Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
23, 1973
T, HUTSON, _|R ET AL
Filed NOV. l1. 1971
3,767,726
Wwf/W '
ATTORNEYS
3,767,726
2
reaction system feedstock results in elimination of ethyl fluoride from the product stream, thus increasing the over all efliciency of the reaction system for desired alkylate
3,767,726
Thomas Hutson, Jr., and Cecil O. Carter, Bartlesville, Okla., assignors to Phillips Petroleum Company Filed Nov. 11, 1971, Ser. No. 197,835
Int. Cl. C07c 3/54 U.S. Cl. 260--683A2
ACID
product.
It is an object of this invention to provide a process for the alkylation of isoparaffin with an olefin. Further, it is
an object of this invention to provide an economical al
8 Claims
an alkylation promoter such as a higher olefin in a process 10 in which there is formed unavoidably an alkyl fluoride. It ABSTRACT OF THE DISCLOSURE is a still further object of this invention to provide an In the alkylation of an isoparaflin with an olefin in the alkylation process in which the alkyl fluoride is removed presence of hydrofluoric acid as catalyst wherein the total from the product stream with facility and returned to the feed stream is converted in part to alkyl fluoride, the reactor feed streams. Another object of the invention is alkylation reaction eflluent stream containing alkyl fluo to provide a process as described wherein internal recycle ride is contacted with liquid hydrogen fluoride which has streams are used to increase the efficiency of the process in been treated by countercurrent extraction with a stream
used to extract the alkyl fluoride from the alkylation re action eflluent stream and both the alkyl fluoride enriched butane stream and the alkyl fluoride enriched hydrogen fluoride stream are recycled to the alkylation reaction
efficiency of removal of alkyl fluoride from the alkylation reaction eflluent prior to fractionation of the reactor ef fluent. zone. Other aspects, concepts, objects, and the several advan tages of this invention are apparent from this disclosure, BACKGROUND OF THE INVENTION 25 the drawing, and the appended claims. This invention relates to alkylation. In one of its as SUMMARY OF THE INVENTION pects, it relates to the production of an alkylate by alkyla tion of an isoparaflin with an olefin employing hydrogen According to the present invention, in the alkylation of
fluoride 'as the catalyst. In another of its aspects, the in an isoparaflin with an olefin, eg., isobutane with ethylene, vention relates to an alkylation operation in which the 30 a higher olefin, eg., propylene, isobutylene, and mixtures
total alkylation feed stream contains alkyl fluoride, e.g., ethyl fluoride, or in which operation alkyl fluoride is pro duced. According to a concept of this invention, hydrofluoric
alkyl fluoride, for example, ethyl fluoride or alkylate range fluorides, from an alkylation reactor eflluent is subjected
acid supplied as the extraction medium for removal of
to a prior countercurrent extraction with a predominantly
thereof, wherein there is formed unavoidably an alkyl uoride, eg., ethyl fluoride, there is provided a process which comprises treating the effluent from the alkylation
reaction to separate the eflluent into an alkylate contain
tion with a hydrofluoric acid stream, producing a recycle isobutane stream to increase the efficiency of the hydro isobutane stream by fractionation of the alkyl fluoride fluoric acid as extracting agent for the alkyl fluoride. In 40 free hydrocarbon stream, extracting at least part of the
fluoride.
extracting agent to produce the hydrofluoric acid stream used for extraction of th'e hydrocarbon phase, and re cycling the alkyl fluoride containing extractants to the re 45 action zone. The drawing is a diagrammatic representation of an alkylation operation according to this invention.
Referring now to the drawing, there are fed to the re
moter such as BF3 or higher olefins such as propylene, iso butylene, or mixtures thereof. In such an alkylation it is possible that from about 10 to about 2O weight percent or more of the ethylene will react to form ethyl fluoride.
It is known that higher concentrations of ethyl fluoride in the reaction mixture decrease the selectivity in the reaction for producing ethyl fluoride. The amount of ethyl fluoride
olefin used as an alkylation promoter, and make-up iso butane. As later described, these feeds, together with re cycle butane, are fed by line 4 to alkylation riser reactor 5. The reaction mass is passed to settler 16.
We have further conceived that recycle of both the ethyl fluoride enriched hydrofluoric acid from the extraction of the alkylation reactor eflluent and recycle of the ethyl
fluoride~ enriched isobutane contact stream for reuse as
fractionation for recovery of isobutanes, n-butane, alkylate product, propane, ethane, and residual hydrofluoric acid.
produced is, however, sufficient to cause a substantial 8 and cooler 9 to the riser reactor 5. The remaining por loss of feed and catalyst if the ethyl fluoride is not re tion 10 is fed into alkyl fluoride removal tower 11 where covered. it is brought into countercurrent contact with a predomi We have now conceived that the ethyl fluoride can be nantly preferably liquid isobutane recycle stream which 60 recovered more efliciently by extraction of the alkylation removes reaction products, particularly ethyl fluoride and reaction eflluent with hydrofluoric acid which has been alkylate range iluorides, from the hydrofluoric acid. Hy treated by countercurrent contact with a predominantly drofluoric acid of high purity is removed through 12, isobutane stream which produces a hydrofluoric acid which cooler 13, and line 14 to be mixed up with make-up hy can efliciently remove all of the ethyl fluoride from the re drofluoric acid of high purity and fed as extraction agent action eflluent before the reaction effluent is subjected to to extractor 1S. Here the hydrofluoric acid is brought into
settler 6 by 16 and passed to the extractor 15. Hydro fluoric acid now rich with ethyl fluoride and any alkylate range fluorides is removed through 17 and returned to the riser reactor 5.
A hydrofluoric acid phase is removed from settler 6 by 7. The stream is split with a portion returning through
liquid-liquid countercurrent contact with the hydrocarbon phase containing alkylate which has been removed from
3,767,726
ethyl fluoride has been removed exits extractor 15 through
Tons]
18 and is fed to the main fractionation column 19. From the fractionator 19 are removed an alkylate kettle product stream 20, a normal butane vapor side product stream from below the feed point 21, a recycle liquid lsobutane
. . . .
day percent
0.01 67. 20
0
Wt.
131015./
0
dey
side product stream from above the feed point via 22, and
hydro?luoric acid. The overhead product stream 23 is fur
29.98
2. 37 0. O3
0. 41
2 3, 222
2,176
5, 600
0
0
33
165 2
100. 00
0
pane 31 product streams, using HF stripper 35 as shown. The liquid recycle isobutane stream 22 is split -With a portion returning through 24 to conduit 4 and to the riser reactor 5. Another portion is returned through 24 and 15 exchange 25 (optional in some operations) as extracting agent for alkyl fluoride removal tower 11. After counter
current contact with the hydrouoric acid stream in tower
0. 08
1. l() 79. 84 6. 30
12. 68
Total ............................. __ 9, 598. 1 100. 00
115
11, the extract rich isohutane 1s returned through 26, cooler 27, and 28 to riser reactor 5. ln some operations of 20 tower 11, the isobutane 24 can be at least partly vaporized.
EXAMPLE
Tons]
10. 70
0. 87
0. 05
98. 1
5. 6
2,2-dimethylbutane 2,3-d1methylbutane
_ __
__
__
_______ _ _
4. 43 597. 88
16. 61
8. 24
0. 0
0. 0
(l. 62
143.9
70. 5
0
0
___________ __
day percent
29.51
Wt.
Bbls./
day 23
1. 35 0. 0 0. 0 0. 25
0. 74 0. 37
0. 11 0. 00 U. O0 0. 02
0. 06 G. 03
11. 4 0 0 2. 1
6. 1 3. 1
n-Butane_
Butenes. _
0. 30 0 0.45 01. 15 2. 57
6. 02
........ _
59 0 64 7, 90s 320
731
2,2,4-trimethy1pentane ______________ ._
396. 77
8. 36 13. 28
32. 26 3, 262. 9
30
2,2,3-trimethylpentane...
2,3,4-trirnethylpentane...
2,3,3-trirnethylpentane...
2,3-dimethylhexane _________________ ._ 2-methylheptene ____________________ -_ 3,4-dirnethylhexane ___________ __ 3-rnethylheptane_.___.. _______ __ 2,2,rtrirnethylhexane ..... __ Residue ____________________________ __
52. 16
15. 01 0. 0 2. 09 0. 0 0. 25 16. 48
77. 99
6. 52
0. 53
0. 68 1. O8
68. 5 107. 9
4. 24
. 34
408. 8
119. 9 0 16. 5 0 2. 0 148. 7
617. 0
51. 8
100.00
9,082
0.67
________ _
35
l. 22 0. 00 0. 17 0. 00 0. 02 1. 34
.
.
18. ss
0.14
0.19
1,12
114, 666
1,236
6,148
731
.
140.1 23. 4
59. 11
0. 2 0. 04
100.00
192, 164
800 139
.526,228
4. 9
32. 7
0. 1
37. 7
86. 7 4
0. 26
100. 00
320
1
371
71. 28
5. 74
22.63 201,333
27,245
0. 30
192, 164
800
__ __
___
0. 0 3. 8 O. 0
10 . 9
0 O. 04 0
1. 20
0 58 0
1,139
23. 4
0.05
139
91. 70 7. 0G
100. 00
100.00 421,686
5o
25, 827
132
22. 2
0. 05
_ _ __
1. 6 0 47. 1
276 9
0. 04 U 1. 20
91. 70
7. 06
24 0 532
36, 542
2, 710
_- _ 3, 596
100.00 400,864
7l. 28
22. 63
5.74
n-Butane ___________________________ _ _
9, 452
9, 903
1,340
55
100.00
0
39, 80S
o
519.9
131.9
1. 1
0. O5
Ethyl uorldePropane._-__
60
Isobutane _ n-Butane ________ __
Ethane__-.
479. 9 39. 4
_ __ 3, 673_ 9 __ 276. 9
1. 3
10. 73 0. 88
82. 14 6. 19
D. 03
9, 141 445
9
2()
100.00
20,740
1. 6
0. 03
1, 636
40
54
7
94. 2
2. 3
3. 1
0.1
9, 442
762
549
40
Total ____ __ ______________ _; _______ _- 4,473.0 100. 00 Ethane product (30) ____________________ __ 3.8 ________ __
Isobutane .................... _ _
Water ______________________ __
5. 7 ________ __
64
0
1,737
<0. 1
100.0
0
10,793
65
1,737
7. 7
Alkylate propert1es:
API gravity __________________________ __ 76
Ethylene ........................... __
Ethane.____
7. 7
.
4. 85
O. 08
1. 14
8, 889
1, 236
117
317
94.8
74. 53 6. 53 12.79
100.00
99, 580
Reactor conditions:
3,767,726
4:1 10:1
90
(2) separating said mixture into an alkylate-contain ing hydrocarbon phase and a hydrofluoric acid phase,
190
60
Alkylate yield:
98
2.72
after delineated, thereby transferring alkyl fluoride from said alkylate-containing hydrocarbon phase to
10
It has been observed, as stated before, that an increased amount of ethyl fluoride in the reactor retards the forma tion of more ethyl fluoride and that recycle of the ethyl iluoride to the reactor also increases the conversion of ethyl iluoride to alkylate so that an additional amount of
uoride,
acid phase separated from the reaction mixture there by transferring alkyl fluoride from said hydrofluoric
and
include isobutane and/or isopentane. The oleiins, in addi tion to the required ethylene, can include propylene, butylenes, amylenes, and hexenes, either alone or in 20
combination. The ranges of isoparaflins to olens in mole ratios can be about 1.5:1 up to about 20:1 or higher. The catalyst to hydrocarbon volume ratios can be about
1:1 to about 10:1.
(6) recycling said hydrouoric acid stream containing alkyl fluoride and the isoparain stream containing
25
separated from the reactor effluent thereby transferring than about 5 percent, and acid soluble oils. alkyl uoride from the hydrouoric acid phase to the 30 Reactor temperatures can be about 40 F. to about isobutane to obtain the trted hydrouoric acid stream 175 F. with pressures being suicient to maintain the
now preferred liquid phase system. The weight ratio of liquid hydrofluoric acid solvent to
used for extraction of the hydrocarbon phase and the iso butane containing extracted alkyl uoride is recycled to
the reaction zone.
3. A process according to claim 2 wherein the isoparain is isobutane which is passed as extraction agent in con tact with at least part of the hydrouoric acid phase
ethylene.
alkyl fluoride to the reaction zone. 2. A process according to claim 1 wherein olefin is
produces a normal butane stream, an alkylate product stream, and a stream containing ethane and propane. Although the invention has been described as being pri 5. The process according to claim 4 wherein the stream marily applicable and the now contemplated best mode 40 containing ethane and propane is further treated to re is as production of diisopropyl from isobutane and ethyl move residual hydrofluoric acid, said hydrofluoric acid ene reacted in the presence of a hydrouoric acid cata
art.
stream using a high purity hydrouoric acid produced 55 by stripping reaction product from the hydrouoric acid phase of the reactor product euent.
being recycled to the reaction zone. 6. The process according to claim 1 wherein at least promote an increased conversion of ethylene to alkylate. It will be obvious to one skilled in the art in possession 45 one higher olefin is present in the alkylation feed mixture as an alkylation promoter. of this disclosure having studied the same that the inven 7. A process according to claim 7 wherein the iso tion and its concepts can have other applications. parain is isobutane. Reasonable variation and modification are possible with 8. The process according to claim 6 wherein the higher in the scope of the foregoing disclosure, the drawing and the appended claims to the invention the essence of 50 ole?ins are chosen from the group consisting of propylene which is that alkyl fluoride can be effectively removed and isobutylene. from an alkylation reactor euent stream before fraction References Cited ation of the alkylate containing hydrocarbon portion of UNITED STATES PATENTS the reactor euent by the extraction of the hydrocarbon
lyst, it is known that an amount of a heavier oleiin will
3,073,878 3,204,010 1/1963 8/1965 Johnson _______ __. 260-683.48 Van P001 ______ __ 260-683.42
3,410,759>
11/1968
comprises:
We claim: DELBERT E. GANTZ, Primary Examiner 1. A process for the alkylation of an isoparafn with olen in the presence of a hydrouoric acid catalyst which 60 G. J. CRASANAKIS, Assistant Examiner
260-683.48