 bar.
3. Patenttivaatimuksen 1 tai 2 mukainen menetelmä, tunnettu siitä, että vetypi- toisuus propaanissa on välillä 0-4 mol-%.
4. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, tunnettu siitä, että polymerointi suoritetaan kahdessa tai useammassa Saijaan kytketyssä loop-reaktorissa. 20
5. Jonkin edellisen patenttivaatimuksen mukaisella menetelmällä saatu polyeteeni, tunnettu siitä, että polyeteenillä on korkea sulaindeksi, kuten esim. 50-500. I ') f) r\ J ‘ s *+. s
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI906427A FI89929C (fi) | 1990-12-28 | 1990-12-28 | Foerfarande foer homo- eller sampolymerisering av eten |
| JP4502099A JP2707366B2 (ja) | 1990-12-28 | 1991-12-18 | エテンのホモ重合または共重合方法 |
| EP92900835A EP0564488B1 (en) | 1990-12-28 | 1991-12-18 | A method for homo- or copolymerizing ethene |
| DE69125025T DE69125025T2 (de) | 1990-12-28 | 1991-12-18 | Verfahren zur homo- oder copolymerisation von ethen |
| US08/066,004 US5391654A (en) | 1990-12-28 | 1991-12-18 | Method for homo- or copolymerizing ethene |
| PCT/FI1991/000397 WO1992012181A1 (en) | 1990-12-28 | 1991-12-18 | A method for homo- or copolymerizing ethene |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI906427 | 1990-12-28 | ||
| FI906427A FI89929C (fi) | 1990-12-28 | 1990-12-28 | Foerfarande foer homo- eller sampolymerisering av eten |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| FI906427A0 FI906427A0 (fi) | 1990-12-28 |
| FI906427L FI906427L (fi) | 1992-06-29 |
| FI89929B FI89929B (fi) | 1993-08-31 |
| FI89929C true FI89929C (fi) | 1993-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| FI906427A FI89929C (fi) | 1990-12-28 | 1990-12-28 | Foerfarande foer homo- eller sampolymerisering av eten |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5391654A (fi) |
| EP (1) | EP0564488B1 (fi) |
| JP (1) | JP2707366B2 (fi) |
| DE (1) | DE69125025T2 (fi) |
| FI (1) | FI89929C (fi) |
| WO (1) | WO1992012181A1 (fi) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3242150A (en) * | 1960-03-31 | 1966-03-22 | Phillips Petroleum Co | Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone |
| US3324093A (en) * | 1963-10-21 | 1967-06-06 | Phillips Petroleum Co | Loop reactor |
| DE2409839C2 (de) * | 1974-03-01 | 1982-11-18 | Basf Ag, 6700 Ludwigshafen | Verfahren zum Herstellen kleinteiliger Olefinpolymerisate |
| US4182810A (en) * | 1978-04-21 | 1980-01-08 | Phillips Petroleum Company | Prevention of fouling in polymerization reactors |
| CA1162700A (en) * | 1981-01-30 | 1984-02-21 | Kiyoshi Kawai | Process for producing ethylene polymers |
| US4582816A (en) * | 1985-02-21 | 1986-04-15 | Phillips Petroleum Company | Catalysts, method of preparation and polymerization processes therewith |
| US4754007A (en) * | 1985-03-08 | 1988-06-28 | Enron Chemical Company | Copolymerization of ethylene |
-
1990
- 1990-12-28 FI FI906427A patent/FI89929C/fi not_active IP Right Cessation
-
1991
- 1991-12-18 EP EP92900835A patent/EP0564488B1/en not_active Expired - Lifetime
- 1991-12-18 JP JP4502099A patent/JP2707366B2/ja not_active Expired - Lifetime
- 1991-12-18 US US08/066,004 patent/US5391654A/en not_active Expired - Lifetime
- 1991-12-18 WO PCT/FI1991/000397 patent/WO1992012181A1/en not_active Ceased
- 1991-12-18 DE DE69125025T patent/DE69125025T2/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2707366B2 (ja) | 1998-01-28 |
| FI906427A0 (fi) | 1990-12-28 |
| DE69125025T2 (de) | 1997-08-14 |
| WO1992012181A1 (en) | 1992-07-23 |
| EP0564488A1 (en) | 1993-10-13 |
| US5391654A (en) | 1995-02-21 |
| FI89929B (fi) | 1993-08-31 |
| EP0564488B1 (en) | 1997-03-05 |
| JPH06504074A (ja) | 1994-05-12 |
| DE69125025D1 (de) | 1997-04-10 |
| FI906427L (fi) | 1992-06-29 |
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