AU611473B2 - Method of obtaining butene-1 - Google Patents

Description

Position: t P Director GRIFFITH HASSEL FRAZER G.P.O. BOX 4164 SYDNEY, AUSTRALIA 011 P 'q A-A4 -21332/88, BCEM14PHAA 4 P CTHHTERREKYAbHOR1COECTBE6 H MEKAYHAPOAJAI 3A5IBKA, OHYBJIHKOBAHHAA B COOTBETCTBHH4 C AOIJ3OPOM 0 IIATEHTHOA1 KOorIEPAUI4H4 (PCT) (51)3Owwpeo ax rcu: Aiam (11) Homtp mew4cjynpo~woi nyammamm: WO 89/00553 Mo~e~ew .Al (43) Aam t .jjyn.)apceuo* uyfl~mcaiI C07C 11/08, 2130 26 mapq, 1989 (26.01.89) (21) Homep meegAy~apoAmoff 3aBaIKH PCT/SIU88/00129 na 1173)A, yyi. KocbffxtHa,, 6, KB. 9 (SU) [DYACH- KOVSKY, Fridrilch Stepanovich, Moscow (22) Aa~a mexcxyHapoAWoli nouaqwE HBAHqEB r-elprof CTenaH,)BHq [SU/SUI; Jlenim- 26 mi 1988 (26.05.88) rpaxA 199226, yn. HmaRa, g. 36, KB, 37 (SU) [iVA- NCHEV, Sergei Stepanovich, Leningrad rEP- MAIIlER AHaTOmL4f 14BaHOBHq [SIJ/SU]; ByzeH- (31) Homep lip~opirreTHofi 3ajmfKH.* 4267266/04 hoBcx 357920, CTahJpor1ObCKmHs Kpafl, M~pTanr 175a, A. 5, KIB. 5 (SU) [QERMASHEV, Anatoly Ivanovich, (32) Aa~a upliopifreTa: 13 mona 1987 (13.07.87) Budennovsk HETPOB I0pviM MaKCHMOB~tI [SU/SU]; BygeHHOMC 357920. mHxpopafoH 17, (33) Crprn~a upuc~pireTa: SU KB. 37 [PETROV, jury Maximovich, Budenanvsk JIA3YTHH BwjepHA~ HrHamheBHq (71) 3asinureim (64,q 8cexyKa3aHrnbx zocja~apcm8, Kpome US): [SWI/SI)]; rpo3Hbif4 364048, yn. TtimkiP~e~a, A. 77 HHCTI4TYT XHMWIqECKOf4 ODH311KI AKA- (SO) [LAZUTIN, Valery Ignatievich, Grozrty ,aEM14H HAYK CCCP Mocirsa 117977, AIUEHKO BajiepHAf AniexceeBHq [SU/SU]; rpo3yna. KOCbirHHa, g. 4 (SU) [INSTITUT KHIMICHES- HM~r 364048, rip. .JIeHHHa, a. 117, KB. 85 [YA- KOI FIZIKI AKADEMII NAUK SSSR, Moscow TSENKO, Valery Alexeevich, Grozny F ArPO3HEHCKHf4 0$HJI}IAJI OXT4kICKO- BYTJMHHOB Man-Ax CajmxoBwq [SU/SUI; Ka3amr1 ro HAY

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-Ho-nPOH3BOJACTBEHHOrO O,51- 420015, ynr. Owoimnasi, j. 94a, KoprI. 2, KB. 41 (SU) EAHHEHHA eflIJIACTflOJIHMEP)> [SU/s"Cr]; [GABUTDINOV, Malik Salikhovich, Kazan rpo3Hbli 364048 [PROZNENSKY FILIAL OKHTINqSKOGO NAI)CHNO-PROIZVOIDST- (74) AreHT: TOPrOt1O-rPOM 3 YENNOGO OBIEDINENIA ((PLASTPOLIMERB, CCCP; MocKBa 103735, yii, Kyf6ifuieaa,gr 5/2 (SI) Grozny [THE USSR CHAMBER OF COMMERCE AND INDUSTRY, Moscow (72) H3o6peTaTeJnI, H ll1o6peTaTemn/3axnu'rejm (moibxo ttaa US): CEP17I4- EHKo raiMqHa CTenaHoBHa [su/SU]; rpoifibiH (81) YKBaicnie roey~ap.'ema: AT (eBpon(icicRA 7 raTeHT), 364051,yg. Pa6oqaq,n.6-4,n.43 (SU) LSERG.IENKO, AU, BE (eBpofixCK~i naTeuT), BR, CH (eBponeft- Galina Stepanovna, Grozny )KYKOB Aim- cicwi naTeHT), DE (eBponefcimf rnaTeHT), Fl, FR TOP HBaHoBi44 17po31Lilj 364007, yii, Heij- (eBpone~cxHf1 naTeHT), GB (eppone~cKnft naTeHT), Te3aBAocX,?l, a. 4, KB. i (SU) [ZHUKOV, Wktor HU, IT (eeporefKHA' rnaTeHT), JP, LI) (eisponeg- Ivanovich, r~rozny BEJIOB reH~aA~f1 flDT- CKHH naTeHT), NL (eBponeiHcKM naTelr), NO, RO, poBHti tepiioronboBxa 142432, MOCKoecvas SE (eBporief~icxri riaTePT), us 06J1., ILlxOnbHbnd 6ynbBap, g. 5, KB, 53 [IBELOV, Gennady Petrovich, Chernogolovka JabJN-I Orty~nmwouaa KOBCK4 (IijI-,pHx (2"TenaHoBHq [SU/SU]; Moc- (G omternow o mevfctynapowuooM riouc,,e (54) Title: METHOD OF OBT.AJIiNG BUTENE-1 (54) Hamnanie H306peTCeiIm, CrIOCOB IIOJIYxIEHWIA BYTEHA-l (57) Abstrect Butene-1 is obtained by dimerisation of ethylene bt the presence of a catalyst mixture of titanium tetraalcoxidetriaikylaluminium in a hydrocarbon solvent and by subsequent rectification of a reaction mass prepared by means of dimerisation in the presence of a crmpound chosen from a, group which includes aliphatic mnono- and diatomic spirits, allplaatic simple aud cyclic ethers, aliphatic ketones, amides of carbonic acids. A A APR 1989 (57) PettepaT: 1olyeBme d-y~eHa-I ooymec,2BmqoT lyemm mei z an- Aiena B lpmIC7TCTB1fla icaT~amn;vex cmO 1 c2Temu Te TpaaitocoI~gg Tln Talla Tpz aj1inuaaElMMH1fl~ B yraeBQ.OpOgAOM pac.mBOPnlTeile nociieymie. peHcTR MII t. .peaicnzom.o2 maccu, Opa3oBanialI ip~ AoepR 3aTgu B flpiiOTBfl COO rJIIHIHA, Budpamioro m is n HBu, BM~JIaKomefd aml~'qcz ogio- m Anyxa~omnue CnHpTu., axa taTti-eone nPOCTLue i um Fm iecime aiBu, aimw ecme ICBTOEHIMaAN HapdoRBBX BlCJIO!I.

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00 0 PROCESS FOR PRODUCING BUTENE-1 Field of the Art The present invention relates to the chemical and petrochemical industries and, more particularly, to a process for producing butene-1.

Prior Art Known in the art is a process for dimerization of ethylene catalyzed by a system diisobutylaluminium chloride-nickel oleate under different conditions with the production of butene-1. The maximum content of butene-1 in the resulting dimerizate is 59.1% mass and 15 its composition is the following: trans-butene-1 1-23.9% by mass, cis-butene-2 12.0% by mass, butene-1 59.1% by mass, n-butene 5% by mass. In practicing of the process the selectivity with respect to butene-1 is low a great number of side products 20 such as butenes-2 are formed in the dimerizate, whereas for the processes of polymerization and copolymerization butene-1 containing at most 0.2% by mass of butenes-2is required (cf.V.Sh.Fieldblume, "Dimerization and DIS Proportionation of Olefines", 1978, "Khimiya" Publishers, Moscow, p.38).

Also known in the art is a process for dimerization of olefines in the presence of a catalyst which comprises nickel complexes supported on a solid carrier composed of SiO 2 alumosilicate of a mixture of 30 both. The resulting dimerizate consists of 70C by mass of butene-1 and 30o by mass of butenes-2 (US, A, 4000211), In practicing of this process an expensive catalyst is used, the selectivity with respect to butene-1 is low and a high content of butenes-2 is present in the resulting dimerizate.

-2- Known in the art is the production of butene-1 by way of dimerization of ethylene catalyzed by tita-.

nium alkoxide Ti(OR) 4 aluminium trialkyl AIR 3 in a medium of ethers. (See Kinetika i Kataliz, vol.19, iss.1, 1978; P.E.Matkovsky et al. "Dimerization of Ethylene", p.263).

However, the use of ethers as the reaction medium is inapplicable on a commercial scale due to their high costs and a strong narcotic effect.

Furthermore, in the production of butene-1 by way of dimerization of ethylene on a catalytical system Ti(OR)-AIR there are encountered, first of all, :the problem of recovering butene-1 from a mixture of products formed in the dimerization of ethylene (bu- S*.t tene-1, hexenes, octenes, polymer, catalyst) and, r*e L/jpecially, the problem of separation and isolation of the catalyst which can be fully soluble in the reaction mixture. In this case two procedures can be used: the removal of the catalyst prior to distillation of hydrocarbons either by lowering solubility 0: and filtration or centrifugation, or by way of a two- -phase extraction, for example, with water; 25 straight distillation of bydrocarbons (non- -converted ethylene, butene-1, hexenes and other oligomers) at which the catalyst remains at the bottom of the distillation apparatus; it is still soluble, but concentrated in oligomers (CS, B, 187822).

From the economic standpoint this procedure is preferable since it enables elimitation of an intermediate stage of the two-phase washing or separation of solid particles; the residue is obtained in a small amount and it can be readily removed, e.g. by calcination.

At the same time, it has been noticed in practice N1? 3that during evaporation a rather elevated temperature is maintained in order to obtain the most effective concentration of the catalyst; however, this elevated temperature causes secondary reactions of isomerization and polymerization of butene-1.

Also known in the art is a process, wherein butene-1 is obtained by way of dimerization of ethylene in the presence of a catalytical system Ti(OC 4

H

9

)-AIR

3 upon a continuous supply of ethylene, a hydrocarbon solvent and solutions of the catalyst components in a hydrocarbon solvent (FR, B, 2581381), The reaction mass withdrawn from the reactor is delivered to fractionation (distillation or rectifi- 15 cation).

i* In a commercial implementation of this process th@ quality of butene-1 is gradually reduced due to the formation of butene-2. The latter appears as a *S result of fractionation due to isomerization of butene-1 on the products of the catalytical system. The higher the temperature in the rectification or distiltlation column, the longer: is the average residence time of the reaction mass in the column, the more S intensive is the process of isomerization, the higher 25 is the content of butene-2 in butene-1. At a temperature within the range of from 90 to 1200C the content of butene-2 in butene-1 can vary from 1 to 4% by volume which does not meet the requirements imposed on the raw materials employed in processes of homo- and copolymerization.

To partly inhibit the reaction of isomerization of butene-1 into butene-2, prior to the beginning of rectification the rea ion mixture is added with a modifying agent selecte from the class of amines such as oyolohexylamine, 2-ethylhexylamine, dimbutylamine.

The amount of the adued amine is varied within the L/ ,i4 YL^ r -4range of the molar ratio between the amine and titanium (contained in the reaction mixture) of from 0.1:1 to 10:1, preferably from 0.3:1 to 2:1.

The use, as the modifying agents, of amines S i.e.compounds which are, as a rule, very toxic (maximum allowable concentrations for the overwhelming majority of amines mentioned in FR, B, 2581581, are far below 10 mg/mn) hindersa wide-scale commercial application of this process.

Disclosure of the Invention The present invention is directed to the prcvision, by selecting a new class of compounds employed as modifying agents inhibiting the reaction of isomea rization of butene-1 into butene-2, of such a process 0 for producing butene-I which would make it possible *to obtain the desired product of a higher purity while using less toxic compounds.

This object is accomplished by that in a process ,i for producing butene-1 comprising dimerization of ethylene in the presence of a catalytical system titanium tetraalkoxide-aluminium trialkyl in a hydrocarbon solvent, followed by rectification of the reaction ""mass in the presence of a mzdifying agent, according to the present invention as the modifying agent use is 25 made of a compound selected from the group consisting Sof aliphatic mono- or dibydric alcohols, aliphatic ethers or cyclic ethers, aliphatic ketones, amides, carnoxylic acids.

*Owing to the present invention it has become pos- 30 sibl to,increase the purify of the resulting butene-1 by 2.0-9.3 times as compared to the desired product obtained by the process of FR, B, 2581381 while avoiding the use of toxic compounds.

According to the present invention, it is advisable, when using aliphatic moto- or dihydric alcohols, I '7 p,; A C/I j aliphatic or cyclic ethers, aliphatic ketones as the modifying agent, to carry out the rectification at a molar ratio of the modifying agent to the aluminium trialkyl of the catalytical system equal to 1-3.

The present invention enables the production of butene-1 using compounds with a maximum allowable concentration within the range of from 200 to 500 mg/m To perform the process in the presence of less volatile compounds according to the present invention, it is advisable, when using amides of carboxylic ids as a modifying agent, to carry out the rectification s. at a molar ratio of the modifying agent to aluminium trialkyl of the catalytical system ranging from 0.25 S* 15 to 3.00.

Best Way of Carrying the Invention into Effect Further objects and advantages of tha present invention will now become more fully apparent from the following detailed description of the process for producing butene-1 and examples illustrating this process The process for producing butene-1 according to 25 the present invention consists in the following steps: 25 catalytic dimerization of ethylene; deactivation of the catalyst; recovery of butene-1 from the products of dimerization of ethylene.

30 The stage of the catalytical dimerization of ethylene is conducted ia a reactor provided with a mechanical stirrer or not having it and comprises: continuous or discontinuous supply, into the reactor, of solutions of the catalyst components or a mixture 3 thereof in a hydrocarbon solvent, a continuous supply of ethylene, a discontinuous withdrawal of the dimeri- 6 zation products from the reactor.

As the catalyst use is made of a bicomponent catalytical system consisting of compounds of titanium tetralkoxide of the general formula Ti(OR) 4 and aluminium trialkyl of the general formula AIR' 3 wherein R and R' are alkyl radicals containing 1 to 6 carbon atoms.

The molar ratio of the components of the catalyst

AIR'

3 to Ti(OR) 4 can be varied within the range of from 1 to 100, but preferably, it should be maintained at 2.5-4:1. As a rule, these compounds are employed in the form of diluted solutions. As the solvent for them use can be made of aliphatic hydrocarbons (butene, S 15 pentane, hexane, heptane), aromatic hydrocarbons (ben- S* s zene, toluene), or doefines (butene-1, pentenes, hexe.nes) or mixtures thereof.

The stage of the catalytic dimerization of ethylene is conducted at a temperature within the range of from 20 to 1000°C, preferably from 50 to 8000.

The time of residence of the catalyst in the reactor can be varied from several minutes to several S.e •hours depending on the conditions of the dimerization stage.

25 The products of dimerization of ethylene formed in the reactor are withdrawn therefrom together with the solvent into an intermediate vessel, wherein the catalyst is deactivated by way of adding, to the reaction mixture, of the modifying agents according to 30 the present invention (aliphatioc mono- or dihydric alcohols, aliphatic or cyclic ethers, aliphatic ketones or amides of carboxylic acids).

Such deactivation ensures inhibition of the reaction of isomerization of butene-1 into butene-2 at the subsequent stage of recovering butene-1 from the reaction mixture. The recovery of butene-1 (reotifica- -7tion) can be carried out in a rectification column, the temperature in the column still being maintained within the range of' from 80 to 100'C.

As the monohydric aloohol use can be made of' 3I.

0 As the aideso'coyic acids HRO use can be madef for ecample, dimethylf gyomideeio (maximumloal al oerati -aton is 26000 mg/r3,ns 3 )la elhect ofdi'ydio alcehs sith as eaielylotensigyco of' vaur (atiu lowbl retc'ctontenperatoe (90 to/ CI 15 diny achorda, is ithpy ther prest in eton$ the modiyic aethes use in buc ae amor that its metaximum ola, raioxp toalminum trallae contrain the retionms e note more than fo xape see:*Asthe mimu moarboatio betwde the cadfyngmd agnentado A -R (1he usg ma- n dhdrcal horom etaerior coc evrstons) is equiale to

I.I

8 -j -8 1 or (when using amides of carboxylic acids) to 0.25.

When the components are present in the reaction mass supplied to deactivation in a smaller than the above-specified lower limit, the content of butene-2 in butene-1 is not reduced. It is inadvisable to maintain the ratio between the components above the upper limit according to the present invention, since no further improvement of the quality of butene-1 is attained. This is due to the fact that upon introduction of the modifying agent in amounts non-ensuring the minimum ratio according to the present invention free aluminium trialkyl is still present in the reaction mass which, upon reaction with the titanium-containing 15 component of the catalyst at an elevated temperature, •forms active centros contributing to isomerization of butene-1 into butene-2. Upon introduction of the modifying S: agent in an amount ensuring the ratio above the one according to the present invention, no further improvement in the purity of butene-1 is reached, since the probability of origination of the isomerization centres 600$6 is reduced to zero already at the upper limit value of 3 and a further increase of this value will result only i in overrated consumption of the modifying agent and in 25 increased costs of the production of butene-1.

The use of the modifying agents according to the present invention in the above-specified proportions relative to the aluminium trialkyl improves the purity I **of the rLcovered butene-1 by 2.0-9.3 times (at the 30 account of inhibition of the reaction of isomerization of butene-1 into butene-2).

Furthermore, the use of the compounds according to the present invention as modifying agents provides the following additional advantages duo to a lowered rate of consumption of butene-1 in the reaction of its isomerization into butene-2 the yield of butene-1 upon

>I

vf_" its factionatiori is naturally increased;- the toxicity of the production is lowered, since the employed modi- Lying agents are less toxic (by 3 to 10 and Mote times) as Compared to the Modifying agents (amiaes) employed .n the process disclosed in FR, 13 2581581.

For a better understanding of the present invention, some specif ic examples are given hereinbelow by way of 'Lllustration.

Example 1 Solut .ons of Ti(OC,4H 9 4 and Al(i-4H 9 )3 in pentane, a solv~nt (penitane) ,anid ethylene are continuously Oil 91Led into a 0.5 mn 3 reactor. The Catalyst Concentration 64 *@is I g/l. The rieaction Cf dIMerIZation i s condi,,cted at 6 the temperature of 500C. The reaction mass withdrawn 46: 15 from the reactor is supplied to distillation after a preliminary additi on thereto of isopropanol In the ratio of I n~ol pet', Mol of Al(C'4H,), preseent In t~he 0"t reaction mass. The distillate obtained after such distillation has thq following compositiOLA, ethylene- 9,96., bu'are 0.4~2, butene-1 81.5u, bi~tene-2 4660.:004'4, hexenes 5.53, the solvent 2.09.

Goes Examples 2 through Butene-1 is produced in a manner' similar to that *6e described in the foregoing Example 1. Vhowever, the 25 reaction mass Is subjected to rectification in the Presence of methylethyl-ke tone (Examnples 2$3 arnd 4), (Isoainyl alcohol (Axamzples 5 and diethylene glycol.

Exam'ple 7, ethylene glycol. (JXa3.Ple,8) acetamide (j (Example berizamide C.Lixample The composition of the distillate after rectification is shown in Table I hexeinbelow.

Example 1I Butene-1 isa produced in a manner sirillar to that

F

of Example I1 hereinbefore, except that use is macde of Al(i-4 H 9 3 and into the reaction mass withdrawn from the reactor isopropanol is added in the ratio of 3 mol of the alcohol per mole of Al(i-CLJ 9 )3.

The distillate after such dlstillatin has the following composition, ethylene butane 0.40, butene-1 81.7$, butene-2 0.24, hexenes 5.10, the solvent Example 12 Butene-1 is produced in a manner similar to that described in Example 1, except that into the ai reaction mass withdrawn from the reactor diethylene glycol is introduced in the ratio of 1 mole per mole 0 of Al(C 2 i 5 3 The distillate composition after the disllatiphr is the following, Y- ethylene 10.1, butane 0.45, butene-I 81.50, buatene-2 0.50, i* *hexenes 5.75, the solvent 1.98.

Example 13 Butene- 1 is produced in a manner similar to 0 r 20 that of Example 11, except that into the reaction mass withdrawn from the reactor diethylene glycol is introduced in the ratio of 3 moles per mole of Al(i-CqH 9 5 bThe composition of the diattllate after the distillation is the following, 4: athylao 9Q.0, butane 0.45, buteae-1 81.80, butene 2 0.20, hexaneo 5.55, the solvent 240.

'*,Example 14 Butene-I to produced in a manner similar to that described in Example I hereinbefore, except 0 that into the reaction mass withdrawn from the reactor diisoamyl ether is added in the ratio of le per mole of Al(C 2 5 3 After the distillation the composition of the distillate is the following, t othylene 9.98 butane 0,41, butene-I 81.61, g 3 5 butene-2 0.49, hexeues 5.43, the solvent 2.08.

groups contain from 1-6 carbon atoms; followed by rectification of the reaction mass in the presence of a modifying agent, characterized in that the modifying Example Butene-1 is produced as described in Example 1, except that into the reaction mass withdrawn from the reactor diisoamyl ether is introduced in the ratio of 3 moles per mole of Al(0 2

H

5 3 The composition of the distillate after the distillation is the following, ethylene 9.96, butane 0,42, butene-1 81.67, butE'e-2 0,15, hexenes 5.51, the solvent 2 .29 *Example 16 Butena-1 is produced as in Example 2 hereinbefore, except that into the reaction mass withdrawn from *the reactor dioxane is introdu.ced in the ratio of 1 male per mole of Al(i-C 4H9) 34 I the distilltion t distillat3 hag the following composition, ethylene .901 butane 0.40, utene-1 81 .49, butene-2 0.54, h exenes 5.67, the solvent 2 .03 Example 17 Thtene-1 is produced in a manner similar to that of the foregoing Example 16, except that dioxane is added in the ratio of 3 molev per mole of A1(i-C 4 9 3 After the distillation the compooition of the distil- .late is the following, ethylene 9.96, butane O044, butene-1 81,70, bptene-2 0.30, hexenes the solvent 2.09.

Example 18 Butene-1 is produced as in Example 1, except that into the reaction mass withdrawn from the reactor dimsthylformamide is introduced in the ratio of 0.25 mole per mole of Al( 2 H 5) 3 After the distillation the distillate has the following composition, ethylene 10,0, butanc 0 .40, butene-1 81 .67, butene-2 0.35, hexenes 5.58, the solvent 2.00, Example 19 Butone-1 is produced as in Examplo 1, except that

L

1 12 dimethylformamide is introduced in the ratio of 3 moles per mole of Al(i-C 4

H

9 3 The resulting distillate has the following composition, ethylene 9.98, butane 0.44, butene-1 81.80, butene-2 0.1, hexenes 5.56, the solvent 2.12.

Example Butene-1 is produced as in Example 1, except that into the reaction mass discharged from the reactor methylethylketone is introduced in the ratio of 1 mole per mole of Al(C 2

H

5 3 The resulting distillate has the following composition, ethylene 10.01, butane 0.42, butene-1 81.6, butene-2 0,4, hexenes 5.56, i the solyent 2.00.

15 Example 21 Butene-1 is produced as in Example 1 hereinbefore, except that methylethylketone is added in the ratio of 3 moles per mole of Al(i- 4

H

g The resulting distillate has the following composition, ethylene 10.3, butane 0.43, butene-1 81.77, butene-2 0.25, hexenes 5.18, the solvent 2.07.

Example 22 Butene-1 is produced in a manner similar to that described in Example 1 hereinbefore, except that as the solvent use is made of heptane and as the modifying 1 agent acetone. After the distillution the distillate has the following composition, ethylene 11.57, butane 0.40, butene-1 81.75, butene-2 0.25, hexenes 5.08, the solvent 0.95.

Example 23 Butene-1 is produced as in Example 1, except that as the solvent use is made of the hexane fraction, while the modifying agent is acetone. After the distillation the composition of the distillate is the following, ethylene 11.27, butane 0,41, butene-1 81.78, butene-2 0.22, hexenes 5.07, the solvent 1,25, J s nn 1 3FES989 I PATFNT OFFICE p I 13 0S a 0 0 S 0 06 00 0 0 0* 0 Sr 0 *000 Example 24 Butene-1 is produced as in Example 1, except that into the reaction mass withdrawn from the reactor isoamyl alcohol is introduced. The distilla.e has the.

following composition after the distillation, ethylene 9.94, butane 0,40, butezie-1 81.58, butene-2 0.30, hexenes 5.77, the solvent 2.01, Example Butene-1 is produced as in Example 15 hereinbefore, except that into the reaction mass withdrawn from the reactor diethyl ether is introduced. After the distillation the distillated has the following composition, ethylene 10.02, bu tane 0.43, butene 81 15 butene-2 0.45, hexenes 5 .62, the solvent 2.00.

Example 26 Butene-1 is produced in a manner similar to that described in Example 15 hereinbefore, except that into the reaction mass tetrahydrofuran is introduced, After the distillation the composition of the distillate is the following, ethylene 10.0, butane 0.40, butene-1 81.71, butene-2 0.29, hexenes 5.58, the solvent 2 .02.

Table 1 Examp Components, by mass Sol- Modi- Molar les bu- venti fying ratio ethy'- bu- bute- bute- he- agent of molene tane ne-1 ne-2 xenes difier to AIR 3 1 2 3 4 5 6 7 8 9 2 3 4 4f 10.3 0.40 80.7 0.67 57 2 .33 Methylethylketone 10.7 0.44 31.2 0.20 5.4 1.80 ditto 11.0 0.46 81., 0.28 15 .7 0I.66 ditto 0.5:1 5:1 7:1 CF UeHpaLaHabp ,~ucxaa Pec.xy76naia Pecny6nHKa CG KoHro KR Kopeftcnag Pecnyfntxa CH fIBeftjUapliSq LI AHXTeHUTWtHH CM KamepyH LK LfpH JaHica DE (t ehepaTqHaARPecny6niI~caepMaHHH LU ThaKceM6ypr DK aa MC MoHaMo FT 'irnwg MG Magaracmap SE Hneeu SN CeHeraz SU CoaeTCKHfi COlO3 TD 4aa TG Toro US CoeAHreHHbHw' LU-Tam AmepHXcu il b iiiiiii 14 Table 1(cortinued) 5 6 71 8 ~1 2 37 4 6 7 8 10 9 10.5 10.4 10.3 12.0 11 .1 11.4 0.41 0.43 0 .42 0.35 0 .30 0.35 81 .6 21 .8 81 .6 81.1 80.5 80 .9 0 .75 0 .25 0 .7 C 5.6 5 .4 5.5 1 .09 1 .72 1 .48 1 .10 2 .75 1 .55 Isoamyl alcoho?.

Ditto Diethylene glycol Erhylene glycol Acetamide Benzamide 0 .4:1 0.7 :1 4:1 2:1 0.3:1 0.5514.9 0 Ct 6c 0 50 C

S

.t 04 d 0t 0 00 0 .40 0 .70 4 .9 5 .1 i, Industrial Applicability 15 The present invention is useful in the priduction of polybutene, a copolymer of ethylene and butene-1,, methylethylketone, acetic acid, maleic anhydride, ethylene oxide using butene-1 as the starting feedstock.

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Claims (3)

1. A process for producing butene-1 using compounds with the maximum allowable concentration within the range S of from 200-500 mg/m 3 comprising: dimerization of ethylene at a temperature within the range of 20-100"C in the presence of a catalytical system: titanium tetraalkoxide-aluminium trialkyl in a hydrocarbon solvent, wherein the alkyl and the alkoxide groups contain from 1-6 carbon atoms; followed by S 0@ 0 rectification of the reaction mass in the presence of 15 a modifying agent, characterized in that the modifying agent is a compound selected from the group consisting of aliphatic mono- or dihydric alcohols, aliphatic ethers, cyclic ethers, aliphatic ketones, or amides of carboxylic acids. S

2. A process according to claim 1, characterized in that upon using aliphatic mono- or dihydric alcohols, So** o: aliphatic ethers, cyclic ethers or aliphatic ketones as the modifying agent, the rectification is conducted at a 25 molar ratio of the modifying agent to aluminium trialkyl S* of the catalytical system equal to 1-3.

3. A process according to claim 1, characterized in that upon using amides of carboxylic acids as the 30 modifying aent, the rectification is conducted at a molar ratio of the modifying ag'Ant to aluminium trialkyl of the catalytical system equal to 0.25-3.00. DATED THIS 26th day of February 1991 INSTITUT KHIMICHESKOI FIZIKI AKADEMII NAUK SSR and GROZNENSKY FILIAL OKHTINSKOGO NAUCHNO-PROIZVOID A LI, By their Patent Attorneys GRIFFITH HACK CO '44 6S/ln