FI86867C - Flerstegsprocess foer framstaellning av polyeten - Google Patents
Flerstegsprocess foer framstaellning av polyeten Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
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- 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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
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- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- 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
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- 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
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- 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
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- 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
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- 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
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Description
86867
Monivaiheprosessi polyeteenin valmistamiseksi Flerstegsprocess för framställning av polyeten 5
Keksintö koskee prosessia bimodaalisen ja/tai leveän molekyylipainojakautuman omaaavan polyeteenin valmistamiseksi monivaiheprosessilla.
Tietyissä käyttötarkoituksissa, kuten valmistettaessa kalvoja, pulloja, kaapelin-10 päällysteitä ja putkia ekstruusio- tai puhallusmenetelmillä, kapean molekyyli-painon omaava polyeteeni ei ole tyydyttävä sen huonoista virtaavuusominai-suuksista ja huonosta prosessoitavuudesta johtuen. Siksi on ehdotettu erilaisia tapoja leveän molekyylipainon omaavan polyeteenin valmistamiseksi.
15 Eräs tapa molekyylipainojakautuman leventämiseksi on sekoittaa alhaisen molekyylipainon omaavaa polyeteeniä ja korkean molekyylipainon omaavaa polyeteeniä joko mekaanisesti tai liuoksessa. Mekaanisella sekoituksella on kuitenkin hyvin vaikeaa saada aikaan riittävän homogeenista tuotetta ja liuos-sekoituksessa tarvitaan kalliita laitteistoja, joten nämä menetelmät ovat joko 20 epätaloudellisia tai epäkäytännöllisiä.
Molekyylipainojakautuman leventämistä on yritetty saada aikaan myös sopivalla katalyytin valinnalla. Tällä tavalla aikaansaatava molekyylipainojakautuman leventyminen on kuitenkin melko vähäistä. Myös katalyyttien aktiivisuus pyrkii 25 laskemaan nopeasti ja sen takia tuotteesta joudutaan poistamaan katalyyttijää-miä pesemällä, mikä tekee prosessista epätaloudellisen.
Molekyylipainojakautuman leventämiseksi tunnetaan myös erilaisia monivaihe-prosesseja käyttäen erilaisia vetykonsentraatioita eri vaiheissa. Tämä voidaan 30 saada aikaan joko polymeroimalla korkeassa vetykonsentraatiossa ensimmäisessä vaiheessa ja alhaisessa vetypitoisuudessa toisessa vaiheessa, tai päinvastoin. Edellisessä tapauksessa on välttämätöntä poistaa reagoimattomat kaasut ja vety ensimmäisen vaiheen jälkeen. Jälkimmäisessä tapauksessa tavanomaiset Ziegler-katalyytit pyrkivät menettämään aktiivisuuttaan polymeroinnin ku-35 luessa jo ensimmäisessä vaiheessa. Polymeroitumisnopeus, joka on alussa 2 86867 korkea, alenee toisessa vaiheessa johtuen katalyytin alentuneesta aktiivisuudesta ja korkeasta vetykonsentraatiosta. Sen seurauksena viipymäaika toisessa reaktorissa tulee paljon suuremmaksi kuin ensimmäisessä reaktorissa. Tämä merkitsee suurempaa reaktorikokoa toisessa vaiheessa ja koko prosessin vai-5 kcampaa hallittavuutta.
Monivaiheprosesseissa voidaan käyttää erilaisia polymerointimenetelmiä. Tunnettuja monivaiheprosesseja ovat esimerkiksi nestefaasi-nestefaasiprosessit, kaasufaasi-kaasufaasiprosessit sekä nestefaasi-kaasufaasiprosessit. Esimerkkei-10 nä nestefaasi-nestefaasiprosesseja koskevista patenttijulkaisuista voidaan mainita US 3 592 880, EP 057 420, EP 237 294, GB 2 020 672, US 4 352 915 ja EP 057 352. Esimerkkeinä kaasufaasi-kaasufaasiprosesseja koskevista patenttijulkaisuista voidaan mainita GB 1 505 017, EP 040 992 ja US 4 420 592. Esimerkkeinä nestefaasi-kaasufaasiprosesseja koskevista patenttijulkaisuista 15 voidaan mainita referensseinä GB 1 532 231, US 4 368 291, US 4 309 521, US 4 368 304 ja US 283 512.
Esilläoleva keksintö koskee monivaiheprosessia, jossa käytetään nestefaasi-kaasufaasiprosessia. siksi viimeksimainittua patenttijulkaisujen ryhmää tarkas-20 teilaan seuraavassa lähemmin tekniikan tason esittämiseksi tällä alueella.
GB 1 532 231 koskee kaksivaiheista nestefaasi-kaasufaasiprosessia, jossa ensimmäisessä vaiheessa olefiinia polymeroidaan nestemäisessä monomeerissä.
25 Nestefaasi erotetaan polymeeristä ja tuloksena oleva konsentroitu seos siirretään kaasufaasireaktoriin. Koska tämän julkaisun mukaan nestefaasipolyme-rointi suoritetaan nestemäisessä monomeerissä, on selvää että prosessia ei voida lainkaan soveltaa eteenin polymerointiin. Toinen tämän prosessin haitta on alhaisen molekyylipainon omaavan polymeerin liukeneminen nestemäiseen 30 monomeeriin, mikä aiheuttaa haittoja tuotevirtojen käsittelyssä.
US-patentissa 4 368 291 esitetään kaksivaiheinen nestefaasi-kaasufaasipolyme-rointiprosessi, jossa olefiinia polymeroidaan nestemäisessä hiilivedyssä sekoi-tustankkityyppisessä reaktorissa. Ensimmäisen polymerointivaiheen jälkeen
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3 86867 polymeeripartikkeleita ja nestemäistä hiilivetyä sisältävä seos siirretään kokonaisuudessaan kaasufaasireaktoriin. Eräs haitta tässä prosessissa on se, että suuria määriä ensimmäisessä vaiheessa käytettyä hiilivetyväliainetta siirretään kaasufaasireaktoriin, missä se häiritsee polymerointiolosuhteita. Molekyylipai-5 non kontrollointi on myös tavanomaisessa sekoitustankkityyppisessä reaktorissa vaikeaa. Raskaamman laimentimen erotus on myös vaikeampaa ja epätaloudellista.
US 4 309 521 ja US 4 368 304 koskevat erikoiskatalyyttejä, joita voidaan 10 käyttää nestefaasi-kaasufaasiprosesseissa. Nämä julkaisut eivät tarjoa mitään hyödyllistä informaatiota itse prosesseista.
Lopuksi EP 283 512 koskee monivaiheprosessia, jossa käytetään tiettyä spesifioitua katalyyttiä. Tämän julkaisun mukaan nestemäistä propeenia tai muuta 15 nestemäistä olefiinia esipolymeroidaan ensin nestefaasireaktorissa, esimerkiksi loop-reaktorissa viipymäajan ollessa 10 sekunnista 400 sekuntiin, jonka jälkeen polymerointiseos kokonaisuudessaan siirretään kaasufaasireaktoriin, jossa polymerointia jatketaan kaasufaasissa. Tämä prosessi on siten samanlainen kuin edellä mainittu GB 1 532 231 eikä tätä prosessia voida käyttää eteenin 20 polymeroinnissa. Loop-reaktorivaihe on pelkkä esipolymerointivaihe. Tähän julkaisuun viitataan tässä vain sen takia, että siinä mainitaan loop-reaktori kaasufaasireaktorin yhteydessä.
Tämä keksintö perustuu siihen yllättävään havaintoon, että käyttämällä loop-25 reaktoripolymerointia inertissä alhaalla kiehuvassa hiilivedyssä (nk. light diluent-prosessi) yhdessä kaasufaasipolymeroinnin kanssa on mahdollista saavuttaa erityisiä etuja, jotka eivät olisi mahdollisia käytettäessä edellämainittuja tavanomaisia nestefaasi-polymerointeja yhdessä kaasufaasipolymeroinnin kanssa.
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Siten esilläolevan keksinnön kohteena on aikaansaada prosessi, joka tekee mahdolliseksi bimodaalisen ja/tai leveän molekyylipainojakautuman omaavan polyeteenin valmistamisen, jolla on erinomaiset sulavirtausominaisuudet ja ekstruusio- ja valuominaisuudet. Tämä johtuu siitä, että loop-reaktorin käyttö 4 86867 mahdollistaa paremman lämmönsiirron reaktioseoksesta ja siksi tasaisemman lämpötilaprofiilin sekä suuremman suspensiotiheyden ja siten paremman sekoittumisen kuin konventionaalisten sekoitinreaktoreiden käyttö.
5 Edelleen loop-reaktorin käyttö mahdollistaa lyhyemmät viipymäajat ja korkeammat polymeerin sulaindcksit, koska siinä voidaan käyttää korkeampia vetykonsentraatioita ja siki on mahdollista saavuttaa kapeampi molekyylipai-nojakautuma slurryvaihetuotteessa. Lyhyt viipymäaika loop-reaktorissa yhdistyneenä kaasufaasireaktorin joustavuuteen sallii tiheydeltään alhaisemman 10 tuotteen valmistamisen ja helpommat laatumuutokset. Edelleen loop-reaktorin ja yhden tai useamman kaasufaasireaktorin yhdistelmän käyttö sallii erilaisten katalyyttien käyttämisen ja siten joustavuuden katalyyttien valinnassa.
Nämä kohteet saavutetaan keksinnön mukaisessa monivaiheprosessissa bimo-15 daalisen tai leveän molekyylipainon omaavan polyeteenin valmistamiseksi eteeniä polymeroivan katalyyttisysteemin läsnäollessa monivaiheisessa reak-tiosekvenssissä, jossa ensimmäinen reaktiovaihe on nestefaasipolymerointivai-he ja sen jälkeen tulevan reaktiovaiheen muodostaa yksi tai useampi kaasu-faasipolymerointivaihe. Keksinnön mukaisesti ensimmäisessä reaktiovaiheessa 20 polymeroidaan eteeniä loop-reaktorissa inertissä alhaalla kiehuvassa hiilivety-väliaineessa viipymäajan ollessa vähintään 10 minuuttia, reaktioseosta poistetaan loop-reaktorista ja ainakin huomattava osa inertistä hiilivetyväliaineesta erotetaan ja polymeeri siirretään yhteen tai useampaan kaasufaasireaktoriin, missä polymerointi suoritetaan loppuun eteenimonomeerin ja valinnaisesti 25 vedyn ja/tai komonomeerin läsnäollessa.
Yleisesti keksinnön mukaisessa prosessissa voidaan käyttää mitä tahansa etee-nipolymeerien valmistukseen sopivaa katalyyttiä. Sellaisia katalyyttejä ovat mm. Ziegler-katalyytit, jotka sisältävät siirtymämetallia Periodisen alkuainetau-20 lukon ryhmistä IV, V tai VI, yhdessä kokatalyytin, tavallisesti alkyylialumiini-yhdisteen kanssa. Suositeltava siirtymämetalli on titaani ja katalyytit voivat olle tuettuja eli epäorgaanisella kantajalla, kuten silika, alumina tai silika-alu-mina, tai ne voivat olla ilman erillistä kantajaa.
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Suositeltavia katalyyttejä ovat esimerkiksi suomalaisissa patenttihakemuksissa 905430, 902123, 901895, 900842, 906323, 905703, 895526, 894266, 893621, 892153 ja 872459 esitetyt katalyytit. On kuitenkin huomattava, että keksinnön mukainen prosessi ei ole katalyyttispesifinen ja siksi siinä voidaan käyttää mitä 5 tahansa sopivan aktiivisuuden ja säädettävän molekyylipainon antavaa katalyyttiä.
Ensimmäinen vaihe keksinnön mukaisessa prosessissa suoritetaan loop-reakto-rissa, johon syötetään inerttiä hiilivetyväliainetta, eteeniä, vetyä, katalyyttiä ja 10 valinnaisesti komonomeeriä. Loop-reaktori voi olla tavanomaista rakennetta, johon sisältyvät elimet eri syöttökomponenttien syöttämiseksi reaktoriin, elimet polymeeri-hiilivetysuspension kierrättämiseksi reaktorin läpi, lämmönsiir-toelimet polymerointilämmön poistamiseksi ja elimet polymeerisuspension poistamiseksi reaktorista.
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Polymerointiväliaineena käytetään inerttiä alhaalla kiehuvaa hiilivetyä. Esimerkkejä hiilivedyistä ovat alifaattiset hiilivedyt, kuten propaani, butaani, pentaani, heksaani, heptaani ja oktaani sekä alisykliset hiilivedyt kuten syklo-heksaani ja sykloheptaani. On mahdollista käyttää myös yhden tai useamman 20 edellä esitetyn hiilivedyn seosta.
Katalyyttiä, mieluimmin hiilivetylietteenä ja yhdessä kokatalyytin kanssa, inerttiä hiilivetyväliainetta, eteeniä, vetyä ja valinnaisesti komonomeeriä syötetään jatkuvasti loop-reaktoriin. Reaktioseosta kierrätetään jatkuvasti reaktorin läpi, 25 jolloin muodostuu partikkelimuodossa olevan polyeteenin suspensio inertissä hiilivetyväliaineessa. Loop-reaktorin reaktio-olosuhteet valitaan siten, että vähintään 20 %, mutta mieluimmin 40-90 % kokonaistuotannosta polymeroi-tuu loop-reaktorissa. Lämpötila voidaan valita väliltä 75-110 °C, edullisesti väliltä 85-100 °C. Reaktoripaine voidaan valita väliltä 40-90 bar, edullisesti 30 väliltä 50-65 bar. Viipymäajan tulee olla vähintään 10 min, mutta edullisesti viipymäaika on kuitenkin välillä 1-2 tuntia. Vedyn moolisuhde eteeniin valitaan riippuen halutun tuotteen sulaindeksistä, mutta biniodaalisen polyeteenin valmistuksessa se tulee olemaan välillä 0-1,0.
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Erityisiä etuja saavutetaan, jos inerttinä hiilivetyväliaineena käytetään ylikriittisessä tilassa olevaa hiilivetyä, edullisesti propaania. Tämä merkitsee sitä, että reaktio suoritetaan sellaisissa olosuhteissa, joissa lämpötila ja paine ovat yläpuolella sen reaktioseoksen vastaavien kriittisten pisteiden, jonka muodostavat 5 eteeni, propaani, vety ja mahdollinen komonomeeri, mutta lämpötila on alempi kuin muodostuvan polymeerin sulamispiste. Siten lämpötila loop-reaktorissa tulee olemaan välillä 95-110 °C ja paine välillä 60-90 bar.
Käyttämällä ylikriittistä propaanifaasia on mahdollista käyttää korkeampia 10 vetykonsentraatioita kuin alikriittisissä olosuhteissa olisi mahdollista tai jos käytettäisiin isobutaania tai muita hiilivetyjä. Tuotteen liukeneminen on vähäisempää ja hiilivedyn (propaanin) ja vedyn eriottaminen flash-tekniikalla on helpompaa. Ylikriittisissä olosuhteissa reaktorissa esiintyy käytännössä vain yksi reaktiofluidi, jossa ei ole erotettavissa neste- ja kaasufaaseja, ja tämä 15 antaa hyvän lämmönsiirron, kaasujen vapaan sekoittumisen fluidiin ja reak-tioväliaineen alhaisen viskositeetin.
Reaktioseosta poistetaan joko jatkuvasti tai jaksottain tavanomaisella tavalla loop-reaktorista. Inertti hiilivetyväliaineseos sekä mahdollinen komonomeeri ja 20 vety, mikäli sitä on käytetty, poistetaan polymeeripartikkeleista tavanomaisella tavalla, esimerkiksi flash-tekniikalla. Hiilivetyväliaine, jäljellä olevat monomeerit ja vety voidaan kierrättää takaisin loop-reaktoriin.
Konsentroitu polymeeriseos syötetään sitten kaasufaasireaktoriin. Tämä reak-25 tori voi olla tavanomainen fluidipetireaktori, vaikka muunkin tyyppisiä kaasu -faasireaktoreita voidaan käyttää. Fluidipetireaktorissa peti käsittää muodostuneita ja kasvavia polymeeripartikkeleita samoinkuin katalyyttikomponentteja. Peti pidetään fluidisoidussa tilassa johtamalla kaasumaisia komponentteja, ': kuten eteenimonomeeria sellaisella virtausnopeudella, joka saa hiukkaset 30 toimimaan fluidina. Fluidisointikaasu voi sisältää myös inerttejä kantokaasuja, kuten typpeä, sekä haluttaessa myös vetyä modifiointiaineena.
Toisessa vaiheessa käytettävä kaasufaasireaktori voi toimia lämpötila-alueella 60-115 °C, edullisesti 70-110 °C. Paine voi olla alueella 10-25 bar eteenin 7 86867 osapaineen ollessa välillä 4-20 bar. Vedyn moolisuhde eteenin on edullisesti alhaisempi kuin loop-reaktorissa. Siten vedyn konsentraatio kaasufaasireakto-rissa voi olla välillä 0-10 mol-%.
5 Kaasufaasireaktoriin voidaan haluttaessa syöttää myös erilaisia komonomeere-jä. Näitä komonomeerejä ovat esimerkiksi propeeni-. 1-buteeni, penteeni, 1-hekseeni, 1-okteeni tai 4-metyyli-l-penteeni.
On myös edullista käyttää sellaista kaasufaasireaktoria, joka on varustettu 10 sekoittajalla. Sekoittaja auttaa pitämään reaktoripinnat puhtaina ja parantaa kaasun jakautumista reaktoriin.
Keksintö ei ole rajoitettu kaksivaiheprosessiin. Yhden kaasufaasireaktorin sijasta on mahdollista käyttää kahta tai jopa kolmea kaasufaasireaktoria loop-15 reaktorin perässä.
Keksinnön mukaista prosessikonfiguraatiota kuvataan edelleen seuraavassa viittaamalla oheisen piirustuksen kuvioon, jossa loop-reaktoria on merkitty viitenumerolla 10. Katalyyttiä syötetään katalyyttisäiliöstä 11 katalyyttisyötti-20 men 12 avulla katalyytin siirtolinjan 13 kautta loop-reaktoriin 10. Eteeniä linjasta 14, alhaalla kiehuvaa hiilivetyä linjasta 15, vetyä linjasta 16 ja valinnaista komonomeeriä linjasta 17 syötetään loop-reaktoriin 10 linjan 18 kautta. Loop-reaktorissa 10 reaktioseosta kierrätetään sopivilla kierrätyselimillä (ei esitetty) ja samalla polymeroitusmislämpöä poistetaan jäähdyttämällä reaktoria 25 tai reaktioseosta jäähdytyssysteemin (ei esitetty) avulla.
Loop-reaktorista 10 polymeeri-hiilivetyseos syötetään flash-erottimeen 20 yhden tai useamman poistoventtiilin 19 ja tuotteen poistolinjan 21 kautta. Polymeeripartikkeleista poistetut hiilivetyväliaine, jäljellä oleva monomeeri ja 30 komonomeeri ja vety poistetaan flash-erottimesta 20 linjan 23 kautta joko laimentimen talteenottoyksikköön (ei esitetty) linjan 24 kautta tai kierrätetään takaisin loop-reaktoriin linjan 25 kautta. Polymeeripartikkelit poistetaan flash-erottimesta linjan 22 kautta kaasufaasireaktoriin 30.
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Kaasufaasireaktorin 30 alaosassa on polymeeripartikkelien muodostama peti, joka pidetään leijutilassa puhaltamalla kaasumaista monomeeriä, komonomee-riä ja vetyä linjan 37 kautta reaktorin 30 pohjaan ja kaasunjakolevyn 31 läpi. Kaasumaisia komponentteja poistetaan jatkuvasti reaktorin 30 huipusta linjan 5 34 kautta ja kierrätetään kompressorin 36, jäähdytyslaitteen 35 ja linjan 37 kautta takaisin reaktorin 30 pohjaan. Reaktoriin 30 voidaan syöttää myös eteeniä linjasta 33, komonomeeriä linjasta 40, typpeä linjasta 41 ja vetyä linjasta 42. Reaktori 30 voi olla varustettu mekaanisella sekoittimella 38 reakto-ripintojen pitämiseksi puhtaina ja kaasun jakautumisen parantamiseksi. Tuo-10 tetta poistetaan jaksottain tai jatkuvasti kaasufaasireaktorista 30 linjan 39 kautta tuotteen talteenottosysteemiin (ei esitetty).
Vaikka kuviossa on esitetty vain yksi kaasufaasireaktori, on selvää, että on mahdollista käyttää kahta tai useampaa kaasufaasireaktoria keksinnön mukai-15 sessa prosessissa oheisten patenttivaatimusten mukaisesti.
Keksintöä kuvataan oheisien suoritusesimerkkien avulla.
Esimerkit 1-8 20
Eteenin kaksivaihepolymeroinnissa käytettiin pilot-mittakaavaista loop-reakto-ria, jonka kapasiteetti oli noin 50 kg/h ja kaasufaasireaktoria, jonka kapasiteetti oli n. 75 kg/h sisältäen myös loop-reaktorista tulevan tuotteen. Eteenin lisäksi käytettiin loop-reaktorissa komonomeerinä 1-buteenia ja kaasufaasi-25 reaktorissa 1-buteenia ja 1-hekseeniä. Modifiointiaineena käytettiin vetyä. Loop-reaktoriin lisättävä katalyytti oli valmistettu PCT-hakemuksen FI90/00279 esimerkissä 1 esitetyllä tavalla. Loop-reaktorissa käytettiin reak-tioväliaineena propaania tai isobutaania.
30 Loop-reaktorista tulevasta tuotteesta poistettiin kaasumaiset ja kaasuuntuvat jakeet flash-säiliössä, jonka jälkeen tuote siirrettiin kaasufaasireaktoriin, jossa polymerointia jatkettiin, Esimerkeissä 2, 3, 7 ja 8 tutkittiin pelkästään loop-reaktoripolymerointia. Polymerointiolosuhtcet ja tuotemoninaisuudet on esitetty oheisessa taulukossa.
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TAULUKKO
Esimerkki 123 45 678 5 _____
Loop-reaktori
Hiilivety C3 iC4 C3 C3 C3 iC4 iC4 ic4
Tuotanto nopeus (kg/h) 24 17 14 20 22 30 18 20
Katalyyttisyöttö (g/h) 12 2 8 15 4 5 20 8 10 Katalyytin aktiivisuus (kg/g) 2,0 8,5 1,8 1,3 5,4 6,0 0,9 2,5 Lämpötila (°C) 95 95 85 85 75 95 92 91
Kriittinen lämpötila (°C) 85
Paine (bar) 65 47 65 65 65 50 15 Kriittinen paine (bar) 50
Eteenipitoisuus (mol-%) 7,6 8,7 7,8 6,8 7,1 8,5
Vetypitoisuus (mol-%) 1,9 1,0 1,2 0,7 1,5 1,8 1-Buteenipitoisuus (mol-%) 0,0 0,0 7,6 7,5 11,7 0,0
Viipymäaika (h) 0,5 1,2 1,7 1,1 1,0 1,3 20
Tuotteen tiheys (kg/m3) 978 967 944 929 943 971 936 935
Sulaindeksi MFR2 96 8 260 150 148 140 1,7 0,2 D(Mw/Mn) 3,5 4,0 25 Kaasufaasireaktori
Tuotantonopeus (kg/h) 25 10 29 27 Lämpötila (°C) 85 75 75 85
Paine (bar) 20 20 20 20 30 Eteenipitoisuus (mol-%) 10 15 31 10
Vetypitoisuus (mol-%) 0,8 3,0 8,1 0,1 1-Buteenipitoisuus (mol-%) 0,8 3,8 7,8 0,0 ' 1-Hekseenipitoisuus (mol-%) 0,0 0,0 0,0 0,9 •.: Viipymäaika (h) 3,7 5,4 6,8 2,5 ' . 35
Lopputuote
Tuotantonopeus 49 30 51 57
Katalyyttiaktiivisuus (kg/g) 4,0 12,5 11,4 40 Tuotteen tiheys (kg/m3) 948 929 928 955 - : - Sulaindeksi MFR2 0,7 0,8
Sulaindeksi MFR5 0,6 0,8 D(Mw/Mn) 12 9 23 45 Putken painetesti 5,3 MPa >3200— 4,6 MPa >3200- D = Molekyylipainojakautuma (Mw/Mn) 50 C3 = propaani iC4 = isobutaani
Keksinnön mukaisella prosessilla voidaan tuottaa bimodaalisia tuotteita, joissa on säädettävä molekyylipainojakautuma D(Mw/Mn). Esimerkeissä 1, 4 ja 6 10 86867 tuotteiden molekyylipainojakautumat D olivat 12, 9 ja 23. Keksinnön mukaisella prosessilla kyetään vieläkin laajempaan vaihteluväliin. Normaaleissa unimodaaleissa tuotteissa vastaavat D-arvot Ziegler-tyyppisiä katalyyttejä käytettäessä ovat yleensä 3,5-6. Keksinnön mukaisessa prosessissa loop-reakto-5 ri tuottaa kapean molekyylipainojakautuman omaavia tuotteita. Esimerkissä 2 ja 4 mitatut arvot D = 3,5 ja 4,0 ovat tyypillisiä arvoja.
Esimerkeissä 5 ja 6 valmistetuista tuotteista ekstrudoitiin putkia prosessoita-vuuden ollessa hyvä. Esimerkin 6 putkille suoritettiin painetestit pitämällä 10 putkia paineissa 5,3 ja 4,6 MPa yli 3200 H (testien yhä jatkuessa), mikä osoittaa putkien hyvää lujuutta. Unimodaalisesta lineaarisesta polyeteenistä ei voida valmistaa vastaavat ominaisuudet omaavia putkia.
Loop-reaktoriprosessi tekee mahdolliseksi korkean vetypitoisuuden käyttämi-15 sen, varsinkin käytettäessä superkriittistä propaania laimentimena. Kuten esimerkkejä 1, 5 ja 6 suoritettaessa havaittiin, ei mitään kaasukuplien muodostumista ollut havaittavissa. Sulaindeksi MFR2 voi olla niinkin korkea kuin 260 ilman mitään ongelmia (esimerkki 3).
20 Loop-reaktorilla voidaan tuottaa alhaisen tiheyden omaavia tuotteita käytettä-. ·. essä ylikriittistä propaania laimentimena. Pelkän propaanin kriittinen lämpöti la on n. 92 °C ja kriittinen paine n. 45 bar (g). Esimerkin 1 olosuhteissa kriittinen lämpötila oli n. 85 °C ja kriittinen paine n. 50 bar (g), mikä tarkoittaa ylikriittisiä olosuhteita. Käytettäessä muita hiilivetyjä reaktioväliaineena liukoi-25 suus estää pääsemästä tiheydessä arvon n. 945 alapuolelle (heksaanilaimennin) tai alle n. 935 (isobutaanilaimennin). Esimerkin 4 mukaisesti on mahdollista päästä tiheyteen 929 kg/m3 sulaindeksin ollessa hyvin korkea (MFR2 = 150) ilman reaktorin tukkeutumista. Esimerkkiä 7 suoritettaessa havaittiin, että käytettäessä isobutaania laimentimena reaktori tukkeutui tiheyden ollessa 30 936 kg/m3 ja sulaindeksi MFR2 ollessa 1,7. Käytettäessä isobutaania laimenti mena onnistuttiin pääsemään tiheyteen 935 kg/m3 sulaindeksin MFR2 ollessa alhaisempi (0,2), kuten esimerkki 8 osoittaa.
Claims (6)
1. Monivaiheprosessi bimodaalisen ja/tai leveän molekyylipainon omaavan polyeteenin valmistamiseksi eteeniä polymeroivan katalyyttijärjestelmän läsnä-5 ollessa monivaiheisessa reaktiosekvenssissä, jossa ensimmäinen reaktiovaihe on nestefaasipolymerointivaihe ja toisen reaktiovaiheen muodostaa yksi tai useampi kaasufaasipolymerointivaihe, tunnettu siitä, että ensimmäisessä reaktiovaiheessa eteeniä polymeroidaan loop-reaktorissa (10) inertissä alhaalla kiehuvassa hiilivetyväliaineessa viipymäajan ollessa ainakin 10 minuuttia, 10 reaktioseosta poistetaan loop-reaktorista (10) ja ainakin huomattava osa iner-tistä hiilivetyseoksesta erotetaan ja polymeeri siirretään yhteen tai useampaan kaasufaasireaktoriin (30), missä polymerointi suoritetaan loppuun eteenin ja valinnaisesti vedyn ja komonomeerin läsnäollessa.
2. Patenttivaatimuksen 1 mukainen prosessi, tunnettu siitä, että poly merointi ensimmäisessä vaiheessa suoritetaan korkeammassa vetykonsentraa-tiossa korkeamman sulaindeksin omaavan polymeerin valmistamiseksi, ja myöhemmissä vaiheissa eteeniä tai eteeniä ja komonomeerejä polymeroidaan alhaisemmassa vetykonsentraatiossa alhaisen sulaindeksin ja alhaisen tiheyden 20 omaavan eteenihomopolymeerin tai kopolymeerin valmistamiseksi.
3. Patenttivaatimuksen 2 mukainen prosessi, tunnettu siitä, että vedyn moolisuhde eteeniin nähden on alueella 0-1 mol/mol, edullisesti alueella 0-0,5 mol/mol. 25
4. Jonkin edellisen patenttivaatimuksen mukainen prosessi, tunnettu siitä, että inertti hiilivetyväliaine on valittu ryhmästä propaani, butaani, pen-taani, heksaani, heptaani ja oktaani.
5. Patenttivaatimuksen 4 mukainen prosessi, tunnettu siitä, että inertti hiilivetyväliaine on propaani. 1 Jonkin edellisen patenttivaatimuksen mukainen prosessi, tunnettu siitä, että polymerointi loop-reaktorissa (10) suoritetaan ylikriittisissä olosuh- 86867 teissä, jolloin polymerointilämpötila ja paine ovat kyseisen hiilivetyväliaineen, monomeerin, vedyn ja valinnaisen komonomeerin muodostaman seoksen vastaavien kriittisten pisteiden yläpuolella ja polymerointilämpötila on alhaisempi kuin syntyvän polymeerin sulamispiste. 5
7. Patenttivaatimuksen 6 mukainen prosessi, tunnettu siitä, että poly-merointi loop-reaktorissa (10) suoritetaan lämpötilassa 95-110 °C ja paineessa 60-90 bar. 10 13 86867
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI906428A FI86867C (fi) | 1990-12-28 | 1990-12-28 | Flerstegsprocess foer framstaellning av polyeten |
| DE69114696T DE69114696T2 (de) | 1990-12-28 | 1991-12-20 | Mehrstufiges verfahren zur herstellung von polyethylen. |
| ES92900629T ES2079844T3 (es) | 1990-12-28 | 1991-12-20 | Proceso en varias etapas para producir polietileno. |
| JP4501688A JP2529923B2 (ja) | 1990-12-28 | 1991-12-20 | ポリエチレン合成の為のマルチステ―ジプロセス |
| EP92900629A EP0517868B1 (en) | 1990-12-28 | 1991-12-20 | Multi-stage process for producing polyethylene |
| PCT/FI1991/000406 WO1992012182A1 (en) | 1990-12-28 | 1991-12-20 | Multi-stage process for producing polyethylene |
| DK92900629.4T DK0517868T3 (da) | 1990-12-28 | 1991-12-20 | Flertrinsproces til fremstilling af polyethylen |
| AT92900629T ATE130316T1 (de) | 1990-12-28 | 1991-12-20 | Mehrstufiges verfahren zur herstellung von polyethylen. |
| US07/920,569 US5326835A (en) | 1990-12-28 | 1991-12-20 | Multi-stage process for producing polyethylene |
| DE199292900629T DE517868T1 (de) | 1990-12-28 | 1991-12-20 | Mehrstufiges verfahren zur herstellung von polyethen. |
| NO923334A NO179286C (no) | 1990-12-28 | 1992-08-26 | Flertrinnsprosess for fremstilling av polyetylen |
| GR950403657T GR3018786T3 (en) | 1990-12-28 | 1996-01-25 | Multi-stage process for producing polyethylene. |
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| FI906428A FI86867C (fi) | 1990-12-28 | 1990-12-28 | Flerstegsprocess foer framstaellning av polyeten |
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| FI906428A0 FI906428A0 (fi) | 1990-12-28 |
| FI906428A7 FI906428A7 (fi) | 1992-06-29 |
| FI86867B FI86867B (fi) | 1992-07-15 |
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| US (1) | US5326835A (fi) |
| EP (1) | EP0517868B1 (fi) |
| JP (1) | JP2529923B2 (fi) |
| AT (1) | ATE130316T1 (fi) |
| DE (2) | DE69114696T2 (fi) |
| DK (1) | DK0517868T3 (fi) |
| ES (1) | ES2079844T3 (fi) |
| FI (1) | FI86867C (fi) |
| GR (1) | GR3018786T3 (fi) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3428619A (en) * | 1965-05-27 | 1969-02-18 | Phillips Petroleum Co | Suspension handling |
| US3622553A (en) * | 1967-12-18 | 1971-11-23 | Phillips Petroleum Co | Agitated reactor and gas fluidized bed reactor in series for polymerization of vinyl chloride |
| GB1532231A (en) * | 1975-04-18 | 1978-11-15 | Ici Ltd | Polymerisation process |
| DE2803281C2 (de) * | 1978-01-26 | 1982-12-02 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur mehrstufigen Polymerisation von Äthylen, allein oder zusammen mit anderen Olefinen |
| JPS6023764B2 (ja) * | 1980-02-27 | 1985-06-10 | チッソ株式会社 | α−オレフイン重合体を製造する方法 |
| EP0057420B1 (en) * | 1981-01-30 | 1986-05-07 | Sumitomo Chemical Company, Limited | Process for producing ethylene polymers |
| US4538018A (en) * | 1983-12-13 | 1985-08-27 | Phillips Petroleum Company | Surface conditioning in olefin dimerization reactors |
| CA1284549C (en) * | 1986-09-26 | 1991-05-28 | Fathi David Hussein | Process for the polymerization of propylene |
-
1990
- 1990-12-28 FI FI906428A patent/FI86867C/fi not_active IP Right Cessation
-
1991
- 1991-12-20 DE DE69114696T patent/DE69114696T2/de not_active Expired - Lifetime
- 1991-12-20 US US07/920,569 patent/US5326835A/en not_active Expired - Lifetime
- 1991-12-20 EP EP92900629A patent/EP0517868B1/en not_active Expired - Lifetime
- 1991-12-20 ES ES92900629T patent/ES2079844T3/es not_active Expired - Lifetime
- 1991-12-20 DE DE199292900629T patent/DE517868T1/de active Pending
- 1991-12-20 WO PCT/FI1991/000406 patent/WO1992012182A1/en not_active Ceased
- 1991-12-20 AT AT92900629T patent/ATE130316T1/de not_active IP Right Cessation
- 1991-12-20 DK DK92900629.4T patent/DK0517868T3/da active
- 1991-12-20 JP JP4501688A patent/JP2529923B2/ja not_active Expired - Lifetime
-
1992
- 1992-08-26 NO NO923334A patent/NO179286C/no not_active IP Right Cessation
-
1996
- 1996-01-25 GR GR950403657T patent/GR3018786T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO923334D0 (no) | 1992-08-26 |
| FI86867B (fi) | 1992-07-15 |
| DE517868T1 (de) | 1993-07-22 |
| JPH05504786A (ja) | 1993-07-22 |
| EP0517868A1 (en) | 1992-12-16 |
| DE69114696D1 (de) | 1995-12-21 |
| EP0517868B1 (en) | 1995-11-15 |
| NO179286C (no) | 1996-09-11 |
| ES2079844T3 (es) | 1996-01-16 |
| NO923334L (no) | 1992-08-26 |
| WO1992012182A1 (en) | 1992-07-23 |
| GR3018786T3 (en) | 1996-04-30 |
| NO179286B (no) | 1996-06-03 |
| FI906428A0 (fi) | 1990-12-28 |
| ATE130316T1 (de) | 1995-12-15 |
| DK0517868T3 (da) | 1996-03-18 |
| DE69114696T2 (de) | 1996-04-11 |
| US5326835A (en) | 1994-07-05 |
| FI906428A7 (fi) | 1992-06-29 |
| JP2529923B2 (ja) | 1996-09-04 |
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Legal Events
| Date | Code | Title | Description |
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| PC | Transfer of assignment of patent |
Owner name: BOREALIS POLYMERS OY |
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| PC | Transfer of assignment of patent |
Owner name: BOREALIS POLYMERS OY |
|
| MM | Patent lapsed |
Owner name: BOREALIS POLYMERS OY |