United States Patent Office 63.

2,872,304
Patented Feb. 3, 1959
3. i: , , , &-

2,872,304
ant. These are conventional expedients in the art, and
any other, type of odorizing equipment may also be en
- ODORIZED GAS AND METHOD FOR ODORIZNG ployed.
a pipe lineThe odorant
at the is about
rate of generally added to
0.2 pound to 3.0
the pounds
gas in
THE SAME 5 of odorant per million cubic feet of gas with the pre
: John L. Eaton, Whitemarsh, Pa., and George E. Hinds, ferred rate being about 1.5 pounds of odorant per million
Houston, Tex., assignors, by mesne assignments, to cubic feet of gas. - - - --
Pennsalt Chemicals Corporation, a corporation of The invention will be further illustrated by reference to
. . Pennsylvania the following specific examples:
No Drawing. Application December 23, 1953 0 EXAMPLE 1
Serial No. 400,098
18 Claims. (Cl. 48-195)
Preparation of tertiary butyl ethylsulfide
A two gallon autoclave was charged with 1261 grams
This invention relates to alkylthioethers containing at l8 ES SE"SE yap A. Earl5. of
--- - ... 0, 8 - butw. tan, 4.72

least one tertiary EEE and relates also to the sodium hydroxide dissolved in 2308 grams of water, this
ust these Eas as gas f SA fracti fliqui- being the calculated amount of water to yield a saturated
atural gas, the propal and butane re ions S. t qu d salt solution if the reaction goes to completion. The re
ified petroleum gases, and some types of manufacture 20 agents were chilled before charging and the autoclave was
gases possess practically no inherent odor, and odoriza rapidly closed after charging was completed. The auto
tion of these gases, so that they will be detectable at clave was then heated, with continuous agitation, to a
low concentrations in the atmosphere, has been practiced temperature of 150° C. in 45 minutes, maintained at a
for many years. i. In the gas, industry, it is standard prac- temperature of 150° C. for 15 minutes, rapidly cooled,
tice to add a controlled amount of a strongly odoriferous 25 and
material to act as a warning agent in the case of a gas
discharged, using conventional precautions to avoid
loss of volatile components. .
leak, and many States have laws requiring that gas be After distilling of unreacted ethyl chloride, the oil
odorized to a specified minimum level as a safety measure. ... layer was steam distilled, dried azeotropically, and frac
Adequate odorization is not only a safety measure but tionally distilled. Ethyl chloride and mercaptain heads
results also in substantial economies since pipe line leaks, 30 were removed and 1511 grams of product were obtained
which may amount in the aggregate to considerable gas as a cut boiling at 119 to 119.5 C.
loss, may be promptly detected and repaired. Also, these
leaks would not be detected if the gas were not odorized. EXAMPLE 2.
Gas odorants in current use belong to the general cate- a ---4--- - -
gory either of mercaptains or organic sulfides. Odorants 35 Preparation of tertiary butyl isopropy sulfide
in either category may be pure compounds or mixtures, A two gallon autoclave was charged with 910 grams
and may be used in concentrated form or diluted with
relatively inodorous materials. Mercaptains have a higher
ofride,tertiary butyl mercaptan, 800 grams of isopropylchlo
and a solution of 450 grams of sodium hydroxide in
odor intensity but are easily oxidized by traces of oxygen 2850 grams of water, The autoclave was heated to a
in a pipe line to relatively inodorous disulfides. Organic 40 temperature of 126 C. in 40 minutes and was held at a
sulfides are of lower odor intensity than mercaptains, but temperature of 125 to 135° C. for 70 minutes, during
are stable to pipeline oxidative conditions so that, if which time the pressure varied between 80 and 100
added to the gas in sufficient amount, the odor will be P.S. l. g. The autoclave was cooled to a temperature of
transmitted unimpaired over long distances. 25 C. and discharged. 1,580 grams of crude oil layer
An odorant of acceptable quality should be harmless
and neither toxic nor nauseating, non-corrosive, chemi-
as were recovered haying a specific gravity of 0.840.
The Engler distillation of this layer was as follows:
cally inactive, insoluble in water, inexpensive and readily °C. C.
available, burn completely without harmful or odorous IBP--------------- 370 60---------------- 55
products of combustion, be stable and not adsorbed by 1----------------- 39.0 70---------------- 64
mains or meters, and should possess a penetrating odor 50 5------------ 40 80---------------- 98
similar to the artificial gas smell. 10---------------- 42 90---------------- 132
In accordance with the present invention, alkylthio- 20---------------- 43.5 95---------------- 135
ethers containing a tertiary alkyl group are used as sulfide- 30---------------- 45 FBP--------------. 141
type odorants, possessing the oxidation stability common 40---------------- 48 Recov------------- 97
to thioethers and possessing a higher odor intensity than 55 50-----------
other alkyl thioethers. -- - -
'50.5 -

Among the compounds which are useful as odorants in 1163 grams of neutral crude product were fractionally
accordance with the invention may be mentioned tertiary distilled. After removing unreacted isopropyl chloride and
1. 3 u. and
butyl, methyl, ethyl, propyl, and isopropyl sulfides, .. .. tertiary
errrrry butyl
1, mercaptan,
reus, 142.5 grams
haili ofoftertiarybutyl
12 or ; , a
tertiary amyl, methyl, ethyl, propyl, and isopropyl sul- 60 isopropyl sulfide were recovered, boiling at 132° C. and
fides. Other compounds of this type may also be em- having a specific gravity of 0.815.
ployed, the alkyl chain length being limited only by the : EXAMPLE.3
vapor pressure of the compounds, i. e., the compounds a.
must have a vapor pressure sufficiently high that the com- Preparation of tertiary amyl ethyl sulfide
pound may be vaporized into the gas stream in a pipe line 65 A two gallon autoclave was charged with 1050 grams
in amount sufficient for adequate odorization. It is also (10.1 mols) of tertiary amyl mercaptan, 450 grams (11.2
essential that a tertiary carbon atom be directly linked to mols) of sodium hydroxide, and 660 grams (10.2 mols)
the sulfur atom. of ethyl chloride in 2000 grams of water. The auto
In practice, odorization is usually effected by means of clave was then heated, while subjecting the mixture to
an injection type odorizer in which the odorant is pumped 70 agitation. The temperature was maintained at 130 to
into the gas stream and vaporized, or a metered portion 140° C. for two hours, during which time the pressure
of gas is passed over a wick and saturated with the odor- varied from 80 to 100 p.s. i.g. The autoclave was
 2,872,304
3.
cooled to 24 C. (pressure 5 p.s. i.g.), vented, and dis
charged. 1,482 grams of oil layer, and 2,646 grams of Threshold, Ibs1109 C. F.
saline solution were obtained. Titration of the water
layer indicated that 77.5% of the total sodium hydroxide Odorant Observer A. Observer B
had been consumed. The crude oil layer had a specific
gravity of 0.831 and the Engler distillation of this layer order as
listed
order order as order
reversed listed reversed
was as follows:
o C. tert-BuSET----------------- 0.55 0.3 0. A 0.2
60 -------------- 136.0 tert-Ann SET.--------- 1.5 0.65 0.2 0.3
70 -------------- 143.5 Mixed AnSMe-------------- 2.7 1, 1 2.4 0.4
80 -------------- 148
90 15 It will be obvious to those skilled in the art that many
modifications may be made within the scope of the pres
ent invention without departing from the spirit thereof,
5 and the invention includes all such modifications.
We claim:
1. A method of odorizing a gas which comprises mix
1110.5 grams of crude product were fractionally dis ing the gas to be odorized with a compound having the
tilled, and after distilling off the unreacted mercaptain 20
structure
and ethyl chloride, 465 grams of tertiary amyl ethyl sul R-S-R.
fide were recovered as a clear colorless liquid boiling in which R is selected from the group consisting of tert
at 146 to 148.5 C. and having a specific gravity of butyl and tert-amyl radicals and R1 is selected from the
0.840. group consisting of methyl, ethyl, propyl, and isopropyl
EXAMPLE 4 radicals.
A room test procedure was used to estimate odor 2. A method of odorizing a gas which comprises mix
thresholds of various materials. The test consisted of ing the gas to be odorized with a compound having the
structure
the vaporization of successive increments of a dilute eth R-S-R.
anolic solution of the odorant to be evaluated into a
nitrogen stream which was passed at a uniform rate into 30 in which R is a tert-butyl radical and R1 is selected
an electric fan which circulated the odor throughout a from the group consisting of methyl, ethyl, propyl, and
closed room, the exact time of each injection being re isopropyl radicals.
corded. This room had a volume of 1233 cubic feet. 3. A method of odorizing a gas which comprises mix
A panel or six observers was seated at random in the room ing the gas to be odorized with a compound having the
prior to the start of the test, in clear view of a clock. Structure
At the end of the test, each observer independently re R-S-R.
corded the earliest time at which odor had become ap in which R is a tert-amyl radical and R is selected from
parent to him. The odorant concentration in the room the group consisting of methyl, ethyl, propyl and iso
at any given time was calculated from the known injec propyl radicals.
tion schedule of the odorant solution and thus the thresh 40 4. A method of odorizing a gas which comprises mix
old concentration for each observer was determined. ing the gas to be odorized with a compound having the
As shown by the following table, tertiary butyl ethyl Structure
sulfide was rated as stronger than mixed lower alkyl R-S-CH-CH3
ethyl sulfides by three of the five observers, with one ob
server considering the intensities equal and one consider in which R is selected from the group consisting of tert
ing the tertiary butyl ethyl sulfide as weaker. Four out butyl and tert-amyl radicals.
of the six observers considered tertiary butyl methyl 5. A method of odorizing a gas which comprises mix
sulfide as equal to the corresponding ethyl sulfide, with ing the gas to be odorized with a compound having the
one rating the methyl homologue stronger and one rating Structure
it weaker: R-S-CH
in which R is selected from the group consisting of tert
TABLE butyl and tert-amyl radicals.
6. A method of odorizing a gas which comprises mix
Threshold value, lbs./108 C. F. ing the gas to be odorized with a compound having the
55 structure

Odorant
Observer Average R-S-CH-CH-CH
faint definite
in which R is selected from the group consisting of tert
F percep- percep butyl and tert-amyl radicals.
tion tion 60 7. A method of odorizing a gas which comprises mix
ing the gas to be odorized with a compound having the
Me-tert-BuS.------- 0. Structure
Et-tert-BuiS---------
Mixed lower alkyl
ethylsulfides.
8 : CE

One observer fails to detect at indicated level.

Two observers fail to detect at indicated level.
Comparisons between tert-BuSET, tert-AmSET, and
mixed amylmethyl sulfides were made, using an apparatus
which presents, to the nose of the observer, a definitely
known concentration of odorant in gas-air mixture. The
tests, as originally conducted, were duplicated two days
later, but with the order of presentation of the odorants
reversed, to cancel out any effect the order of presenta
tion may have on the observations.
65 R-S-E-h
C
in which R is selected from the group consisting of tert
butyl and tert-amyl radicals.
8. A method of odorizing a gas which comprises mix
70 ing the gas to be odorized with tert-butyl ethyl sulfide.
9. A method of odorizing a gas which comprises mix
ing the gas to be odorized with tert-butyl methyl sulfide.
10. A method of odorizing a gas which comprises mix
ing the gas to be odorized with tert-butyl isopropyl sul
75 fide.
 2,872,304
5 6
11. A method of odorizing a gas which comprises mix
ing the gas to be odorized with tert-butyl propyl sulfide.
12. A method of odorizing a gas which comprises mix
ing the gas to be odorized with tert-amyl ethyl sulfide.
13. A method of odorizing a gas which comprises mix
ing the gas to be odorized with an alkyl thioether having
a tertiary carbon atom linked to the sulfur atom and
having a vapor pressure sufficiently high that the con
pound may be vaporized into a gas stream in a pipe
line in amount sufficient for adequate odorization.
14. A method of odorizing a gas which comprises mix
ing the said gas with an alkylthioether having a tertiary
carbon atom linked to the sulphur atom and having a
vapor pressure sufficiently high that the compound may
be vaporized into the said gas, the said thioether being
present at a concentration of 0.2 to 3 pounds per million
cubic feet of gas.
15. An odorized gas comprising a major proportion
of a member of the class consisting of natural gas, man
ufactured gas and mixtures thereof, and a minor pro
portion of an alkyl thioether having a tertiary carbon
atom linked to the sulphur atom, said thioether being
present at a concentration of 0.2 to 3 pounds per million
cubic feet of gas.
16. An odorized gas comprising a major proportion
of a member of the class consisting of natural gas, man
ufactured gas, and mixtures thereof, and a minor pro
portion of an organic sulfide having the structure
in which R is selected from the group consisting of tert
butyl and tert-amyl radicals and R1 is selected from the
group consisting of methyl, ethyl, propyl, and isopropyl
radicals, said organic sulfide being present at a concen
tration of 0.2 to 3 pounds per million cubic feet of gas.
17. An odorized gas comprising a major proportion
of a member of the class consisting of natural gas, man
ufactured gas and mixtures thereof, and a minor pro
portion of an organic sulfide having the structure
in which R is a tert-butyl radical and R1 is selected from
the group consisting of methyl, ethyl, propyl, and iso
propyl radicals, said organic sulfide being present at a
concentration of 0.2 to 3 pounds per million cubic feet
of gas.
18. An odorized gas comprising a major proportion
of a member of the class consisting of natural gas, man
ufactured gas and mixtures thereof, and a minor pro
portion of an organic sulfide having the structure
in which R is a tert-amyl radical and R1 is selected from
the group consisting of methyl, ethyl, propyl and iso
propyl radicals, said organic sulfide being present in the
20 gas mixture at a concentration of 0.2 to 3 pounds per
million cubic feet of gas.
References Cited in the file of this patent
UNITED STATES PATENTS
25 1944,175 Frey ------------------ Jan. 23, 1934
2,001,715 Fisher ----------------- May 21, 1935
OTHER REFERENCES
“Warning Agents for Methyl Chloride in Refrigeration
30 Systems.” The Roessler and Hasslacher Chem. Co., 10
East 40th St., New York, N.Y. (1930), pp. 30, 31.
Vogel et al.: "Chemical Society Journal,” 1943, pages
16-24. wo
“Warning Agents for Fuel Gases,” Fieldner et al.,
35 Bureau of Mines, page 17.