Alkenylation of o-xylene with 1,3-Butadiene Over Base Catalysts

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o-xylene 1,3-Butadiene

* **^†

*S-Oil( )

**

(2002 7 30 , 2002 9 17 )

Alkenylation of o-xylene with 1,3-Butadiene Over Base Catalysts

Jong Seok Lee, Soo Chool Lee, Min Ho Kil, Il Seok Choi*, Jae Sung Lee** and Jae Chang Kim^†

Department of Chemical Engineering, Kyungpook National University, Daegu 702-701, Korea

*S-Oil Corporation, R & D Center, Ulsan 689-890, Korea

**Department of Chemical Engineering, Pohang University of Science and Technology(POSTECH), Pohang 790-784, Korea (Received 30 July 2002; accepted 17 September 2002)

NaK alloy, Na metal Na metal o-xylene 1,3-butadiene alkenylation OTP(ortho-tolyl pentene) . NaK alloy ! metal "#$% &'()

* +,- ultrasound . / ! 0/ 12 345 emulsion 67- "#$% &'(89: ;

<= >?$% @(8 9 AB. Na metal ! "#$% &'()* +, ;.' CDEF GH2 "#

IJKL MN (induction) (O CD. Na metal ! PQR 80 %

;<= (O R S 9 AB. T slurry Q-L UV 85 % - W X5 YZ [L \E ]. ^ 1,3-butadiene _^ OTPO ` IJKX 1,3-butadiene a &'7 `E _ oligomer a &'EF ;<= &'7 >?$' bc PQ

de.

Abstract−The alkenylation of o-xylene with 1,3-butadiene to make OTP(ortho-tolyl Pentene) was carried out over liquid phase NaK alloy, Na metal and the metallic sodium dispersed on the specific support such as NaX and Al₂O₃. Liquid phase NaK alloy showed the improved conversion and selectivity when they were pretreated by ultrasound to increase the dispersion.

For the case of metallic sodium, the induction period for the formation of homogeneous metal sodium solution with high dispersion was needed before the reaction. In the case of metallic sodium dispersed on support, more than 80 % conversion could be obtained without induction period regardless of supports used. But 85% of the metallic sodium was resolved into the reaction mixture after reaction for 7 hours. The amount of byproducts, oligomers, produced from OTP and 1,3-butadiene increased with the amount of 1,3-butadiene introduced and the selectivity to OTP was in inversely proportional to the conversion.

Key words: Alkenylation, OTP, o-xylene, 1,3-Butadiene, Na Metal

1.

Polyethylene napthalate(PEN) Polyethylene terephthalate(PET)

PET

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.

PEN/ 0 19961 23 2.3 million lb45 200014 23 12 million lb, 200514 23 34 million lb 61 78 !"

9. :;< PEN / =>? NDC(naphthalenedicarboxylate)/

@7> %A$ PEN BCD&/ 80%( E NDC/ &F

PET/ DG? PTA(purified terephthalic acid)4 HI J 10K&> HL PET4 I &F MNO P$ Q. ?I PETR PEN (

S HT UVI5 PET W XY Z$. [\]

^_$ Q[1].

NDC/ BC` 2,6-DIPN(diisopropyl naphthalene) a`, 2,6- MIBN (methyl-6-isobutyl naphthalene) a`, Henkel b`, 2,6- DMN a` Q. :;< 2,6-DIPNY DGCc/ dBe &

$ Qf Henkel b`Y T g. : U 2,6-DMN a`

"h / &i & jY k&#$ Q.

†To whom correspondence should be addressed.

E-mail: [email protected]

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670

"h#_ Q PEN@ U & $ lm) Amocon/

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rs$, DMT( dehydrogenation t( qI5 1,5-dimethyl naph- thalate(1,5-DMN)( ZY , isomerization/ t( uv 2,6-dimethylnaph- thalene(2,6-DMN) BCp. :w$ xy t 2,6-DMN a

z NDCA( Z @.

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~ , 45 9 lm Q. n9 l|w }~Y Na

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lm Q[2].

;p 6 4] K2CO₃, Al₂O₃4 K metal 5

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$ #_ Q[4-7].

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& 4 ' O I5 " NaK alloy(

ultrasound ¡w -a]4 ¢£ $,

¤_ lm) Na metal 6/ ¥¦ D? § 6 / &i ¨#©.

2.

2-1.

[\45 o-xylene(98.5%)Y Junsei Chemical Co./ Bª n

$ 1,3-butadiene(99.5%)Y Matheson Co./ Bª n.

Na metal(99%)Y Aldrich Chemical Co./ Bª nf glove box «45 ]¬ I tI5 n. " NaK(Na 77.2%, K 22.8%) Callerly Chemical Co./ Bª n.

Na metal 6 ®¯ °`(dry method), wet method, wet- evaporation rs Q[8]. ®¯ °`Y ( 350^oC45 3

3 b¡wp glove box«45 Na metalo ( ±w ²³´

µ4 ¶$ ·+ ¸¹º5 150^oC45 x:»¼ ½ 13

5 4 º °`. [\45 Al2O₃R zeolite X( 4 9 Na metal 6( BCf

6( " slurry 4 .

Alkenylation b 6/ 9 Na ¾>o alkenylation U

« ¿ U/ Na/ ¾> lÀ I Atomic Absorption Spec- troscopy(AAS, Simadzun, AA-680)( . Alkenylation U Á

# %a(byproduct)o 6/ H¦3/ " lÀ

I Elemental Analyzer(EA, Elementern, Vario EL)R Thermal Gravimetric Analysis-Differential Scanning Calorimetry(TGA-DSC, Rheometricn,

STA 1,500)( -Â. ¿Ã Á/ -ÂY Gas

Chromatography(]Ä, DS6200)( f, columnY HP-1 capillary column(Hewlett Packard) n.

2-2.

O-xyleneo 1,3-butadiene/ AlkenylationY Fig. 145 < semi- batch ( . " NaK/ M }~/ -a]( 8&

º I ultrasound ¡w( Å sonication ' ultrasonic cleanerR ultrasonic horn system . Ultrasonic cleaner( p sonication

' BRANSON 3210(47 kHz) n. Glove box «45 3

²³´µ 4 o-xyleneo S>/ NaK( Æp ÇÈ5R É Vº$, cleaning bath «4 ' 2-33 Ê sonication . Ë 3 ²³´µ 4 ·+( Æ$ cleaning bath/

Ì] "Í y I ÎÏS 10-15^oC ±.

Ultrasonic horn system p sonication ' BRANSON 450 sonifier( n. o-xyleneo NaK( 3 ²³´µ4 ¶Y ÐÌ bath 3 ²³´µ / Ì]( C5 metal horn ¶$ D

3Ê sonicationp. Sonifier45 transducer4 / 8Ñ 9 ultrasound& metal horn qI ÒÓ bc9. 6 jY intensity/ ultrasound& ÔÁ Ëd4 Õ Î Ö p.

Na metal< Na metal 6( p M, 4 o

¾× BC9 6( ¶$ ·+( Ø- Ùm «/ @( Bu p heating mentle I5 Ì]Ú "Í. Ì]4 ] c 1,3-butadiene @75 Û. 1,3-butadiene/

±>Y ±>C(MFC: BROOKS 5850E)( n Æ.

bTY o-xylene Ü $ ÝÞ]R bTY ßo à

a.

Conversion(%)=[1− ]×100

Selectivity(%)= ×100

3.

3-1.  NaK alloy

Fig. 2R Fig. 345 " NaK alloy 6( p Alkenylation/ b To ÝÞ]( <«©. Ultrasound/ ¡w áo( lÀ

!H [\ ÊSp C®45 sonication ¡w( p 6R Àâã ¡w ä 9 6/ bTo ÝÞ]/ E( Fig. 2R Fig. 34 <«©.

Glove box «45 o-xylene 98 go NaK 0.1 g 4 Æ$,

( ·+ purge5 ultrasonic cleaning bath45 2.53 Ê sonication å. Ë ¡ß4 æ$ çèp o-xyleneo NaK/

éV eE ê£ë/ ìí î5 emulsion ïp.

Sonicated NaK( 6 n M4 40 -/ bTo Ý

Þ]& 12%, 82%<, sonication ðY M4 60 -/ b To ÝÞ]& 6%, 20%] gß l Q. p ñ M ¿ ñ ÝÞ] 34 ¢³ ò+. R à sonication ¡w( p

(mole of unreacted o-xylene) (mole of reactant o-xylene)

(mole of OTP) (mole of reactant o-xylene)

Fig. 1. Schematic diagram of apparatus for alkenylation.

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jY ? l Q©.

Fig. 445 ultrasonic intensityE4 ¢£ / áo( ó?

ÊSp C®45 ultrasonic intensityr î z alkenylation ) ZY Éo. Ultrasonic intensity( C

I ultrasonic cleaning bath& Àô “Ultrasonic horn system”(450 sonifier, Branson) n. Fig. 4 NaK 0.1 g 5-3 18, 35, 50, 60 watts sonicationp Ì] 125^oC45 13Ê

p Éo. Ultrasonic intensity& 8&¾4 ¢³ o-xylene/ bT ] 3.6, 5.4, 9.3, 12.4% 8& <õ. Ultrasonic intensity

& 18 watts] gY M4 sonicationÊ NaK emulsion D¦

ö ^_ ð ó? Q©.

Fig. 545 gY ultrasonic intensity45 sonication 3 E4 ¢

£ / áo( lÀ ultrasonic intensity 18 watts45

5, 30-3 sonicationp o ultrasonic intensity 60 watts45 5-3 sonicationp / Éo( <«©. Ë Ì] 125^oC

$ 3Y 13, 6>Y 0.1 g. Ultrasonic intensity& 18 watts45 30-3 sonicationp MR ultrasonic intensity& 60 watts4 5 5-3 sonicationp M/ bT 13.2, 12.4%$, ÝÞ]& 60, 65%/ Éo( . ultrasonic intensity& gY M4 W ÷ ø 3Ê sonication ¡w( Ör NaK/ emulsionï ^

_f jY Z Q ó?. [B ultrasound / source ultrasonic cleaning bath( n M4 Fig. 2R Fig.

345¡ù 2.53 ] sonication¡w( Ör ÊSp Z

Q©.

Fig. 2. Effect of sonication on the activity of NaK alloy.

(reaction temp.: 125^oC, NaK: 0.1 g)

Fig. 3. Effect of sonication on the selectivity to 5-ortho-tolyl pentene.

(reaction temp.: 125^oC, NaK: 0.1 g)

Fig. 4. The effect of ultrasound intensity on the activity of NaK alloy.

(reaction temp.: 125^oC, reaction time: 60 min, NaK: 0.1 g, sonication time: 5 min)

Fig. 5. The effect of sonication time on the activity of NaK alloy.

A: ultrasound intensity 65 watts, sonication time=5 min B: ultrasound intensity 18 watts, sonication time=30 min C: ultrasound intensity 18 watts, sonication time=5 min (reaction temp.: 125^oC, reaction time: 60 min, NaK: 0.1 g)

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672

Fig. 645 l|w }~/ ú¹4 ¢£ sonication/ áo( lÀ

NaK, K, Na metal / l|w }~ ultrasonic intensity 60 watts, 10-3 sonication Ì] 150^oC45 3 60-

/ Éo( H. Fig. 645 û o-xylene/ bT NaK/

M4 12.4% ]< Na üY K metal/ M4 1% r

<õ. / l|w }~/ sonication o45 NaK/ M

emulsion/ ï D¦ö ^_r Na üY K metal/ M

emulsion ï# ðý Ëd nG9. SonicationY "

/ NaK/ -a]( 8&z emulsion ïºÅ áo& Q

< }~ M ./ -a]( 8&ºÅ áo þ

.

3-2. Na metal

Na metal o-xyleneo 1,3-butadiene/ Alkenylation45 6 n

p 2 Éo45 %- gY u< ä

lm ÿ$[9] [B / [\45 û }~/ -a]( j

p sonication ¡w] áo( þ. ;p Éo Na

metal «4 -a# _ $ Qf

Na metal/ gY ¦Y }~/ gY 6 ¦4 ?

gY -a] Ëd Á#_ Na metal 6 [\ )

. Fig. 7Y Na metal b ð$ p o 140^oC/ o-xylene ~45 x:»¼ ½ 33 Ê Na metal

-a p Éo. Ë butadiene 130 ml/min, o-xylene 106.2 g, 6 0.3 g n. "/ NaK 64 HI5 Na metal / gY Ëd4 6> 3K 8&º$ Ì]( 140^oC 8&z [\.

Fig. 745 û Na metal ð$ [\p 6 23%

Û< 33 Ê x:»¼ ½ p [\p

6 30- «4 Û#©. Ë Z Q b To ÝÞ] E& ä©f t Û 3 13 30-

] ³. Y Na metal ð$ [\ Ë 2

3 Ê ð$ 6& Ø- -a9 Û9

?. R à Na metal 6] NaK Alloy6R à 6(

-a jY Z Qß l Q©< s

6/ C® c³ ÒÓ H ä©.

[\o ] $ ? autoclave(autoclave engineers

group)( Na metal ðY o ;( n

33 Ê p [\p 45 ñ M ¿ñ45

ä©. $ / ;( n autoclave «45 Na

metal MR " / x:»¼ ½( n 33

Ê M( HI ;( n Na metal

p M Æ. µ& 2-3 mm ] # Q©f x:»¼

½( p M À ÛY Æ.sr -¾ Q©. [ B ;( n $( np M4 Na metal 6 ä_ K metal ¾× ¶_ $ #_ Q

[10]. ÀÒÚ óp D?Y è# ðýr Na metal/ ¦Y }~./ ¦ dB³ }~/ -a]4 ÒÓ? Q ß /p.

3-3.  Na metal

Fig. 845 Al2O₃R NaX( n 30 wt% Na metal

z [\p Éo( Na metal/ ÉoR H. 1,3-butadiene 130 ml/min, 6 0.3 g n. Al2O₃ BET 3 m²/g (Shinyo Pure Chemical Co.)R 156 m²/g(Aldirch Chemical Co.)? ñ

&( n. Na metal 6 Û 23 %

Û#©$ 30 wt% Na/Al2O₃Y 13 %, NaX( n

p 30 wt%Na/NaX 30- «4 Û#©. 4

9 Na metal/ M 6 BC o45 }~/ -a]& 8&#_

% $ Qf / % H

Y zeolite / M, áo 3 S Q

©. 4 Na metal np MR Na metal :

np M Û 3/ E Q©< Û9

/ ~]R bT45 E ä ó?. Al2O₃/ M £ Al2O₃( n< àY M <«$ Q$ Û 3 p à. Al2O₃/ M

E4 /p ä À [\[45 BC9

6 Al2O₃ «% @ % 4 Na metal -a

?.

Fig. 6. Activities of various alkali metal at 150^oC.

A: NaK alloy, B: K metal, C: Na metal(sonication time: 10 min,

reaction time: 60 min, alkali metal: 0.1 g) Fig. 7. The reactivity of sodium metal at 140^oC.

(A) no stirring before the reaction, (B) stirring with magnetic bar for 3 hours before the reaction.

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®¯ °` rÃ 6 U 30 wt%Na/NaX 64 I b, R U / Na ¾> H -ÂI ý. 30 wt%Na/NaX(

34 ¢³ 6( o D+-Â Na/ - Âp Éo( Table 145 <«©. np NaX 12%/

Na ¾$ Q$ 30 wt%Na/NaX 6 Na 32.2%? ó?

. 33 o <Ì 6( AAS -Âp Éo Na

19.9%, 73 15% 32.2% 7F _ Q

l Q. 33 4 9 6/ 39%]/ Nar Ä$ <

U4 À <÷$ 73 4 15%r ÄÀ Qö 9.

Y 9 Na metal $# ð$ 73 4 85%&> À <÷$ Qß /p. p 1,3-butadiene Ùw ð

$ o-xylene «45r 6( 73 Ê op 6/

Na Y 14.6% 9 Na metal U 13%& ÄÀQ ó?

. butadieneo "ä o-xylene4 "=>/ Na À <÷

$ Qß /p.

Fig. 9 U « S> ² D+-Â

-Âp Éo. 23 « Na ¾>Y 382 ppm, 43 779 ppm, 73 869 ppm 8&. )4 ¢³

4 #_ Q Na metal U À <÷$ Qß /

f 73 U/ À Q Na 0.15 g ]. Table 1o Fig. 9/ Na ]& £ Y 9 Na ~4 À <÷]

$ Æ. ¤_ <R U4 ,p /p.

R à ¡ß S 6( rs I 4 9 Na metal

¡ß /]R cw 45 ¤_ <R ?

. Ë 4 þr 9 Na

metal -aº 6 3 $

Q.

3-4. !

Fig. 10Y 1,3-butadiene/ ±> 130 ml/min, 75 ml/min, 35 ml/minS Ë/ <«$ Q. 1,3-butadiene/ ±> _s bT Y ò+r ÝÞ]& XÀ Q. Butadiene/ @7

~] 8&4 ¢£ bT/ 8& o>/ o-xylene4 p>/

butadiene @7 [\ °¯ , ! butadiene/ · bc p

4 ?p "9. ÝÞ]( # 9 %Y

? butadiene 3/ ? dimerizationo butadieneo Á/ ÉV Fig. 8. The effect of dispersion on the catalytic activity of various catalysts.

Table 1. The concentration of sodium in catalyst

Catalyst Concentration(Na)

Na form X zeolite 12.0%

30 wt%Na/NaX 32.2%

Filtering cake(after 3 h) 19.9%

Filtering cake(after 7 h) 15.1%

Filtering cake(after 7 h, without butadiene) 14.6%

Fig. 9. The concentration of sodium in mother liquid as a function of reaction time.

Fig. 10. The effect of butadiene flow rate on the activity and selectivity of 30 wt% Na/NaX catalyst.

, : conversion and selectivity at BTD flow rate : 35 ml/min

$, %: conversion and selectivity at BTD flow rate : 75 ml/min

, : conversion and selectivity at BTD flow rate : 130 ml/min

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674

4 /p oligomer/ ï4 ?f, p ? butadiene/ @7

~]4 ¢³ bTo ÝÞ]& H&5 î Y ÝÞ]/

9 ò+ 0? oligomer/ ï4 ?¾ lm$ Q. OTP4

p ÝÞ]( jö ± I5 &ip gY bT ±

5 Á -w ±w 't9.

Oligomer ï4 p butadiene/ () I5 butadiene

±>4 ¢£ %a/ ï ßo à -ÂI ý. 1,3-butadiene

±> 130 ml/mino 75 ml/minS Ë 30 wt%Na/NaX( 6( n

73 Ê Ø- z bT H*p "+45 o

(Advancen, No. 5C)( 6( -w$ 190^oC, dry oven4 5 123 Ê ®Cå. R à ®C9 6( -,

Elemental Analyzer(EA)( q o9 6 cake «/ -+

R +/ ¾> -Â. -ÂÉo 75 ml/min 1,3-butadiene Ù . M -+/ ¾>Y 8.9 wt%, +/ ¾>Y 2.8 wt% <õ.

130 ml/min 1,3-butadiene Ù. M -+ ¾> 15.1 wt% 8

&$ +/ M 3.4 wt% 8&. o Á? xylene o OTP& 6/ -+ / ¾>4 ' I5 o-xylene o OTP& 1:1 éV9 4 zeolite X( ¶$ 243 Ê stirring

$ àY C®45 ®Cp -Âp Éo -+/ ¾>Y 1.3%, +

/ ¾>Y 2.7% <õ. ;p Éo o-xylene üY OTP -+

/ ¾>4 þ$, 9 / D?Y %a4 ?¾

$ Qf 1,3-butadiene/ ±> 8&0 4 /#

-+/ ¾> jÀ Y %a/ ï4 1,3-butadiene

'$ Qß 1$ Q.

H¦ ±Ô ·/ lÀ I 1,3-butadiene/ ±

> 130 ml/minS ËR 75 ml/min/ C®45 , EA/ G ÜHR ÊSp °` TGA-DSC/ G( ÜH. H(

I5 o-xyleneo OTP& éV9 4 zeolite X( ¶$ 243 stirring p , EA45 -Âp o àY C®45 Ü G( ÜH.

TGA-DSC/ [\ C®Y 120^oC45 25- Ê 4 w

239 < £ ± ·+ - 45 Bu. : 120ôC% 700ôCÚ @( Ùw5 15ôC/min/ ÍÌ ~] -Â

[11, 12]. Fig. 1145 û 130 ml/min 1,3-butadiene Ù . / G45 300^oC%445 > î( $ 500^oC

%445] 5Y > îR ¾× âö ò+>] ?. 1,3-butadiene / ±> 75 ml/min ò+ > îR âö ò+& 130 ml/min

¡w / G4 HI µö ò+$ Qf o-xyleneo OTP( ¶$

't#f [B " NaK( OTP( BC \ t

/ @45 bTY 10% « C 74 ä D? Á

9. p 8ö ï9 oligomer 9 64 /#_ H¦

4 ÒÓ? D? 9 $] Q_[13], %a Á 9B

jY bT 45] OTP4 p jY ÝÞ]( ±º @

Ý :O ;0.

4.

"/ NaK alloy( sonication ¾ < ~]R ÝÞ "

# ó?. ultrasound4 / "/ NaK alloy&

6 ÛY Æ. = emulsion ïI -a]( j Ëd.

Ultrasonic intensity& 8&0 ~]& 8& M f, ultrasonic intensity& gY M4 ÷ø 3Ê sonication

Ör Ø-p Z Q©.

}Ú o-xyleneo 1,3-butadiene/ Alkenylation45 Na metal 6 n Ë 6 gu< u/ ä

lm Q< Na metal] b Ø-p 3Ê -az r p 3(induction time) ä jY

Z Qß ó?.

®¯ °` BC9 4 9 Na metalY }~/ -a]&

jÀ5 -a9 "/ NaK üY b ¡w9 Na metalo ±nö

% 3 ä p < 73 4

85% " 45 ¤_ <ÿ. [\45 9 ®¯ 6 BC`Y %4 Na metal -az 4

þ$ 6( p "[\45 "=>/ Na metal

À <÷> " 4 2& ~#_Ö p.

°` ~ 2#_Ö p.

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8. Fushimi, N., Kedo, K., Inamasa, K. and Takagawa, M.: U. S. Patent 5,334,794(1994).

Fig. 11. The result of TGA-DSC of Na/NaX after treatment at various conditions.

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Alkenylation of o-xylene with 1,3-Butadiene Over Base Catalysts

  o-xylene 1,3-Butadiene  

Alkenylation of o-xylene with 1,3-Butadiene Over Base Catalysts

o-xylene 1,3-Butadiene