close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3039261

код для вставки
3,039,251
United States Patent 0
Patented June 19, 1962
2
1
(e) 3,4 - dimethyltetrahydrothiophene -l,1- dioxide (de~
rived from 2,3-dimethylbutadiene sulfone), B. Pt.
3 039 251
274°—275° 0/760 mm.
PRODUCTS AND PROCESS’ FOR PURIFYING GASES
Jonas Kamlet, New York, N.Y., assignor to El Paso Nat
Methods for the synthesis of these compounds are de
scribed by Backer iand Bolt, Rec. Trav. Chem. 54, 538
44 (1935); de Roy and van Zuydewijn, Rec. Trav. Chem.
ural Gas Products Company, El Paso, Tex., a corpora
tion of Texas
No Drawing. Filed Oct. 2, 1959, Ser. No. 843,914
15 Claims. (Cl. 55—29)
57, 445-455 (1938); Farlow) (to du Pont), US. Pat
ent 2,233,999 (1941); I. G. Farbenindustrie, French Pat
ent 847,254 (1939); Evans, Morris and Shokal (to Shell),
This invention relates to a series of products and a
process for the purifying of gases. More particularly, 10 US. Patents 2,360,859 to 2,360,862 (1944); Morris and
Van Winkle (to Shell), US. Patent 2,435,404 (1948),
this invention relates to a series of products and a proc
and elsewhere.
ess for the joint and simultaneous removal of Water, hy
drogen sul?de, mercaptans and carbon dioxide from nat
For simplicity,'the compounds above described will be
referred to in this speci?cation by the following abbre
ural and synthetic gas and gas mixtures, such as nat
‘,1,‘I,1~
ural gas, petroleum and gasoline re?nery gases, coal 15
gas, water gas, synthesis gas, producer gas, coke oven
gas, pipeline gases, et cetera. These gases consist essen
vi-ations:
_
THTD-tetrahy-drothiophene- l , l -dioxide
3-MTHTD—-3-methyltetrahydrothiophene-1,l-dioxide
2-MTHTD-2-methyltetrahydrothiophene-1,l-dioxide
tially of hydrocarbons, hydrogen, carbon monoxide, ni
trogen and mixtures thereof.
2,5-DiMTI-ITD—2,5 - dimethyltetrahydrothiophene-1,1-di
A tremendous technology has developed and many
ox de
‘
hundreds of patents have issued to the present time, de
3,4-DMTHTD——3,4 - dimethyltetrahydrothiophene-l,l-di
scribing a multiplicity of products and processes which
oxide
e?ect the dehydration of such gases, the removal of hy
The presence of water, water vapor or moisture in
drogen sul?de, the removal of mercaptans and the re
moval of carbon dioxide therefrom. In almost all cases, 25 many gases, especially such gases as are transported
through pipelines over considerable distances (such as
individual reagents and usually separate treating proc
natural gas, pipeline gas, etc.) is highly undesirable.
esses are required to elfect these results.
There is a tendency for crystalline hydrates to form with
The basis of my invention is the ?nding that simultane
ous removal of water (i.e. dehydration), removal of hy 30 some of the components of said gases, which may clog
or ‘otherwise inhibit the free ?ow of the gases. In addi
drogen sul?de, removal of mercaptans and removal of
tion, the higher the moisture content of said gases, the
carbon dioxide from gases may be eifected by contacting
greater will be the corrosivity of these gases on the ex
said gases with at least one member of the group of
compounds of the general formula:
V 1135
posed metallic parts of the pipeline.
The tetrahydrothiophene-1,1-dioxide and the homo
logues thereof, above described, are highlyhygrosc'opic
and will effectively remove the moisture content of gases
with which these agents are contacted. Typical vapor
pressures of such compounds may be given by the fol
lowing table.
will)
TABLE I
where R, R’, R" and R’” are members of the group
consisting of hydrogen and methyl.
Compounds of this type are readily prepared by the
hydrogenation of the sulfones obtained by the reaction
of conjugated drenes of composition
'
Vapor Pressures of TH TD
Temperature, °C.
.145
Pressure-mm. Hg
120 __________________________________ __
156
__
17-3
_
,
>
30
-
50
194 _
210 _
with sulfur dioxide. Typical members of this group of
composition, suitable for use in the process of this in-.
.50
vention are
(a) Tetrahydrothiophene-l,l-dioxide (derived from bu
223
100
15.0
_____
_
230
133° C. at 6 mm. Hg, 290 C. at 760 mm. Hg.
(c) 2 - methyltetrahydrothiophene -1,1- dioxide (derived
from piperylene sulfone), B. Pt. 279‘?—280° 0/760 60
mm.
(d) 2,5 - dimethyltetrahydrothiophene -1,1- dioxide (de
rived from hexadiene-2,4 sulfone), B. Pt. 278°-280°
C./ 760 mm.
198
~ 201
The boiling points of typical mixtures of such com
pounds and water may be given by the following table.
tadiene sulfone), M. Pt. 26°, B. Pt. 110° C. at 3 mm.
Hg, 285° C. at-760 mm. Hg.
55
(b) 3 - methyltetrahydrothiophene-1,1- dioxide (derived
from isoprene sulfone), M. Pt; minus 5° C., B. Pt.
20
TABLE II
Boiling Point of Aqueous Solutions of TH TD at 664 mm.
Percent water by volume:
Boiling Point
, s
‘_____
15 _
30
-_
142.2
108.4
_
____
100.0
This demonstrates the relative ease with which such so~
lutions, after having absorbed water from gases with
3,039,251
3
4
which they have been contacted, can be regenerated by
distilling off the said water.
The technic of gas dehydration by the use of liquid
absorbents for moisture is very well known. As a rule,
TABLE v
{Absorption of HZS in THTD at 664 mm. Hg at 80° F.
concentrated ‘solutions of said liquid absorbents are
passed countercurrent to the gas being dried down
Gaseous rnl.
H28 absorbed
per liquid
ml. THTD
Percent H18 in nitrogen
through the contractor, and then through a heat exchange
unit to a regenerator where the water removed from the
gas is distilled o?, usually under reduced pressure.
The performance of the tetrahydrothiophene-1,1-diox
ide absorbents of this invention may be judged by the
depression of the dew points of a typical natural gas
treated by the well known procedure of the art. The
following table describes the result observed in the treat
ment of a wet natural gas, at diiferent pressures.
15
Absorption of H28 in 3-MTHTD at 760 mm. Hg at 80° F.
TABLE HI
Absorbent
Contact
Pressure,
Wet
Gas,
p.s.i.g.
° F.
Absorbent Dew Point
Rate,
GalJlb.
Depres
sion,
Water
° F.
20
5.0-
1. 07
25.0. _
Content
500
500
500
750
1, 000
00
500
500
86
82
84
86
86
85
86
86
3. 2
6. 4
9. 0
6. 4
6. 4
o. 4
6. 4
(i. 4
62
72
84
71
78
70
69
71
500
85
6. 4 .
70
25
3. 80
50.0__
__
7.20
100.0-
___
14. 10
The absorption of hydrogen sul?de by typical tetra
hydrothiophene-l,l-dioxide compounds of this series was
also determined at advanced pressures, using mixtures of
H28 and nitrogen. The following results were obtained.
30
It is. not intended in any way to limit this invention in
any manner to a speci?c procedure for the dehydration
of gases by the compounds above described, or of regen
Dioxide
Test N o ___________________ __
quired for pipeline transmission. Such a gas can be pro
duced ‘with a 65° F. dew'point depression under the con
ditions given in the following table.
TABLE VI
Absorption of Hydrogen Sul?de by Tetrahydrothioplzene
erating the said absorbent solutions. Any of’the technics
well known in the art may be employed. As a rule, the
use of these compounds, in concentrations between 95.0%
and 99.5% by weight, at contact temperatures with the
gases of fromv 50° F. to 110° F. will produce dew point
depressions of between. 45° F. and 105° F.
A 7 lb. gas (ie a gas containing not more than 7 lbs.
of water per million standard cubic feet) is usually re
45
_;_
80
6010____________________________________ __
88
800’
93
_.__
1000-
__ __ _
_ _ _ i __
1400; _________________________________ __
104
4
5
704. 3
723. 5
759. 8
146. 8
81.0
38. 7
12. 25
50
762. 9
5. 91
100
84. 74
'Calc. HzS‘p.s.i.a., 60° F ____ ..
282. 7
158. 2
85. 4
43. 2
absorption ______________ __
705.4
694.1
727.0
816. 4
sorption (Cale) _________ __
147. 0
93.1
49. 5
12. 2
sorption (Tutweiler) .... _.
19. 5
11.9
7.17
3. 41
90
57
45
18
H28 p.s_.i.a., 60° F., after ab
Moles Has/mole THTD by
123
70
52
13
0.362
0. 228
0.180
0. 074
0.282
. 0.207
0.053
776. 9
0.95
100
S66. 4
858. 5
0. 45v
2.6
,
mole percent ____________ __
0. 495
0.010
The tetrahydrothiophene-l,l-dioxide compounds of this
97
1200“. _________________________________ __ 102
3
21. 50
70
759. 2
ml.
Hrs absorbed/m1.
'I‘HTD by gage _________ __
ml.
H25
absorbed/n11.
Contact temperature, ° F.
TH’I‘D by mole ercent...
.
68 50 Moles Hi8 lmoleT TD by
gage _____________________ __
400 ___________________________________ __
2
90
841.1
Mole percent HzS after ab
200
1
ler)
ml. THTD-_
Cale. Total p.s.l.a., 60° F
Total p.s_.i.a., 60° F., after
TABLE IV
Absorber pressure, p.s.i.a.:
Gaseous ml.
HES absorbed
per liquid
m1. 3-MTI-ITD
Percent HiS in methane
55 invention ‘are also excellent agents for the removal of
mercaptans from gases. The following table describes
the mercaptan absorbing capacity of a typical compound
After the» gas hasbeen dehydrated to. the-required ex
of this group. A gas mixture of methyl mercaptan in
tent-,- it may be freed of its water content by any of the
nitrogen . was employed.
well known procedures-of the art, e.g. by distilling off the 60
water ‘at', atmospheric pressure, or by vacuum regenera
TABLE VI-I
7 tion (eg. by, distilling oif the water under reduced pres
sures of 50 to 400 mm. Hg).
Technics for the dehydration of gases by liquid mois
ture; absorbents are. described in. detail in thereport on 65
“Gas Puri?cation” appearing in Chemical Engineering
for June 15, 1959, and in the- Proceedings of the Gas
Conditioning Conference for 1957 (University of Okla
homa)‘.
'
The tetrahydrothiophene-l,l-dioxide compounds'of this
QHBSH Content
in nitrogen per
100 s.c.f.
Pressure,
p.s.i.a.
Absorbent
CHzSE
Content
Ca aeity of
after Absorption,
grams
ml. meroap
tan per ml.
liquid
Alijsorbent
absorbent
70
12.58 grams ______ ._
967
THTD _ __
5. 32
0.08
14.10 grams ______ __
84
THTD--.
3.15
0. 06
invention are also excellent agents for the removal of
The ability of the tetrahydrothiopheneil,l-dioxide com
hydrogen sul?de from gases. The following table de
pounds of this invention to remove carbon dioxide from
scribes the absorption of hydrogen sul?de in a typical
gas streams may be judged by the results reported in the
compound of this series.
75 following table:
3,039,251
TABLE VIII
Absorption of Carbon Dioxide by Tetrahydrothiophene
Dioxide
TestNo __________________________________________ __‘1
Total p.s.i.a. before TH’l‘D _______________________ ._
002, p.s.i.a. before THTD____
Mole percent 004 ___________ __
2
3
4
5
718.7
26.4
719.1
42.6
710.5
84.9
716.7
156.3
701.1
205.6
708.3
258.1
737.1
381.9
682.9
533.1
3.2
5.8
11.0
21.4
28.4
37.2
52.9
80.5
86.0
100.00
801.5
100. 00
802.0
100.00
792.4
100.00
799.3
100. 00
781.9
100. 00
789.9
100. 00
822.1
100.00
751.1
100. 00
1,075.2
_
M1. THTD Added08.10. Total p.s.i.a__
__
6171819
964.1
781.9
Cale. 004115.15 _______________ __
29.4
47.5
94.7
174.3
229.3
287.
425.9
594 5
872.0
Total p.s.i.a. After Absorption"
780.6
790.5
771.2
763.4
743.9
742.1
731.9
660.1
944.9
002 p.s.i.a. After Absorption ______ __
Mole percent 002 After Absorption_ __
M1. Cozabsorbed/ml. THTD by gage,
Ml. C02 absorbed/ml. THTD by mole
Moles Col/H1016 'l‘H’l‘D by gage _____ __
14.5
2. 5
8.8
3.5
0. 035
36.0
4. 5
6.8
6.5
0.027
73.5
9.1
12.5
10.0
0.010
138.4
18.0
21.2
19.8
0.085
191.3
24. 3
22.4
24.4
0.090
240.0
32.1
28.2
32.8
0.113
335.7
48. O
53.2
49.4
0.213
493.0
76. 7
59.9
62.9
0.240
741.7
82. 2
70.9
87.3
0.308
0.014
0.026
0.040
0.079
0.098
0.131
0.198
0.252
0.350
_
-
Moles Cos/mole THTD by Mole perce
All pressures are at 60° 13‘.
All volumes are at 60° 1?‘. and 760 mm. Hg.
The internal volume of the absorption vessel was 967.6 ml.
Mole percent C09, determined by gas analysis (Orsat).
In all cases, the homologous compounds of the series
of this invention, i.e. THTD, 3-MTI-1TD, Z-MTHTD, 2,5DMTHTD and 3,4-DMTI-ITD exhibit closely similar solu-
vention, 15% of diethanolamine and 5% of water. The
flow rate of the inlet gas was 800 s.c.f. per hour and the
treating solution ?ow rate was about 1.0 gal./ min. The
bilities for hydrogen sul?de, methyl mercaptan and other
inlet gas contained 9.2% carbon dioxide and 2.6% of hy
mercaptans and carbon dioxide, and are almost equally as 25 drogen sul?de. The treated gas analyzed as follows:
e?icient in the removal of water and the depression of the
dew 901m of Sand sases-
,
00.,
It should be understood that the tetrahydrothiophene-l,
Absorbent
His grains
Dew Point
Percent Per 100 59f.
Deiguiwvn.
l-dioxide and its homologues may be used by themselves,
.
or in admixture with each other, in the puri?cation of 30
THTD _____ -_
gases. These may 'also be used in con1u11ct1on
w1th‘ other.
'
‘
3_MTHTD__
M
L6
go
2-MTHTD- _ __
4. 7
0. 9
84
agents now extensively employed in the pur1?cat1on of
gases, such as diethylene glycol, triethylene glycol, propylene carbonate, monocthanolamine, diethanolamine, N
2, 5_DMTHTD__
3, 4_DMTHTD__
50
5_ 0
L3
1,0
70
72
ti n mus b egplgefla teh i .f ‘.3 Prof 11° 5 0 1S mven'
9d may 6 fste or me P n ymg O gazes over efvery
was contacted with the various tetrahydrothiophene-l,1
dioxide compounds of this invention, in each case ‘as ‘99%
,
.
.
.
.
rnethyldiethanolamine, alkazid (alpha aminoproprionic 35
acildt) et fitera'
. t d th t th
d t f th. .
'
4.4
1.2
76
EXAMPLE 111
A natural gas, at a contact pressure of about 800 p.s.i.g.
a‘. e ratnget O dean??? .ltrii’. pressuzfa's 3.“ composl lonts‘ 40 vsolutions with 1% of water. The flow rate of the inlet gas
‘ Is no .12 in a 0t Hm tls mvmt ion In any manner?o
was 800 8.0.1:‘. per hour and the treating solution ?ow rate
any specnc emp-vr? ure gr empera‘ure raggc; any $11891 P
was about 1.0 gal./rnir1. The inlet gas contained 8.8%
Pressure 01 range 0 pres lires or an’, SP 601 C ‘33.15’ coinposl'
carbon dioxide and 1.4% of hydrogen sul?de. The treated
tion of gas or concentration
. .
. of components in sand gas.
.
. gas
analyzed as follows..
The products of this invention may be used for the pun
fying of gases under all of the conditions heretofore em
ployed with other agents for the removal of moisture, ‘15
dehydration, removal of hydrogen sul?de, mercaptans
CO2,
Absorbent
msgmms
and carbon dioxide from said gases.
1
Dew Point
Percent Per 100 s-c-f. Depggjgsion,
'
The following
examples
given to de?ne
to il
h.
.
.
b_ are
1.
. and
.
.ustrate t is inyentlon 1 ut in no way_to 1m1t it to re-
,
THTD _______________________ __
5.6
2.0
84
344111111)
5_9
12
80
agents, proport1ons or conditions described there1n. Ob- 50 g-g/IS‘HTD“
~vious modi?cations and improvements will occur to per-
g-g
3;4_DMTHTD _______________ __
:SOHS skilled in the art.
_
EXAMPLE I
_.5j1__
3%
214
8'0
-
The above gas also contained 11.2 grains per 100 s.c.f.
A natural gas containing 8.2% carbon dioxide and 55 of organically bound sulfur, as methyl mercaptan, ethyl
4.8% hydrogen sul?de (by volume) was contacted at a
mercaptan, etc. Under the above conditions, the treated
?ow rate of 7.5 cu. ft. per hour with the following compounds of this invention, the latter at a ?ow rate of 1.0
gal. per hour. The results obtained were as follows:
Outlet
Gas,OO2.
Absorbent
gas was freed of its organically bound sulfur to the fol
lowing extents:
60
Organic S Content,
Hts-grains Dew Point
per 100 s.c.f. Depression,
percent
Absorbent
THTD _
THTD _________________________ __
3-MTH'J‘D
_
2. 1
3. 4
4. 2
5. 0
84
78
‘
65
2-M'I‘H’1‘D ____ __
.
2.9
7.1
80
2, 5—DM'1‘HTD___
-
3. 6
6. 0
68
3, 4-DM‘1‘HTD ______________ _.
2. 8
5.8
72
15%
0.1
2.9
80
monoethanolamine
20g£iTD1i
1
85%
807 THTD
20 ‘7%N-Methylethanolaniine 80 %
riet
ano amine
_
0 1
0.1
.
grains per 100 s.c.f.,
Ef?uent
° F.
3 0
2.6
.
75
81
3'MTHTD-
_ _ . _ . _ _ _ _ _
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ._
3.8
3-1/1’1‘111‘1)
2-M’I‘HTD-..
4. 0
2. 9
5-DMTH’I‘D-
4.2
3,4-DMTH’I‘D-
__________________ ._
3. 8
EXAMPLE IV
A Synthesis gas made from coal, analyzing about 6.5%
,
.
70 carbon dioxide, 32.5% hydrogen, 50.5% carbon monoxide
and 3.5% nitrogen, was contacted at an ‘absorber pressure
EXAMPLE II
of about 300 p.s.i.g. with the various tetrahydrothiophene
A natural gas, at a contact pressure of about 750
p.s.ig. was contacted with a mixture of 80% of the vari-
1,1-di0xide compounds of this invention, at the rate of
2.0 gals. of absorbent per 100 s.c.f. of the raw gas at a
oustetrahydrothiophene-1,1~dioxide compounds of this in- 75 temperature of 95° F.
3,039,251
7
8
The feed gas contained 450 grains/ 100 s.c.f. of hydro
8. A process for the removal of hydrogen sul?de‘ and
carbon dioxide from gases of the class consisting essentially of hydrocarbons, hydrogen, carbon monoxide, nitro—>
gen sul?de. The treated gas analyzed as follows:
Absorbent
H2S~grains
gen and mixtures thereof containing the same, comprisingv
0 02, Percent
per 100 cu. ft.
contacting said gases with an absorbent containing at‘
least one member of the group of compounds consisting
TH’I‘D __________________________________ _ _
45
3. 4
3-MTHTD___
52
3. 8
2-M THTD ____ _.
50
3. 1
2,5»D MTHTD...
48
3. 6
3,4-DMTHTD _____ __
52
3. 2
of tetrahydrothiophene-l,l-dioxide, 3-methyltetrahydro-l
thiophene-1,1-dioxide, 2 - methyltetrahydrothiophene-1,1
dioxide, 2,5-dimethyltetrahydrothiophene-1, l-dioxide and‘
3,4-dimethyltetrahydrothiophene-1,1—dioxide.
10
9. The process of claim 8 wherein said gases are con-
Having described my invention, what I claim and desire
to protect by Letters Patent is:
tacted with said ‘absorbent at substantially atmospheric
temperature.
-
l. A process for the simultaneous removal of hydrogen
sul?de, water, carbon dioxide and mercapt-ans from gases
10. The process of claim 8 wherein said gases are syn
of the class consisting essentially of hydrocarbons, hydro
thesis gases containing hydrogen and carbon monoxide
gen, carbon monoxide, nitrogen and mixtures thereof con
taining the same as impurities, comprising: contacting said
hydrocarbon-containing gases.
gases with an absorbent containing at least one member of
contain moisture and the moisture content is reduced by
11. The process of claim v8 wherein said gases are
12. The process of claim 8 wherein said gases also
the group of compounds consisting of tetrahydrothio
contacting with said absorbent.
phene - 1,1 - dioxide, 3 - methyltetrahydrothiophene - 1,1
1:3,, The process of claim 8 wherein said absorbent also
fcont?'ains an ethanolamine selected from the group‘ con»
dioxide, 2 - methyltetr-ahydrotlriiophene - 1,1 - dioxide, 2,5- 5
dimethyltetrahydrothiophene - 1,1 - dioxide and 3,4 - di
methyltetrahydrothiophene-1,1-dioxide.
sisting of monoethanolamine, diethanolamine, triethanol
'
ne and N-methyl derivatives of ethanolamine and di
2. The process of claim 1 wherein said'absorbent also _
contains an ethanolamine.
3. The process of claim 1 wherein said absorbent also
contains an =a1kylene glycol.
'
,
4. The process of‘claim 1 wherein said absorbent also ;.
5. The process of claim 1 wherein said absorbent also
4. A process for the treatment of a wet hydrocarbon
gas containing hydrogen sul?de and carbon dioxide as im
pnrities to place said gas in condition for transportation
through pipe lines over a considerable distance, comprising
‘
contains propylene carbonate.
contains ~alpha~amino propionic acid.
hanolamine.
1 contacting said gas with an adsorbent containing at least
.
6. A process ‘for the removal of hydrogen sul?de from
one member of the group consisting of tetrahydrothio
, phene-Ll-dioxide, 3-methyltetrahydrothiophene-1,1-diox
gases of the class consisting essentially of hydrocarbons,
ide, Z-methyltetrahydrothiophene-1,1~dioxide, 2,5 -di
hydrogen, carbon monoxide, nitrogen and mixtures thereof 35 me'thyltetrahydrothiophene-1,l-dioxide and 3,4-dimethyl
containing same, comprising contacting said gases with an
v tetrahydrothiophene-l,l-dioxide to remove hydrogen sul~
Y ?de and carbon dioxide to reduce the moisture content
compounds consisting of tetrahydrothiophene-1,1-dioxide,
of said gas below about seven pounds per million cubic
3 - methyltetrahydrothiophene - 1,1 - dioxide, ‘ 2 - methyl
feet.
tetrahydrothiophene - 1,1 - dioxide, 72,5 - dimethyltetra
15. The process of claim 14 wherein said Wet gas is
40,
hydrothiophene - 1,1 -'dioxide and 3,4 - dimethyltetra
natural gas.
absorbent containing at least one member of the group of
hydrothiophene-Ll-dioxide.
7. A process for the removal of carbon dioxide from
gases of the class consisting essentially of hydrocarbons,
hydrogen, carbon monoxide, nitrogen ‘and mixtures there- 45
of containing same, comprising contacting said gases with .
an absorbent containing at least one member of the group
of compounds consisting of tetrahydrothiophene-1,1-di
oxide, 3 - methyltetrahydrothiophene - 1,1 - dioxide, 2
methyltetrahydrothiophene - 1,1 - dioxide, 2,5 - ‘dimethyl
tetrahydrothiophene - 1,1 - dioxide and 3,4 - d-irnethyltetra
hydrothiophene-l,ledioxide.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,177,068
2,360,861
,Hutchinson ___________ __ Oct. 24, 1939
Pierotti et al ___________ __ Oct. 24, 1944
2,385,704
Hooker et al __________ __ Sept. 25, 1945
FOREIGN PATENTS
728,444
Great Britain _________ __ Apr. 20, 1955
Документ
Категория
Без категории
Просмотров
0
Размер файла
547 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа