QUÁ TRÌNH ALKYL HÓA trong hóa học dầu mỏ

I . MC ĐCH
  
!"#$%&
o 
o '(
 )$*+!, /01(2
34%5%67(8*+!, 9:: %67
/
 '(()!34%5;!$8
8!/
 < =$>?@ABCDE@ABCFG-
%(HI/JK $8*+!3(LM!N
=/
  (3638'O!! *+!N!'P!!M!
!%QR!8'2S/
 0!M!!%QT%U 2*+!
!%VW3(3/X&
o AY8*+!!%%-7!=!%%$%
!%%$37'/
o Z%[34%>!2%2GT%U O!=8!2
/
o \M!2-V*'']
o ZTT[34%*+!, /
II . NGUYÊN LIỆU VÀ SẢN PHẨM
II.1. Nguyên liệu
 A!%QM!!%Q$(7(3/
0!2$^:_^`a'(Z
F
2I
$%b8Z
c

Z
`
/d$(7(381P
$[ (% '2!*e%Q
%!*e /
 d$<%67!%VN!/d7(N
!!%QM!!%VN!"!f%% T[O!
VN!%67(!%V$[*e/JT$%U%Q.
$%74%!%QT!.()!
=%(/
 Eg'OV%-74%UT!%VN!!
%-7(4%f!8-'P!!%Q!M!!%Q/
A!%!"[%!*e%-(;!8"%1%
Quá trình alkyl hóa trang 1
'2Mg%UM!$ (% '2h/E= 8!!
!+!%-7(8-V*(i%"!7(/
 j3!"!%Q34%[!%-V*
-Vk%3733-Vk%Q=-M%[8
%-'P!2%%Q=!/0, -V
kf!!$%CF7C^P=2"!
34%Z
F
*e%U%Q$=!/
 A!%Q2$ N33('%3%
% *el% *%-4%e!$-3(31
34%I!*%!%V"!=*%/
 A!%!!%Q;!M!N8L%
le!'m'P!l%*%+!%*%/A !!
%Q8L%e!V%8%Ul%
% *el%*%-4%2$%lh%!%Q/

II.2. Sản phẩm
 n-Vk&
o \[&
o02 '(/
oZT'O!!%Q/
op%Q-"%[% `79:a/
o qVk&
o5&< @A=$%Q'O!
82 *+!8!/
og!&%Q=-M%19r:÷c::

Z'O!%%Q
'%363/
o d$(7('%3-VN!/
o A!%[N34%8q/
 qVk[%67% r`÷^:aT[-Vk/Z
$-Vk8!b8##F]#cF
#cc7%333<%'O!!!< 
%%Q/
 Z8!*+!&
o s+!818!&, 
C`N[34%'(2N 
%67/0f!-'P!T$%*+!T!
8!/
o s+!%Qf!'O!*+!(
T+!%Q,/
Quá trình alkyl hóa trang 2
o 0!8g44%-%
(i%%i%Q=/
Bảng 1. Trị số octan của một số sản phẩm chính của quá trình alkyl hóa izo-butan

bằng buten
j3 ?@A E@A
t67(3
j37#
j379
##F7%33
#cF7%33
##F7%33
#cc7%33
#c7'%33*
#F7'%33*
9::
9:c
9::
9:D
r9
D`
9::
CD
9::
CC
rC
r:
III . XÚC TÁC
 sef!8%c$%[-&
o seZ
c
o sep
#
q@

F
o sepu
 A!%!(3633()!34%IT-'P!*e
N63%3vR%%/
III.1. AlCl
3
 Z
c
i$!%w2M!!'(*e
 VN!/0%3N=pZ(w2T
-!$!%h!-xh!M!!
'(!$[l'+!.=VN!/
 yT8*e!f%% -PpZQUO
!'()$.=VN!!1!%%
$2VN!Nf!8k(,l%Q
VN!/
III.2. H
2
SO
4
và HF
sep
#
q@
F
sepu
A%Q=
dVN!iO!%Q=1
F79:


Z% (,VN!;!
V%8$'l%9:

Z/
XO!%Q=T)
!V!#`7F:

Z
% (,VN!T
8$()!l/
z- #7c `7D
A"!=-
'P!
CF7CDa {|^ra
0f%!%
VN!
#:7c:e 9:7#:e
Quá trình alkyl hóa trang 3
}8!%

#`7c:t(~O! •:9Ft(~O!
€i!
•%U%Qf!"$%'$!
Th![=*‚'m
'![!$%l%M%f!
Z[=$%!
!%!f%
!Vi! M%
f!/
\V+!I


ƒ/ A%U
0%-%*e

dV%=*i!*‚
%!/
ZT%-%()!!
$/
„2
=
ZpuV+!I
%67(>:9aG/
0V+!I
%67(
V!:ca/
Bảng2. So sánh xúc tác H
2
SO
4
và HF trong quá trình alkyl hóa
 *%p
#
q@
F 
8-'P!=!H%!'U%Q$%f!
8%-%()!!%Q=/0%
p
#
q@
F

[*%$'m$v$q@
#
q@
c
p
#
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 sepu$$[.%!*eN=8!h
9`ap
#
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 A!!f%H%*epu'$!w',T!$%
%TR%(Y&
o 0 8%'puh![+I$=$%'Y
%QM%f!
o y=$[!!puh!
o Jm-VkH',T*e/
 0%%%67(()!(3-'P!*ep
#
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-Vk8!%'O!*epu/

Quá trình alkyl hóa trang 4
A!%Q34% pu p
#
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j3>!(G
C#÷CF
CF÷CD
C9÷Cc
C#÷CF
C`÷Cr
C`÷Cr
^^÷C:
Cc÷C`
Bảng 3. Trị số octan cho bởi loại xúc tác và olefin nguyên liệu
III.3. Xúc tác chứa zeolit
 seN63%f!$%ZA%„}p„g(%Q*e$%
63%3„NZ!.% /
 seN63%3[*VVN!P&3*%'m
*e-Vk$%% /0%%'!*e
%Q=-VN!V%%'O!*epu/
VI. BẢN CHẤT HÓA HỌC
VI.1. Đặc trưng nhiệt động học của phản ứng alkyl hóa
 %67(()!!%Q34%5f!-'P!!%Q
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8!/JY%!%V%Q=+!--ˆY8%
!‰()!T',U[$-Vk/
 03v!%Q/%QVN!-&
d3 9C`~!
j3 9r`~!
d33 140 ~!
VI.2. Cơ sở của quá trình alkyl hóa izobutan bằng butylen
 qVk'O!  $*+!'i-iU
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*V3 %(%/\V+!VN!34%!f!
88!%()!N=$(%/
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(/0f%!%"$%(%'=!!V!f%!%
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 y=(U%(%T8* 3Nv!%V'2-&
jYc{jY#{jY9
Quá trình alkyl hóa trang 5
CH2 = C
CH3
CH3
CH3 - C+
CH3
CH3
+ H+
(bậc 3)
CH2 = C
CH3
CH3
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CH3
CH3
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 A !%Q$Z
F
!%U%QTO!8
$'(g!!%V"!=*e/
 XU(VVN!%67(()!(3(!"(!%%$&
o †%%$(%
o †%%$%T$
o †%%$$-Vk
VI.3. Các phản ứng không mong muốn
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7dVN!(.$%&#Z
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V. CHẾ ĐỘ CÔNG NGHỆ QUÁ TRÌNH ALKYL HÓA
 p%Q-8!8*,M!<'[
!%Q*eI'Vi!%U%QM!!Q
(!"&

o A%Q=VN!/
o 0f%!%VN!/
o 0ŒQ%67(~(3/
o A"!=*%/
Quá trình alkyl hóa trang 6
0 20 40 6 0 80 100
MON
t0CCCCC
88
89
90
91
92
93
o A"!=%67(!O!VN!/
o z-&SO!--% Y8%"!
f%'$!%Vi!/
V.1. Nhiệt độ phản ứng
 n(!"VN!h%Q%Q=V
i!N$ /
Hình 1. Ảnh hưởng của nhiệt độ đến trị số Octan của alkyl hoá.
 \%%Q=+!=l!%V*.!'x +!f!
V+!=VN!% *el%.
!%V8+!8!=%$%ekVN!P
3%!3*+!'.=VN!$
/\ V!%V=SS!%V"!=
%%U8!*%!%V8!>!%V, =R,
G/
 \%!%V%Q= =!%l%$,-ˆ$Y8%
+!=SS!%V%*e+!%Q-

8!/A!"!f%%Q!%V%Q=;!!%V
"!=%'$[*e!%.+!8!/JV%=
V!%Q=O8/
 0!M!!%Q%Q=[8.%l%*e-&
o sep
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%Q=&F…9:
:
Z
o sepu%Q=&#:…c`
:
Z
o se%'w%Q=*e%'h!/
 †%,PT%Q=VN!8S2[ Vi!
M! <%% -V(V8!%Q
-/
Quá trình alkyl hóa trang 7
0 90 92
90
94 96 98 % axit
92
94
96
98
100
100
NO
 03f%!%VN!"!=*e!%V$[*e!%V!f%

T+!%Q=#÷c

Z!V!KT(O$%$[
*e)'%Q-M!R%/
V.2. Độ axit
Hình 2. Sự phụ thuộc thuộc giữa nồng độ axit và chất lượng alkylat
 yT% $Z
F
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^^7C^a>.1CF…CDaG "!=*%-ˆVi! V
+!*$M!!. "!=*%-ˆ
+!.=VN!P3'x .=!%V/
 n$Y.v$%%"!=34%I>
PG*ee!()!8!%(%$!%VN!
/
 A!%%QVIP=V+!=.T
+!% *e!%*eVN!/
 0!%Q"!=*%!%V*.!'%![
o J[;!*%8>3-3N$%'
'(///G
o JH!(i%l8$1VN!P-•!
!%Q[;$%/
 \%=2*eV%8h%b8VN!(O
=8!l%"!=/}8!*%%V!`÷r!~9::[
/
 pb8VN!Q%Q.!

(;!!Vi! "!=*% (=Y
M!V+!KY;!.-ˆ$%U%Q% 
Quá trình alkyl hóa trang 8
0 2 4 6 8 10 12 14 16 18 20
Hiệu suất alkylat %V
Tỷ lệ I/O (mol/mol)
Hình 3. Ảnh hưởng của tỷ lệ I/O tới hiệu suất alkylat
100
95
90
85
80
VN!PM!!.Y-ˆ!%V"!=*%;!
%Q-8!/
V.3. Nồng độ izo-butan
 JV+!I%67(!*%h.+!.=
VN!"!=%67(2V%$v$%!O!VN!!%
!f%%  (=Y=g(%Q!VN!;!T+!
V+!I%67(!*%/
 @34%2INf%!*%8!34%2V%
8%hT$ VN!P/0!M!!%Q!(<Q
%67(~(3>t~@GR%1`~979`~9/
 \%-'P!8!'%67(-l%(3-ˆ$ VN!Pg
(%QVN!334%Vi!. %Q-
+!8!-Vk!.+!, !%V%
*e/0YM!'O!8!'l%67(%%
[%-%-VN!-ˆ/
 Z8!PT[.![R-Vk+!
%+!"!=%67(8!%67(%8'O!T
!%8!/

V.4. Thời gian phản ứng
 0f%!%VN!8*,(i%% .
(V&
o 0.=%Qh%O!VN!V%T!%%Q=O!
VN!HS/
o 0f%!%T%67(I*%V(V
*V!.*VVN!P/
 yT$%Q-v$%f%!%% *el%*ep
#
q@
F
f!1#:7c:
eIpu9:7#:e/
Quá trình alkyl hóa trang 9
 0<Q!%%''(!% (,VN!8.! !
V!9~9 #~9!V!-ˆ8!./
#: F:
`:
#`
r`
9::
D: ^: 9:: aX
A@
Hình 4. Ảnh hưởng của tỷ lệ axit/RH đến chất lượng của alkylat
VI. SƠ ĐỒ CÔNG NGHỆ ALKYL HÓA
VI.1. Quá trình alkyl hóa sử dụng xúc tác H
2
SO
4
VI.1.1. Sơ đồ khối tổng quát.

VI.1.2. Sơ đồ công nghệ của hãng Kellogg
a. Sơ đồ công nghệ
Quá trình alkyl hóa trang 10
9/ 0% (,VN! `/0%67(
#/ 0% (,$ D/0% (,(
c/ 0 r/0(%
F/ 0
b. Nguyên lý làm việc:
 A!%Q34%%67(2% (,!%%Q%% 
(,VN!>9G/pb88=Ž-v% *el%p#q@F
81(%Q.!%281!% (,/A%Q
VN!8()!(%=2'(
!  b  8  V  N!  T  !%    %Q  =  V  N!  i  F:
:
u/  d2
'((%8 % (,$>#G
>cG/d2!!8i$%% (,VN!/d8i<
>cGi=28T% P!%Q
/qVkVN!8 % (,>FGi'(
8      h%  *e    *%  -4%    *%  8    %  %  -%/
p'(l%8 %67(>`G/d2i<
!%%67(8i$%VN!/d28 % (,
(>DGT2-Vk8*‚$%(
%>rG/d2<-Vk(/
c. Cấu trúc lò phản ứng
Quá trình alkyl hóa trang 11
 ?3f!`(Y!b%(YU(=Y=$
$8;![8VN!/Z(Y8
()!w}/Z.%O!I!w!!"%O!O!9
O!N*%O!#O!N/@34%8'x"!f%

`(Yl%ŒQHSl/Xl%3$%VN!!%V%%Q
f-v(.%%67('%QV'%Q%U%T%Q
='m'!/
 y%U%Q%Q% (,-&
7A%Q=&F÷9:

Z
7z-&9÷c†~
#
jYA

a%67( 0ŒQ%67(~34%
9
#
c
F
`
0!(
^c
rD
D^`
`C^
`:`
DrD
c:`
#^#
##9
9^9
9Fc
###

Quá trình alkyl hóa trang 12
Bảng 4. Sự thay đổi nồng độ của các cấu tử vào nồng độ phản ứng trong
reactor/
 yg[ &
o q'P!M!!Qv$l%%QV/AK$
i%Q=T-Vk8!!+!
-/
o q'P!Q.!$1!(Yl%"!=%67(!(/
o q'P!Y.(Ug!VN!T8-Vk
8!$%1U+I!% (,$-v$
3-3/
o }IVN!$=!i-=%Y% (,
i!% (,=/
o q'P!`IVN!% l%(!=% (,[
T$!%'UM!!Q/
VI.1.3. Sơ đồ công nghệ của hãng Stratford
/ Sơ đồ công nghệ
Quá trình alkyl hóa trang 13
9#cF/0% (,VN! ^/EK 999^9C#9/jTN
`D/0% (, C/0% (,$ 9#/0
r/j!! 9:/0h! 9c9F/0% (,w!
9`/0%67( 9D/07( 9r/0!
#:/E( ##/0% (,R%%Q
Quá trình alkyl hóa trang 14
b. Nguyên lý làm việc
pb8'(N34%1O!N>9^G8(>#:G
% (,R%%Q>##Gl%T$*.!V!r
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Z8
%F2()!$F% (,VN!/t67j1O!N

>9CG;!8(% (,R%%Ql%T$*.!
V!r

ZO!l%%67(1O!N>99G2% (,V
N!>9G/se*%1% (,>`G>DG82% (,
VN!>9G/0!% (,VN!>9G*V]b81
% (,VN!>9G(!"$%67('*ep
#
q@
F

    7(  8    -!  %   (,  V  N!  >#G  O!  l%  8!
'(l%N34%T% PVN!/pb81% (,V
N!>#G2Si% (,VN!>9G8-!% (,
>`GT*e>'"!=*ep
#
q@
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H!%V*.!'l%C:aG
*%=22i$%% (,VN!>9G=2V%
!%T%-%/d2I$%i% (,>`G8-!% (,VN!>cG
O!l%8!*%21% (,>DG8!*%l%8!
'(l%N34%T% PVN!/pb1% (,V
N!>cG8-!% (,VN!>FGO!l%8!'(l%
N34%T% PVN!$%88!
/pb81% (,VN!>FG8-!% (,>DG$%
*%82i$%% (,VN!>cG/d2I$%i
% (,>DG8%F2()!T$F% (,VN!
-8% (,h!%>9:G$%% (,>9:G2%(
>!"%67(GK>^G% (,$>CG"%!!

P% (,N-Vk!!>rG2%I-$%!>rG8
i$%>^G>CG"%>rG/d2h!i% (,>rG=28(
% (,R%%QT!"%$>9#G=
2O!N>99GO!l%8!%67(i>9#G/0$%% 
(,>99G2%I-$%8i$%>^G>CG>rG"%% P
I2h!8$% (,VN!>9G/d2h!1% (,>9:G
8(% (,R%%QT$'I!'(
% (,VN!-%h%% (,R%%Q*eT
!I8!*%I-$%!b8"%$% (,w!>9cG
$%*e8 =22i$%I=2V%
!%/pb8I$%i% (,>9cG8(()!l"%$% 
Quá trình alkyl hóa trang 15
(,w!>9FG$%lV%8b8I$%8(
R%%QT!"%$%67(>9`GO!l%
$%67(>x7(G/0$%% (,>9`G%67(8$
O!N>9CGl8V%!%/qVki>9`G8
-!>9DGT7(-Vki>9DG8-!
!$%>9rGTg!5/
c. Lò phản ứng
 }IVN!=(vN=Q.!R%%Q=.!
M!(!='P!Pkb8/
 A!%Q'(2;!'(7*%2
8!IVN!1[2e/
 A;!'(7*%8%e!% 
/A;!M!%PiN=*!!%
!8i$%M!.!R%%Q=%
(,$ +!8!8!(i%M!$
l%8/Af-v28(L-vQ%Q
=!T!%%T!IVN!/
 0!f%!%!2%  IVN!H!-vR%

!8!!%V!%Y&
Quá trình alkyl hóa trang 16
o •!R%%Q='%)+!(UgR%%Q/
o X%Q%Q,[.!R%%Q=+!`:aQ
R%%Q/
o y2=!8gi.!'xT!%V.%*%(,w!
'l%IVN!/
o X%Q% %Q'(Q.!*%8!/
o Xl%'!Ql%IVN!%T;%Q=
'(*%8.$%1O! %V
N!O!8T*V/
VI.2. Quá trình alkyl hóa sử dụng xúc tác HF
VI.2.1. Công nghệ dùng xúc tác HF của hãng Phillips
a. Nguyên lý hoạt động&
A!%Q34%%67(2% (,M>#G% *e
l%*epu81%-%*e%% (,VN!>9G/
d2-Vk<8(Tw!%=%67(>`G-V
k% (,$>cG-($%3>9G/y=
%67(-Vk-Vk<8=Z
c
>DG
=2!%Q% (,/t67(28i
$%% (,VN!/E=2puI8h%f
()!\@p8=%pu/A!f%;!Y.%l%7
(T pu/
b. Sơ đồ công nghệ
Quá trình alkyl hóa trang 17
Quá trình alkyl hóa trang 18
VI.2.2. Công nghệ sử dụng xúc tác HF của hãng UOP
/ Sơ đồ công nghệ

9/0% (,VN! #/0R, c/Z=[
F/0 `/Z=%pu
b. Nguyên lý làm việc :
A!%QZ
c
7Z
F 
8=l%67(28%
%U'I!% *el%pu!% (,VN!>9G/q(=YR
,>#GTpu8(i$%VN!/qVki% (,
R,>#G8=$[>cG/•-Vk
7(/E=8!h%'(,.3-ˆ8
i=F2$%I pu-ˆ% P8%i=`/
VI.3. So sánh quá trình alkyl hóa xúc tác HF và H
2
SO
4
Quá trình alkyl hóa trang 19
Loại xúc tác HF H
2
SO
4
9/pH!%  d%%-
•@d
q4'Z/
\3!!3
#/‘%T
oA%Q=VN!&#`…F:

Z

o0f%!%VN!!w

o?3h%
*e[
oZe‚ M%f!

o#…9:

Z
o?@A%
!%Q34%Z
F
o0< %67Z
F
~@34%h
o\M!2e‚g(%Q
 M%f!
c/Z<%
o0<QZ
`
o
~Z
F
o?@A~E@A
o0%*%
9r…#:
C`7CD~C#7Cc
::`…:9`(~O!
9r…#:
C`7Cr~C#…CF

#:…c:(~O!
F/y%U%QV
N!
- A%Q=V
N!
- z-
- 0<Q
%67Z
F

~34%
c:…F:

Z
D…^†~
#
^…9`
#…9:

Z
c…F†~
#
F…9#
Tài liệu tham khảo:
9/ ZM!!Q (% '2h7}X+p% 
#/ pS'2h[…y%0,A!S
c/ Z-’‚ !U/
-&~~“““/!!3//~”
-|•|–•|•3-|-•-3|“3(•'|D•3'|:Zunu–u•|aca#u
a#u-9/'“'%3%/3a#u4%3

a#u'“'4%3#a#u9C#a#u9F:#cDD/'*•3%|`sA*•7}j7
0'„pnZn•-!|un–ZA†j9\DEdrDpq:7
%}X-u!•-%!#|“:—?rCEn˜dDX4n
MỤC LỤC
Quá trình alkyl hóa trang 20
Lời mở đầu
Quá trình alkyl hóa trang 21