US006789288B2

(12) United States Patent (10) Patent N0.: US 6,789,288 B2

Wij mans et al. (45) Date of Patent: Sep. 14, 2004

(54) NATURAL GAS DEHYDRATION PROCESS 5,141,536 A 8/1992 Schievelbein et al. ...... .. 55/208
AND APPARATUS 5,182,022 A 1/1993 Pasternak et al. ......... .. 210/638
5,209,762 A 5/1993 Lowell . . . . . . . . . . . . . . . . . .. 55/31

Inventors: Johannes G. Wijmans, Menlo Park, 5,234,552 A 8/1993 McGreW et al. ............ .. 203/18
(75) 5,350,519 A 9/1994 Kaschemekat et al. 210/640
CA (US); Alvin Ng, Palo Alto, CA 5,415,681 A * 5/1995 Baker .......................... .. 95/45
(US); Anurag P. Mairal, Fremont, CA 5,453,114 A 9/1995 Ebeling .......... .. 95/166
(Us) 5,490,873 A 2/1996 Behrens et al. 95/160
5,552,023 A 9/1996 Zhou .............. .. 203/18
(73) Assignee: Membrane Technology and Research, 5,554,286 A 9/1996 Okamoto et al. . 210/500
Inc., Menlo Park, CA (US) 5,643,421 A 7/1997 Smith ............. .. . 203/12
5,681,433 A * 10/1997 Friesen et al. 203/39
Notice: Subject to any disclaimer, the term of this 5,725,636 A 3/1998 Gavlin et al. ............... .. 95/231
patent is extended or adjusted under 35 5,766,423 A 6/1998 Smith ........................ .. 203/12
U.S.C. 154(b) by 47 days. 5,772,734 A * 6/1998 Baker et al. .... .. 95/42
5,788,745 A 8/1998 Hahn ............. .. .. . 95/231
5,964,923 A * 10/1999 Lokhandwala .... .. 95/50
(21) Appl. No.: 10/280,147 6,159,542 A 12/2000 Kondo et al. ............. .. 427/245
6,306,197 B1 * 10/2001 Boyce et al. .................. .. 95/9
(22) Filed: Oct. 25, 2002
6,387,269 B1 5/2002 Eltner et al. .... .. 210/640
(65) Prior Publication Data 6,666,906 B2 * 12/2003 Hallman .. ... ... ...

2003/0233934 A1 * 12/2003 Wijmans et al. ............. .. 95/46

. . . . .. 95/52

US 2004/0079228 A1 Apr. 29, 2004

OTHER PUBLICATIONS
(51) Int. Cl.7 .................... .. ........................ .. B01D 53/14
J. Caro et al., Zeolite membranesstate of their develop
(52) US. Cl. .................... .. ....... .. 15/188; 95/46; 95/206;
ment and perspective, Microporous and Mesoporous Mate
95/231
(58) Field of Search ....... .. ..................... .. 95/45, 46,52,
rials, 38, p. 324 (2000).
95/156, 188,206,231; 96/234, 240, 4, * cited by examiner
6
Primary ExaminerDuane S. Smith
(56) References Cited (74) Attorney, Agent, or FirmJ. Farrant
U.S. PATENT DOCUMENTS (57) ABSTRACT
3,651,617 A * 3/1972 Hodgson ................... .. 95/188 Aprocess and corresponding apparatus for dehydrating gas,
3,720,717 A 3/1973 Cox et al. ................. .. 260/593 especially natural gas. The process includes an absorption
4,405,409 A 9/1983 Tusel et al. ............... .. 202/200 step and a membrane pervaporation step to regenerate the
4,755,299 A 7/1988 Bruschke ..... . . . .. 210/640
liquid sorbent.
4,772,295 A * 9/1988 Kato et al. ...... . . . . . . .. 95/50

4,802,988 A 2/1989 Bartels et al. .. .. 210/640

4,857,078 A * 8/1989 Watler ......................... .. 95/50 38 Claims, 9 Drawing Sheets

203

2" 210 220

216

201 Q 208
207

217

202 V

206
U.S. Patent Sep. 14, 2004 Sheet 1 0f 9 US 6,789,288 B2

101

107

108

FIG. 1
U.S. Patent Sep. 14, 2004 Sheet 2 0f 9 US 6,789,288 B2

203

2 210 220
201 207

2(18 217
202 1

219 214 y 206

FIG. 2
U.S. Patent Sep. 14, 2004 Sheet 3 0f 9 US 6,789,288 B2

400
_ 15o-155c

300

Water
flux 20;) _
(9Im2'h) 13o-13ac

100

l l

0 1 2 3 4 5 6
Feed water concentration (wt%)

FIG. 3
U.S. Patent Sep. 14, 2004 Sheet 4 0f 9 US 6,789,288 B2

50

40 -

Vapor 30 -
pressure
normalized ' Oa
water 20 L F '
flux . ' ' .
(glmbh'psid)
10 ~

0 l l a l l l

125 130 135 140 145 150 155 160

Feed temperature (C)

FIG. 4
U.S. Patent Sep. 14, 2004 Sheet 5 0f 9 US 6,789,288 B2

50

40 ~

Vapor 30 _
pressure- .
normalized ' ' I
water 20 _ .
flux ' . .
(g I m2~h~psid)
10 -

0 l l 1 l |
0 1 2 3 4 5 6
Water concentration (wt%)

FIG. 5
U.S. Patent Sep. 14, 2004 Sheet 6 0f 9 US 6,789,288 B2

27C

Natural gas
water
dew point
(0)

-500.1 . L......|1 . 10 100

Water concentration in lean TEG (wt%)

FIG. 6
U.S. Patent Sep. 14, 2004 Sheet 7 0f 9 US 6,789,288 B2

Feed
water vapor
pressure

0.1 1 10
Water concentration in feed TEG (wt%)

FIG. 7
U.S. Patent Sep. 14, 2004 Sheet 8 0f 9 US 6,789,288 B2

10:

Natural gas
1 :- pressure (psia)
Membrane area -
per MMscfd
natural gas _
treated _ 500
2
(m lMMscfd) 1,000
0-1 7 1,500

Q_01 l | l l
0 20 40 60 80 100
Natural gas water dewpoint reduction (C)

FIG. 8
U.S. Patent Sep. 14, 2004 Sheet 9 0f 9 US 6,789,288 B2

10 I

1 .- Pervaporation
Membrane area temperature
per MMscfd - (0c)
natural gas
treated
(m2 / MMscfd) 200
220
0-1 g 240

0.01 ' 1 ' '

o 20 40 so so 100
Natural gas water dewpoint reduction (C)

FIG. 9
 US 6,789,288 B2
1 2
NATURAL GAS DEHYDRATION PROCESS is a packed or multi-tray toWer, With the stripping gas
AND APPARATUS normally ?oWing upWard countercurrent to the descending
liquid glycol. Depending on the stripping agent used, Water,
This invention Was made in part With Government sup hydrocarbons, or both are absorbed from the glycol into the
port under SBIR award number DE-FG03-01ER83272, stripping gas, thus regenerating the glycol for reuse in
awarded by the Department of Energy. The Government has dehydrating the natural gas.
certain rights in this invention. US. Pat. No. 5,643,421, to OPC Engineering, describes a
glycol regeneration process comprising ?ash evaporation to
FIELD OF THE INVENTION recover hydrocarbon components from the spent glycol,
10
folloWed by heating and multiple stripping steps using a
The invention is a process and apparatus for dehydrating vaporiZed solvent as the stripping agent to dehydrate the
gas, such as natural gas. The process uses an absorption glycol. US. Pat. No. 5,766,423, also to OPC Engineering,
system to dehydrate the gas, and a membrane pervaporation uses basically the same process, but includes condensation
unit to regenerate the Water-laden desiccant. of a portion of the once-stripped glycol stream for additional
removal of hydrocarbons.
BACKGROUND OF THE INVENTION 15
US. Pat. No. 5,490,873, to Bryan Research and
Natural gas as obtained from the Well contains Water Engineering, combines condensation of the reboiler over
vapor. Before the gas can be passed to the pipeline, it must
head With further treatment of the lean glycol stream by
stripping against a sidestream of the dehydrated natural gas.
be dried to prevent problems such as hydrate or ice forma
US. Pat. No. 5,453,114, to Ebeling, uses a stripping step to
tion or corrosion. 20 remove hydrocarbons upstream of the glycol reboiler. US.
Glycol dehydration, Which is simple and inexpensive, is Pat. No. 5,209,762, to Gas Research Institute, uses an
currently the most Widely used method of dehydrating integrated combination of condensation and steam stripping
natural gas. The estimated number of glycol dehydration to produce dischargeable Water, organic liquid and an
systems operating in the United States alone is at least organic vent gas that may be useful as fuel.
55,000. 25 US. Pat. No. 5,725,636, also to Gas Research Institute,
In a typical dehydrator, Wet gas is scrubbed With dry adds potassium salts to the glycol to increase Water absorp
glycol to yield a product gas of loWered Water deW point. tion and decrease hydrocarbon absorption in the natural gas
The glycol absorbs not only Water, but also aromatic dehydration step. Since hydrocarbons are less readily
compounds, such as BTEX, and other hydrocarbon vapors. absorbed, the glycol has greater Water-absorbing capacity.
30 The regeneration process also produces a leaner glycol
The Water-rich or spent glycol is passed to a regenera stream and the Water vapor vented to the atmosphere has a
tion system, Which typically includes a ?ash tank, Where loWer hydrocarbon content.
methane and other light gases are ?ashed off, a reboiler and These and other processes can achieve loW Water con
a regeneration still column. The Water-laden glycol is heated centrations in the glycol, Which in turn provides good
to drive off absorbed Water, and dry glycol is recovered for dehydration of the raW gas, resulting in loW deW points in the
35
reuse in the absorber. Unfortunately, this heating also vapor treated gas. They can also reduce, but do not eliminate,
iZes hydrocarbons that have been sorbed into the glycol, and BTEX and other HAP air emissions through the additional
these are expelled, along With the Water vapor, in the hot treatment step. HoWever, most of these processes produce an
overhead vent stream from the still column. additional gaseous or aqueous Waste stream that requires
Although the major component is steam, this overhead 40
on-site or off-site attention such as incineration, disposal, or
vent stream may contain as much as 20 mol % or more of further treatment.
organic compounds, including aromatic and non-aromatic Despite these efforts, a cost-effective regeneration tech
organic vapors. Of these organic compounds, a signi?cant nology that truly minimiZes or eliminates HAP emissions
proportion may be the aromatic compounds benZene, has not been developed. There yet remains a need for such
toluene, ethylbenZene and xylene, together commonly 45 a process.
knoWn as BTEX compounds. These organic emissions are Membranes have for many years been knoWn to be usable
noW classi?ed as HaZardous Air Pollutants (HAPs), and are in pervaporation mode for dehydrating organic liquids. For
subject to emissions regulations both in the United States example, many patents to GFT and others, such as US. Pat.
and internationally. Nos. 3,720,717, 4,405,409 and 4,755,299, describe such
There is, therefore, a need for a simple, reliable and 50 separations using polyvinyl alcohol (PVA) membranes.
cost-effective method to reduce or eliminate the release of A large number of patents to Texaco also disclose per
these organic components. vaporation processes using membranes of various types for
So-called enhanced regeneration systems have been dehydrating organic liquids, such as organic acids. In
used to increase Water removal from the spent glycol, and particular, US. Pat. No. 4,802,988 describes PVA mem
some of these systems can reduce HAP emissions. For 55 branes and processes for treating ethylene glycol/Water
example, US. Pat. No. 5,141,536, to Texaco, describes an solutions to reduce the ethylene glycol content in the per
apparatus With a condenser unit in the reboiler overhead vent meate to loW levels, and US. Pat. No. 5,182,022 describes
to condense hydrocarbon components and some Water, thus a similar process using ion-exchange type sulfonated poly
venting a hydrocarbon-depleted Water vapor stream. US. ethylene membranes to produce a loW-glycol permeate.
Pat. No. 5,234,552 describes a condensation system to 60 US. Pat. No. 5,552,023, to Allied Signal, describes a
recover liquid hydrocarbons and collect remaining hydro process to treat spent deicing ?uid (ethylene glycol mixture)
carbon vapors for use as fuel for the glycol reboiler. US. Pat. using a combination of membrane distillation through a
No. 5,788,745, to Phillips Petroleum, describes the use of porous polytetra?uoroethylene membrane and reverse
both a condenser and a phase separator to recover liquid osmosis. US. Pat. No. 5,554,286, to Mitsui Engineering,
hydrocarbons. 65 describes an A-Zeolite-type membrane for pervaporation
Another technique for glycol regeneration is stripping applications, and includes sample data for dehydration of
against a gas or steam. A typical con?guration for a stripper alcohols.
 US 6,789,288 B2
3 4
US. Pat. No. 5,350,519, to Membrane Technology and This partial pressure difference may be provided in any
Research, describes a process including a condenser to convenient manner, such as by one or more of heating the
condense the glycol reboiler overhead vent stream and feed, cooling the permeate, draWing a partial vacuum on the
recover liquid hydrocarbon components, folloWed by a permeate side, and providing a gas sWeep on the permeate
pervaporation step of the Waste aqueous stream to recover side. It is preferred either simply to heat the feed liquid, thus
additional hydrocarbon components and vent a raising the Water vapor pressure on the feed side of the
hydrocarbon-depleted Water stream. membrane, or to both heat the feed and use a sWeep gas on
the permeate side.
SUMMARY OF THE INVENTION The membrane separation unit may contain any type of
10
membrane capable of selectively passing Water and rejecting
The invention is a process and apparatus for dehydrating the desiccant When operated in pervaporation mode. For
gas, especially, but not necessarily, natural gas. The process example, polymeric membranes or inorganic membranes
uses absorption into a liquid desiccant to dehydrate the gas, may be used. A most preferred membrane is a composite
and pervaporation to regenerate the Water-laden desiccant. membrane having a ceramic support coated With a selective
The pervaporation step can both regenerate the desiccant layer of a Zeolite or silica.
15 The Water concentration in the desiccant stream that
and capture any haZardous organic components that may be
present in a single step. forms the membrane feed may be any value. HoWever, the
Water content Will normally be substantially less than 50 Wt
In a basic embodiment, the process of the invention %, and usually Will be no more than about 20 Wt %, and
includes the folloWing steps: typically might be betWeen about 5 Wt % and 10 Wt %.
(a) subjecting a gas stream containing Water to an absorp The Water concentration in the membrane residue stream
tion step, comprising the steps of: should preferably be sufficiently loW that the desiccant can
(i) contacting the gas stream With a liquid desiccant in be reused in the absorption step Without additional Water
an absorber; removal treatment. Depending on the application, this usu
(ii) WithdraWing from the absorber a dehydrated gas ally means that the Water content of the residue stream
stream; 25 should be beloW 5 Wt %, and typically much loWer, for
(iii) WithdraWing from the absorber a spent desiccant example beloW 2 Wt %, 1 Wt %, 0.5 Wt % or less.
stream comprising desiccant and Water; and The process is particularly useful for treating natural gas
(b) subjecting the spent desiccant to a regeneration step, using glycol as the desiccant. In a typical glycol absorption
comprising: process, lean glycol is contacted With natural gas in a
(i) providing a membrane unit containing a membrane counter-current column. The glycol absorbs Water from the
having a feed side and a permeate side and exhibiting Wet gas. Organic compounds that are also present in the gas,
a pervaporation separation factor in favor of Water such as aliphatic hydrocarbons, and especially BTEX and
over the desiccant; other aromatic hydrocarbons, are soluble in the glycol
(ii) passing the spent desiccant into the membrane unit sorbent and are extracted With the Water.
and across the feed side under pervaporation condi 35 The spent glycol, laden With Water and containing the
tions; sorbed organic components, is heated and sent to the mem
(iii) providing a driving force for transmembrane per brane separation unit, Where it is passed across the surface
meation; of a membrane With a high separation factor in favor of
(iv) WithdraWing from the feed side a residue desiccant Water over organic compounds such as glycol and BTEX
stream depleted in Water compared With the spent 40 hydrocarbons. The vapor permeating the membrane is suf
desiccant stream; ?ciently free of such organic components to meet require
(v) WithdraWing from the permeate side a permeate ments for discharge to the environment.
stream comprising Water vapor. The residue stream, containing lean glycol, the BTEX
The most common desiccants are glycols, particularly aromatics and any other hydrocarbon components, may be
ethylene glycols. 45 recirculated to the absorption column.
The absorption step may be performed in any convenient Thus, in this typical, preferred embodiment relating to
manner that brings gas and desiccant into good partitioning natural gas, the process of the invention includes the fol
contact. Typically, but not necessarily, it is carried out in an loWing steps:
absorption column or toWer by ?oWing the gas stream to be (a) subjecting a natural gas stream to an absorption step,
dried upWard in counter-current contact With the doWn comprising the steps of:
?oWing liquid desiccant. In this case, the drier gas stream is (i) contacting the natural gas stream With glycol in an
WithdraWn from the top of the column and the Water-laden absorber;
liquid sorbent is WithdraWn from the bottom. As just one (ii) WithdraWing from the absorber a dehydrated natural
alternative to the traditional toWer, a membrane contactor gas stream;
can be used for the absorption step. (iii) WithdraWing from the absorber a Water-laden gly
The reduction in Water deW point of the gas achieved in col stream; and
the absorption step depends on the sorbent and the operating (b) subjecting the Water-laden glycol stream to a regen
conditions. DeW point reductions of at least about 40 C. or eration step, comprising:
more can normally be accomplished, and much greater (i) providing a membrane unit containing a membrane
reductions, such as 70 C. or more, are possible in many having a feed side and a permeate side and exhibiting
cases. a ?rst pervaporation separation factor in favor of
The membrane separation step is carried out in pervapo Water over glycol and a second pervaporation sepa
ration mode. That is, the membrane feed stream is in the ration factor in favor of Water over benZene;
liquid phase, the permeate is in the gas phase, and the (ii) heating the Water-laden glycol stream;
driving force is provided by maintaining a permeate partial 65 (iii) passing the heated Water-laden glycol stream into
pressure loWer than the feed saturation vapor pressure for the membrane unit and across the feed side under
permeating components. pervaporation conditions;
 US 6,789,288 B2
5 6
(iv) WithdraWing from the feed side a regenerated desiccant to be heated before entering the membrane
glycol stream; separation unit.
(v) WithdraWing from the permeate side a permeate
BRIEF DESCRIPTION OF THE DRAWINGS
stream comprising Water vapor;
(vi) recirculating at least a portion of the regenerated FIG. 1 is a schematic representation of a basic embodi
glycol stream to the absorption step. ment of the process of the invention.
In this case, the spent glycol that forms the membrane FIG. 2 is a schematic representation of a preferred
feed stream is typically heated to a temperature betWeen embodiment of the process of the invention, including heat
about 150 C. and 250 C., and the preferred membrane type integration and a permeate sWeep.
is an inorganic membrane, such as a silica membrane, that 10 FIG. 3 is a graph of Water ?ux of a silica membrane
can operate Without dif?culty at high temperatures. module as a function of feed Water concentration at tWo
By operating at such a feed temperature, and optionally temperatures.
passing a sWeep gas, such as air, to loWer the partial pressure FIG. 4 is a graph of Water ?ux of a silica membrane
of Water vapor on the permeate side, it is possible to reduce module as a function of feed temperature.
the Water content of the regenerated glycol to a loW level, 15
such as 1 Wt %, 0.5 Wt %, 0.2 Wt % or even less. Thus, the FIG. 5 is a graph of Water ?ux of a silica membrane
module as a function of feed Water concentration.
glycol that is returned to the absorption column is drier than
is the case When glycol is regenerated in a conventional FIG. 6 shoWs the relationship of Water deW point of
reboiler, Which typically reduces the Water content to no dehydrated natural gas as a function of initial feed Water
loWer than about 2 Wt %. 20 concentration in the dehydrating glycol at tWo temperatures.
The use of drier glycol in the absorption step means that FIG. 7 shoWs the equilibrium Water vapor pressure asso
the deW point of the treated natural gas can be reduced ciated With mixtures of Water in triethylene glycol (TEG) at
compared With conventional dehydration. The dehydrated different temperatures.
gas may have a Water deW point as loW as 20 C., 30 C. FIG. 8 is a graph of the membrane area required per
or loWer, for example. 25 MMscfd of natural gas treated as a function of the Water deW
Expressed as a reduction in deW point, the process of the point reduction at three natural gas pressures.
invention is able to achieve reductions of Water vapor deW FIG. 9 is a graph of the membrane area required per
point of as much as 50 C., 60 C., 70 C., 80 C. or even MMscfd of natural gas treated as a function of the Water deW
more. point reduction at three glycol regeneration temperatures.
The membranes provide high separation factors in favor 30
of Water over all organic components. Thus, the BTEX DETAILED DESCRIPTION OF THE
concentration in the Water vapor permeate stream is gener INVENTION
ally Well beloW 1,000 ppmv, and typically no more than The term gas as used herein means a gas or a vapor.
about 100 ppmv, and the glycol content is negligibly small, The terms organic vapor and organic compound as used
such as less than 50 ppmv. These loW levels enable dehy 35
herein include, but are not limited to, saturated and unsat
drators to operate so as to meet various requirements and urated compounds of hydrogen and carbon atoms in straight
regulations in many regions for HAPs emissions. Thus, in chain, branched chain and cyclic con?gurations, including
general, the permeate stream may be safely discharged to the aromatic con?gurations, as Well as compounds containing
atmosphere. oxygen, nitrogen, halogen or other atoms.
In a ?nal aspect, the invention is apparatus for carrying 40
The term BTEX as used herein means one or more of
out a dehydration process, and comprising the folloWing
elements: benZene, toluene, ethylbenZene and xylenes.
The terms desiccant and sorbent are used interchangeably
(a) an absorber, having a Wet gas inlet, a dehydrated gas herein, and refer to agents, usually organic agents, capable
outlet, a liquid desiccant inlet and a spent liquid des of dehydrating gas.
iccant outlet, and being adapted to bring Wet gas into 45
The invention is a process and apparatus for dehydrating
Water-partitioning contact With the liquid desiccant; gas. The process uses absorption into a liquid desiccant to
(b) a membrane separation unit, having a feed inlet, a feed dehydrate the gas, and pervaporation to regenerate the
outlet, and a permeate outlet, and containing an inor Water-laden desiccant.
ganic membrane having a feed side and a permeate The process may be used to treat any gas stream that may
50
side, and characteriZed by the ability to provide per be dehydrated by contact With a desiccant in liquid form.
vaporation separation factors of at least about 100 in
In basic form, the invention includes tWo unit
favor of Water over desiccant and in favor of Water over
benZene When used to treat a liquid desiccant stream
operationsthe dehydration step itself and a membrane
separation step for regenerating the desiccant. The invention
containing about 5 Wt % Water and 1 Wt % benZene at
55 in this form is illustrated in FIG. 1. It Will be appreciated by
200 C.; those of skill in the art that this and the other ?gures
(c) ?rst connection means connecting the membrane described beloW are very simple schematic diagrams,
separation unit feed inlet and the absorber spent liquid intended to make clear the key aspects of the invention, and
desiccant outlet, so that spent liquid desiccant may pass that an actual process train Will usually include many
out of the absorber and into the membrane separation 60 additional components of a standard type, such as
unit; compressors, heaters, chillers, condensers, pumps, bloWers,
(d) second connection means connecting the membrane other types of separation and/or fractionation equipment,
separation unit feed outlet and the liquid desiccant valves, sWitches, controllers, pressure-, temperature-, level-,
inlet, so that regenerated liquid desiccant may pass out and ?oW-measuring devices and the like. The considerations
of the membrane separation unit and into the absorber; 65 and criteria discussed beloW for FIG. 1 also apply to FIG. 2.
(e) heating means positioned betWeen the absorber and Turning noW to FIG. 1, Wet gas stream 101 enters
the membrane separation unit to enable spent liquid absorber 103. The absorber is typically a large tank, toWer
 US 6,789,288 B2
7 8
or column, usually equipped With perforated plates or has sometimes been used is cellulose acetate. Yet other
baffles. Gas stream 101 generally enters at the bottom of the dehydration membranes include chitosan membranes and
absorber and ?oWs upWards toWard the top. A liquid desic ion-exchange membranes, such as NAFION
cant stream, 102, is passed into the absorber, usually at the (polyper?uorosulfonic acid) membranes.
top. Any suitable desiccant, for example glycol, may be used Inorganic membranes comprising hydrophilic materials
Within the scope of the invention. may also be used as dehydration membranes. Such mem
The desiccant trickles doWnWard over the baffles in branes include amorphous silica membranes and membranes
countercurrent exchange With the up-?oWing gas. The des including a Water permeating Zeolite layer, such as ZSM-5.
iccant is chosen for its ability to sorb Water preferentially Zeolite membranes are described, for example, in J. Caro et
over the desired gas components of the gas stream, so that 10 al., Zeolite membranesstate of their development and
Water partitions preferentially into the desiccant. It is perspective, Microporous and Mesoporous Materials, Vol.
acceptable, if they are also present as impurities in the gas 38, 324, 2000, and in a number of patents, such as US. Pat.
stream, for organic compounds, for example aliphatic and Nos. 5,554,286; 6,159,542 and 6,387,269 to Mitsui Engi
aromatic hydrocarbons, to partition into the desiccant. Thus, neering.
a feature of the process is that it is not necessary to use a 15 Such membranes have been developed commercially, and
desiccant that is selective only for Water vapor. can be purchased from Mitsui and Company (USA) of NeW
The dry gas stream exits the absorber as stream 104, and York; Isotronics of Paradise Valley, AriZ.; SulZer Chemtech
may be passed to any destination. The amount of Water Membrane Systems, based in HeinitZ, Germany; and Per
vapor remaining in the dried gas depends on the operating vatech BV of Enter, The Netherlands.
conditions of the absorber and the initial Water content of the The membranes may be homogeneous, asymmetric, or
desiccant. If the Water content of the desiccant is at a loW composite membranes, or any other structure knoWn in the
level, such as 1 Wt %, 0.5 Wt %, 0.2 Wt %, or even less, as art, and may be formed as ?at sheets, holloW ?bers, tubes or
can be achieved by the pervaporation step, the absorption any other convenient form.
step Will be able to produce a dried gas stream that has a The pervaporation unit can include a single membrane
25
loWer deW point than can be achieved by conventional module or a bank or array of multiple membrane modules.
dehydration. The reduction in deW point that can be A single bank of membrane modules is usually adequate to
achieved by the process of the invention may be as much as meet the processing requirements for many applications. If
50 C., 60 C., 70 C., 80 C. or even more. additional processing is desirable, an array of modules in a
The Water-laden or spent desiccant solution, stream multistep or multistage con?guration With recycle of inter
105, is WithdraWn from the bottom of the absorber. mediate streams, as is knoWn in the art, may be used.
FIG. 1 and the above description describe the absorption Transport through the membrane is induced by maintain
step as it is carried out using the traditional absorption tank ing the vapor pressure on the permeate side of the membrane
or column. As mentioned in the Summary section, hoWever, loWer than the vapor pressure of the feed liquid. On the feed
the absorption step can be carried out in any convenient 35 side of the membrane, the partial vapor pressure of any
manner, and the scope of the invention is not limited to any component Will be the partial pressure of the vapor in
particular absorption means. As a non-limiting example, a equilibrium With the feed solution. Changing the hydrostatic
membrane contactor can be used. Such a contactor uses pressure of the feed solution thus has a rather small and
porous membranes to provide a large surface area interface usually negligible effect on transmembrane ?ux or selectiv
betWeen gas and sorbent liquid. Gas ?oWs across the mem 40
ity.
brane surface on the feed side, and is WithdraWn as a HoWever, the vapor pressure on the feed side is a function
dehydrated residue stream, corresponding to stream 104 in of the temperature of the feed solution. Heating stream 105
FIG. 1. Sorbent ?oWs on the permeate side of the membrane before passing it into pervaporation step 106 Will, therefore,
and is WithdraWn thence as a Water-laden desiccant stream, increase the driving force, and is preferred, as is discussed
corresponding to stream 105. The membranes may be in the 45 in more detail With respect to FIG. 2, beloW.
form of tubes, ?at sheets, or ?bers, and may be mounted in The permeate pressure also has a major effect on trans
any appropriate fashion. membrane ?ux. The vapor pressure of a component on the
Stream 105 is passed to membrane pervaporation step permeate side can be reduced in several Ways, for example,
106. Pervaporation is a loW-pressure membrane process that by draWing a vacuum on the permeate side of the membrane,
can be used to separate components of differing volatilities by sWeeping the permeate side to continuously remove
from solutions. The overall separation factor achieved is permeating vapor, or by cooling the permeate vapor stream
equal to the product of the separation achieved by evapo to induce condensation. These options are discussed in more
ration of the liquid and the separation achieved by selective detail in reference to FIG. 2.
permeation through the membrane. The membranes for use Water-vapor-enriched permeate stream 108 is WithdraWn
in the process of the invention may be of any kind that 55 from the permeate side of the membrane. Because the
results in adequate separation factors in favor of Water over membranes are relatively very impermeable to the desiccant
desiccant and in favor of Water over the volatile organic and many other aliphatic and aromatic organic components,
component, if such is present. By adequate separation the organic content of stream 108 is typically loW, such as in
factors, We mean separation factors of preferably at least the loW hundreds of ppmv level or beloW. This stream may
about 100. The membranes also exhibit transmembrane be discharged as vapor to the atmosphere, condensed and
vapor pressure-normaliZed Water ?uxes of, preferably, at discharged as liquid, or sent to any other chosen destination.
least about 10 g/m2~h~psid, more preferably at least about 15 The other stream exiting the pervaporation step is mem
g/m2~h-psid, and most preferably at least about 20 brane residue stream 107, Which is the Water-depleted liquid
g/m2~h~psid. desiccant stream, typically containing less than about 1 Wt %
For use as dehydration membranes, a number of suitable 65 Water. The loW permeability of the membranes to the des
materials are knoWn. Polyvinyl alcohol (PVA) is the most iccant and other volatile organic compounds means that
commonly used commercial material. Another polymer that these components are retained almost completely in the
 US 6,789,288 B2
9 10
residue stream. Stream 107 may be sent to any destination, cleaning out decomposition products), prior art processes
although, in many cases, it can be recirculated, in Whole or that use a reboiler to regenerate the desiccant are normally
part, for further use in the absorption step Without the need operated at temperatures no higher than about 200 C. Under
for additional Water removal treatment. these conditions, the regenerated lean glycol still contains
A particularly useful application is in natural gas about 2 Wt % Water. Even under optimum operating
dehydration, using glycol as desiccant. In the interests of conditions, the loWest Water deW points that can be achieved
clarity and simplicity, therefore, our process is described in the dehydrated gas stream by use of this type of glycol are
hereafter principally as it relates to using a glycol desiccant typically in the range 00 C. to 10 C.
to dehydrate natural gas. HoWever, this is not intended to Such deW points can also be reached Without dif?culty by
limit the scope of the process. Those of skill in the art Will 10 the process of the invention. HoWever, as discussed beloW,
readily appreciate hoW to apply the process of the invention the pervaporation regeneration step used in the present
using other sorbents and treating other types of gas streams process is able to achieve much loWer residual Water content
by folloWing the exemplary teachings speci?c to natural gas in the regenerated lean glycol, for example values such as 1
treatment that are given herein. Wt %, 0.5 Wt %, or 0.2 Wt %. Using this much drier glycol
Turning noW to FIG. 2, this shoWs a preferred embodi 15 as sorbent enables much loWer deW points to be obtained in
ment of the invention as it can be applied to natural gas stream 203. Therefore the Water deW point of stream 203 is
dehydration, and including heat integration and reuse of the typically 0 C. or beloW, and may be much loWer, such as
desiccant. In this case, Wet natural gas stream 201 enters 20 C., 40 C. or even loWer, such as 50 C. or beloW.
glycol absorber 211. Glycol absorbers are used nearly uni The Water-rich or spent glycol solution, stream 202, is
20 WithdraWn from the bottom of the absorber. If the raW gas
versally throughout gas production ?elds and are so Well
knoWn in the art as to need no lengthy description. Natural contains typical amounts of Water and BTEX, for example
gas arriving from one or many Wells enters the bottom of the on the order of 1,000 ppmv Water vapor and 200 ppmv
absorber and ?oWs upWards to the top. The Wet gas is BTEX, then the spent glycol typically contains on the order
usually introduced at the production pressure, typically of 5 Wt % Water and 1 Wt % BTEX.
25
betWeen about 50 psia and 2,000 psia, although the pressure Stream 202 is heated to the desired feed temperature for
may be reduced or increased if desired. Likewise, the gas the pervaporation step. In this regard, similar considerations
may be fed in at production temperature, or the temperature apply as for a conventional regeneration system reboiler.
may be adjusted if needed, such as by an air cooler, to bring That is, the stream should not be heated above the tempera
the gas to the desired temperature. Typically, a gas tempera ture at Which the glycol Will decompose. Thus, depending on
30
ture beloW about 50 C. is preferred. the properties, condition, and use history of the glycol, the
As mentioned above, the absorber is a large tank, toWer or upper limit for this temperature is usually around 250 C. or
column equipped With perforated plates or baffles. A liquid loWer, such as 220 C. or 200 C. HoWever, depending on
glycol desiccant stream, 210, is passed into the top of the other conditions in the pervaporation step, discussed later,
absorber. The glycol used should be reasonably stable loWer temperatures, such as 150 C. or even loWer, may be
35
against heat and chemical decomposition, and should have appropriate. As a general guideline, a temperature in the
a relatively loW vapor pressure. A commonly used glycol is range 150250 C. is most preferred.
triethylene glycol (TEG), Which is cheap, thermally stable In the preferred arrangement of FIG. 2, stream 202 is ?rst
up to about 200250 C. or above, and has good Water Warmed by running in heat-exchanging relationship against
sorption capability. Other glycols, for example monoethyl 40
stream 206 in any convenient type of heat exchanger, 212.
ene glycol (MEG), diethylene glycol (DEG) and tetraethyl Warmed stream 204 is then further heated in heater 213,
ene glycol (T4EG), are also used. To facilitate partitioning, again of any convenient type, to produce heated stream 205.
the glycol sorbent is typically introduced at a temperature a Heated stream 205 passes as a feed stream into membrane
feW degrees, such as about 5 C., Warmer than the incoming pervaporation unit 214, containing membranes 218. FeW
gas. 45 polymeric membrane materials are stable at the most pre
The desiccant trickles doWnWard over the baffles in ferred stream temperatures, that is, above 150 C. Therefore,
countercurrent exchange With the up-?oWing gas. Under the preferred membranes for natural gas dehydration pro
these conditions, Water partitions preferentially into the cesses are inorganic membranes, made from amorphous
more polar glycol. Typically the gas also contains aliphatic silica or hydrophilic Zeolite. The membranes are typically,
and aromatic volatile organic compounds, such as BTEX but not necessarily, in tubular form.
compounds, in amounts of a feW hundred ppmv. These The membranes typically exhibit high separation factors
compounds, and particularly aromatic BTEX compounds, of at least about 100 in favor of Water over glycol and in
are quite soluble in the glycol solution and partition readily favor of Water over benZene and all other BTEX compo
into the desiccant phase along With the Water. As Will be nents. Under typical process operating conditions, separa
discussed beloW, hoWever, this is not a problem as it has 55 tion factors much higher than this may be obtained, such as
been With prior art dehydrators. 500, 1,000 or more. The membranes also exhibit transmem
The dehydrated gas stream exits the absorber as stream brane vapor pressure-normaliZed Water ?uxes of, preferably,
203, and may be passed to a pipeline, to further treatment or at least about 10 g/m2~h~psid, more preferably at least about
to any other destination. 15 g/m2~h~psid, and most preferably at least about 20
The amount of Water vapor remaining in the dried gas 60 g/m2~h~psid.
depends on the operating conditions of the absorber, and, As is illustrated in the Examples section beloW, very little
importantly, the initial Water content of the desiccant. TEG membrane area is required to perform the pervaporation
and other popular desiccants are subject to thermal step. As a general guide, for every million scfd of raW gas
decomposition, Which occurs to a greater or lesser extent treated, the pervaporation step Will typically require less
depending upon the time/temperature history of the desic 65 than 1 m2 of membrane area, and sometimes much less, such
cant. To avoid decomposition of the desiccant (and hence as only 0.2 m2. Therefore, even though inorganic mem
increased operating costs for makeup desiccant and for branes tend to be expensive compared With polymeric
 US 6,789,288 B2
11 12
membranes, system costs are reasonable. High separation more than about 1 Wt %. The presence of BTEX at this level
factors also mean that a single membrane separation step can has no signi?cant effect on the Water sorption capability of
generally be used and this con?guration is preferred in this the glycol.
case. A multistep or multistage con?guration could be used Stream 206 is passed back to the absorption step by means
if additional processing capability is needed, but is usually of pump 215. As Was mentioned above, the preferred
not required. temperature for the glycol entering the absorption toWer is a
As discussed above, transport through the membrane is feW degrees above the gas temperature, and is preferably no
induced by maintaining the vapor pressure on the permeate higher than around 60 C. Therefore, the residue stream
side of the membrane loWer than the vapor pressure of the
should generally be cooled. This is done according to the
feed liquid. On the feed side, high partial pressure for Water
vapor is obtained by heating the feed stream. The permeate
10 preferred design of FIG. 2 by running stream 206 in heat
side of the membrane may be maintained at atmospheric eXchanging relationship With spent glycol stream 202 in heat
pressure. In this case, since the permeate is essentially pure eXchanger 212. Resulting cool stream 209 is further cooled,
Water vapor, the Water vapor pressure on that side Will be such as by air cooling, in cooler 216 and returned as cooled
about 15 psia. lean glycol stream 210 to the absorber.
15 FIG. 2 shoWs the glycol sorption/regeneration as occur
Depending on the temperature of the feed solution, the
driving force for Water vapor permeation Will thus disappear ring in a closed loop, that is With all of the spent glycol being
When the feed side Water vapor pressure has dropped to 15 regenerated and recirculated. It Will be appreciated by those
psia. For a feed stream heated to a temperature roughly of skill in the art that portions of glycol may be WithdraWn
betWeen about 150 C. and 200 C., for eXample, this point from the loop via purge means 219 or added to the loop via
of Zero driving force Will be reached When the glycol fresh liquid desiccant inlet 220 as desired to purge
concentration on the feed side has dropped to roughly contaminants, top up the system, and so on.
betWeen 1 Wt % and 4 Wt %. If a very loW deW point for the In another aspect, the invention includes the equipment,
dehydrated gas is not required, returning a regenerated system or apparatus for carrying out the disclosed dehydra
glycol stream that still contains a feW percent Water, as is tion processes. The invention in a most preferred form in this
25
done in many prior art systems, Will suf?ce. In this case, a aspect can be understood by reference again to FIG. 2.
Water vapor permeate stream Will simply be WithdraWn from The equipment comprises an absorber or absorption unit,
the pervaporation unit at atmospheric pressure. 211 and a pervaporation unit, 214. The absorption unit may
FIG. 2 assumes that a loWer deW point is desired, in Which take any convenient form, but is usually a tank, toWer or
case the Water content of the regenerated glycol must be column equipped With perforated plates or baffles. Other
reduced to a loWer level, such as beloW 1 Wt %. Therefore, types of absorption unit include membrane contactors, for
to loWer the Water vapor pressure on the permeate side, a eXample.
sWeep gas stream 207 is bloWn across the permeate side of Absorber 211 is equipped With a Wet gas inlet line, 201,
the membrane by bloWer 217. Air is a convenient and a dehydrated gas outlet line, 203, a liquid desiccant inlet
preferred sWeep gas, although nitrogen, natural gas, or any 35 line, 210, and a spent desiccant outlet line, 202. Inlet line
other gas that it is acceptable to vent, or for Which a 201 is normally positioned near the bottom of the column
subsequent use can be found, may be used. If air is used, it and outlet line 203 is normally positioned near the top of the
is not necessary to dry the air ?rst, since the partial pressure column. Conversely, inlet line 210 is normally positioned
of Water vapor in the air under normal conditions is less than near the top of the column and outlet line 202 is normally
0.3 psia. Likewise, if natural gas is used, it need not be dry, 40
positioned near the bottom. Thus, column 211 is adapted for
so a slipstream from Wet natural gas stream 201 may be used countercurrent ?oW betWeen gas and liquid, and to provide
as the sWeep gas. The natural gas sWeep stream, laden With Water-partitioning contact betWeen gas and liquid.
Water vapor, may then conveniently be used as boiler or Pervaporation unit, 214, is a membrane separation unit
heater fuel. Since the How of permeating Water vapor is equipped With a feed liquid inlet line, 205, a feed liquid
relatively small, the sWeep stream ?oW rate can be small 45 outlet line, 206, and a permeate vapor outlet line, 208.
also, generally, but not necessarily, on the same order as the Optionally, but not necessarily, the unit may also be
How of permeant gas. equipped With a permeate sWeep gas inlet line, 207.
The pervaporation step separates the feed stream 205 into Unit 214 contains one or more inorganic membranes, 218,
a liquid glycol residue stream, 206, and a Water vapor adapted to operate at temperatures above 1500 C. The
permeate stream 208. OWing to the high separation factor of inorganic membranes can be in any convenient form, such as
the membranes, the permeate stream usually contains only tubes, ?bers or sheets, and may be supported on a ceramic,
traces of BTEX, glycol and other organic components, in metal or other support structure, as Well knoWn in the art.
total usually less than 500 ppmv, and often loWer still, such The membranes themselves are hydrophilic, and preferably
as less than 200 ppmv, 100 ppmv, or even 50 ppmv. This comprise a silica or Zeolite layer, as discussed above With
stream may be discharged. 55 respect to the process embodiments.
Glycol residue stream 206 typically contains less than 1 The membranes are characteriZed by the ability to provide
Wt % Water, but is still laden With essentially all of the BTEX pervaporation separation factors of at least about 100 in
content that Was in the feed stream 205. When the process favor of Water over triethylene glycol and in favor of Water
is in operation therefore, the BTEX content of the circulating over benZene When used to treat a triethylene glycol stream
glycol increases until a steady state is reached, Where the containing about 5 Wt % Water and 1 Wt % benZene at 200
BTEX content of the glycol stream is in equilibrium With the C.
BTEX present in the natural gas stream. At this point, no As shoWn in FIG. 2, the equipment also includes an
additional BTEX is sorbed and the BTEX concentration of optional heat exchanger or heat-exchanging means, 212,
the dehydrated gas, stream 203, stabiliZes at the same level through Which spent liquid desiccant line 202/204 passes, so
as in the raW gas, stream 201, typically about 200 ppmv. 65 that spent liquid desiccant may pass out of the absorber and
Under typical process conditions, this results in an equi be Warmed by ?oWing via the heat eXchanger into line 204
librium BTEX concentration in the circulating glycol of no and thence to line 205 and into the membrane separation
 US 6,789,288 B2
13 14
unit. The heat exchanger is usually a simple shell-and-tube Enter, The Netherlands), containing 55 cm2 of membrane
unit, as Well known in the art, but can be any convenient type area. The silica module Was tested With triethylene glycol
of exchanger. mixtures containing 0.75.5 Wt % Water. The mixture also
Regenerated liquid desiccant line 206/209 also passes contained 0.5 Wt % hexane and 0.5 Wt % toluene. The ?rst
through optional heat exchanger 212, so that regenerated series of experiments Was carried out at about 130 C., the
liquid desiccant ?oWing from the pervaporation unit in line second set at about 150 C. The upper temperature Was the
206 can be cooled by ?oWing via the heat exchanger into limit of the test system, determined by the heat transfer
line 209 and thence to line 210 and back into the absorber. capacity available in the system. The feed ?oW rate Was 0.5
The equipment further includes liquid pump 215 in line gpm. A nitrogen sWeep at a How rate of 2.5 L/min Was
206 to pump regenerated desiccant back to the absorption 10 provided on the permeate side. The results of the experi
toWer. If a sWeep gas inlet line, 207, is provided, a pump or ments are shoWn in FIG. 3, Which plots the Water ?ux of the
membrane as a function of the feed Water concentration.
bloWer, 217, may also be provided to generate a How of
sWeep gas in line 207, across the permeate side of the In all experiments the permeate Was essentially pure Water
membranes and out via line 208. With hexane and toluene present in the loW ppm range. FIG.
15 3 shoWs that the ?ux increases With the Water concentration
Optionally, additional heating means, 213, and cooling
means, 216, may be provided. in the feed and With the feed temperature. HoWever, the
Water ?ux normaliZed for the Water vapor pressure differ
Heater 213 is positioned so that line 204 forms the inlet ential across the membrane is essentially constant at 22
line to the heater and line 205 forms the outlet line from the g/m2~h~psid, as shoWn in FIGS. 4 and 5, Which plot the vapor
heater. The heater itself may be of any type, such as a 20 pressure-normalized Water ?ux as a function of feed tem
gas-?red boiler, an electric heater, or a steam heater.
perature and Water concentration, respectively.
Cooling means, 216, is positioned so that line 209 forms
the inlet line to the cooler and line 210 forms the outlet line Example 3
from the cooler. The cooler itself may be of any type. Permeate samples Were collected during the silica mem
Usually, a simple air cooler Will suf?ce, but Water cooling or 25
brane pervaporation experiments of Example 2, and Were
any other cooling mechanism may be used if desired. analyZed for their hexane and toluene content by GC. The
Optionally, but not necessarily, a purging means, 219, very loW permeation rates of toluene and hexane made
may be added in line 202 (or elseWhere in the loop formed accurate measurements With our equipment dif?cult.
by the absorber, membrane separation unit, and connecting HoWever, representative data are shoWn in Table 2.
lines, as convenient) to enable removal of a portion of spent 30
liquid desiccant. Purging alloWs control of the volume of TABLE 2
contaminants or decomposed desiccant that may build up in
the desiccant recirculation loop. Optionally, but not Feed Equilibrium
necessarily, a fresh liquid desiccant inlet means, 220, may be Concen- Vapor Vapor Pressure
35 tration Pressure Permeate Normalized Flux
added in line 210 (or elseWhere in the loop formed by the Component (Wt %) (psia) Concentration (g/m2 - h - psid)
absorber, membrane separation unit, and connecting lines, as
convenient) to enable fresh liquid desiccant to be introduced Water 5.4 21.6 99.99+ Wt % 35
Triethylene 93.6 0.13 none detected
into the apparatus. Glycol
The invention is noW further described by the folloWing Toluene 0.5 1.5 18 ppmW 0.009
40 Hexane 0.5 8.7 22 ppmW 0.002
examples, Which are intended to be illustrative of the
invention, but are not intended to limit the scope or under
lying principles in any Way. The highest toluene concentration measured Was 50
EXAMPLES ppmW (ppm by Weight) and the highest hexane concentra
45 tion Was 30 ppmW; many samples contained signi?cantly
Example 1 less. Based on the highest concentrations measured at 157
C., the toluene pressure-normaliZed ?ux is on the order of
An experiment Was performed to determine the Water ?ux 10'2 g/m2~h~psid, and the n-hexane ?ux is on the order of
of a Zeolite membrane module (Mitsui USA, N.Y.), contain 10-3 g/m2~h~psid. These ?uxes are orders of magnitude
ing 70 cm2 of membrane area. The Zeolite module Was tested 50 loWer than the Water ?ux of 22 g/m2~h~psid, indicating that
at 100 C. With a triethylene glycol mixture containing 5 Wt the silica membrane Will signi?cantly reduce emissions of
% Water. A nitrogen sWeep Was provided on the permeate BTEX from glycol dehydrators.
side. The How rate of the feed solution Was 0.25 gpm. The
results are shoWn in Table 1. Example 4
55 A set of permeation experiments Was performed in the
TABLE 1 same manner as those of Example 2 using a Zeolite mem
N2 Vapor Pressure brane (Mitsui USA, NY), and a feed mixture of 1 Wt %
Temperature Sweep Water Flux Normalized Water Flux toluene, 1 Wt % hexane, and 15 Wt % Water in isopropanol.
Expt. # ( C.) (L/min) (g/m2 - h) (g/m2 - h - psid) This mixture generates much higher permeation rates than
1 98 5.2 60 23
60 the glycol mixtures used for the previous experiments,
2 100 5.0 130 43 facilitating more accurate measurement and analysis of the
permeate stream. The experiments Were carried out at 80
C., and a nitrogen sWeep at a How rate of 5 L/min Was
provided on the permeate side. Table 3 shoWs a represen
Example 2 65 tative set of data. The Zeolite membrane is very impermeable
TWo series of experiments similar to those of Example 1 to both aromatic compounds and straight-chain aliphatic
Were carried out With a silica membrane module (Pervatech, hydrocarbons.
 US 6,789,288 B2
16
Was assumed to be carried out at 38 C. and the pervapo
TABLE 3 ration step at 220 C. The calculations Were repeated for
three raW gas pressures: 500 psia, 1,000 psia, and 1,500 psia.
Feed The results of the calculations are shoWn in FIG. 8.
Concen- Equilibrium Permeate Vapor Pressure
tration Vapor Pressure Concen- Normalized Flux As can be seen, the higher the natural gas pressure, the
Component (Wt %) (psia) tration (g/m2 - h - psid) lesser is the membrane area required to dehydrate the gas to
the same extent. The membrane area required for the process
Water 15 2.47 99.95 Wt % 69
Isopropanol 83 4.40 530 ppmW 0.02
is very small, less than about 1 m2 per million cubic feed of
Toluene 1 0.15 1.7 ppmW 0.002 gas treated, even When an 80 C. reduction in deW point is
Hexane 1 0.70 2.5 ppmW 0.0006 10 required.
Example 8
As in Example 3, the vapor pressure-normalized ?uxes of A set of calculations Was performed as described in
all of the organic components are orders of magnitude loWer Example 7, except that the raW gas pressure Was noW ?xed
than the vapor pressure-normalized ?ux of Water. 15 at 1,000 psia, and the calculations Were repeated for three
different temperatures for the pervaporation regeneration
Example 58 step: 200 C., 220 C., and 240 C. The results of the
An analysis of the process Was carried out based on the calculations are shoWn in FIG. 9.
experimental data. The analysis Was performed using a As can be seen, the membrane area required for any
process simulator, ChemCad V (ChemStations, Inc., 20 chosen dehydration result decreases as the temperature at
Houston, Tex.), to Which an in-house modeling program for Which the pervaporation regeneration step is performed
pervaporation has been added. The analysis Was carried out increases, because higher temperatures result in higher
in three steps: calculation of Water deW points achieved transmembrane ?uxes. Use of loWer temperatures Would
in the absorption step, (ii) calculation of feed Water vapor require slightly more membrane area.
pressure, and (iii) calculation of membrane area needed to 25 We claim:
achieve a desired reduction in Water deW point of the treated 1. A process for dehydrating natural gas, comprising:
gas. (a) subjecting a natural gas stream to an absorption step,
comprising the steps of:
Example 5 (i) contacting the natural gas stream With glycol in an
Data from the Gas Conditioning Fact Book (DoW Chemi 30 absorber;
cal Co., 1962) Were used to calculate the Water deW point (ii) Withdrawing from the absorber a dehydrated natural
that can be achieved in the absorption step as a function of gas stream;
the initial Water content of the lean glycol (TEG). It Was (iii) Withdrawing from the absorber a Water-laden gly
assumed that the raW gas Was Water-saturated. The calcula col stream; and
tions Were performed at 27 C. and 38 C., tWo temperatures 35 (b) subjecting the Water-laden glycol stream to a regen
that are typical of natural gas streams at the Wellhead and in eration step, comprising:
gas processing plants. The pressure of the natural gas does (i) providing a membrane unit containing a membrane
not signi?cantly affect the relationship between deW point having a feed side and a permeate side and exhibiting
and glycol Water concentration. a ?rst pervaporation separation factor in favor of
40 Water over glycol and a second pervaporation sepa
The relationships between initial glycol Water content and
ration factor in favor of Water over benzene;
dried gas deW point at the tWo temperatures are shoWn in
FIG. 6. As expected, achieving loWer deW points requires (ii) heating the Water-laden glycol stream;
(iii) passing the heated Water-laden glycol stream into
loWer Water concentrations in the lean glycol stream, and the
the membrane unit and across the feed side under
Water concentration in the glycol must be loWer at higher
natural gas/glycol contactor temperatures.
45 pervaporation conditions;
(iv) Withdrawing from the feed side a regenerated
Example 6 glycol stream;
(v) Withdrawing from the permeate side a permeate
The Peng-Robinson equation of state Was used to estimate stream comprising Water vapor;
the equilibrium Water vapor pressure associated With mix 50 (vi) recirculating at least a portion of the regenerated
tures of Water in triethylene glycol (TEG) at different glycol stream to the absorption step.
temperatures. The calculations Were used to generate a series 2. The process of claim 1, Wherein the glycol is selected
of curves, as shoWn in FIG. 7. The curves clearly shoW that from the group consisting of monoethylene glycol, diethyl
the higher the temperature at Which the membrane separa ene glycol, triethylene glycol, and tetraethylene glycol.
tion step is performed, the higher is the Water vapor pressure 55 3. The process of claim 1, Wherein the glycol comprises
on the feed side, hence the better is the driving force for triethylene glycol.
transmembrane permeation of Water. 4. The process of claim 1, Wherein the Water-laden glycol
is heated to a temperature in the range 150250 C. in step
Example 7
(661)
The pervaporation modeling program Was used to calcu 60 5. The process of claim 1, Wherein the regenerated glycol
late the membrane area required to achieve Water deW point stream contains less than about 1 Wt % Water.
reductions of 20 C., 40 C., and so on. The calculations 6. The process of claim 1, Wherein the regenerated glycol
assumed that the raW gas to be treated in the absorption step stream contains less than about 0.5 Wt % Water.
Was saturated With Water vapor at 38 C., and incorporated 7. The process of claim 1, Wherein the regenerated glycol
the calculations and results of Examples 5 and 6. The 65 stream contains less than about 0.2 Wt % Water.
membrane Was assumed to provide a vapor pressure 8. The process of claim 1, Wherein the membrane com
normaliZed Water ?ux of 22 g/m2~h~psid. The absorption step prises an inorganic membrane.
 US 6,789,288 B2
17 18
9. The process of claim 1, wherein the membrane com (iii) WithdraWing from the absorber a spent desiccant
prises a silica membrane. stream comprising desiccant and Water;
10. The process of claim 1, Wherein the membrane (b) subjecting the spent desiccant to a regeneration step,
comprises a Zeolite membrane. comprising:
11. The process of claim 1, Wherein the ?rst pervaporation (i) providing a membrane unit containing an inorganic
separation factor is at least 100. membrane having a feed side and a permeate side
12. The process of claim 1, Wherein the second pervapo
and exhibiting a pervaporation separation factor in
ration separation factor is at least 100.
13. The process of claim 1, further comprising passing a favor of Water over the desiccant;
sWeep gas across the permeate side. 10
(ii) passing the spent desiccant into the membrane unit
14. The process of claim 13, Wherein the sWeep gas and across the feed side under pervaporation condi
comprises air. tions;
15. The process of claim 13, Wherein the sWeep gas (iii) providing a driving force for transmembrane per
comprises natural gas. meation;
16. The process of claim 1, Wherein the membrane, When 15 (iv) WithdraWing from the feed side a residue desiccant
in use in the process, eXhibits a vapor pressure-normaliZed stream depleted in Water compared With the spent
Water ?uX of at least about 10 g/m2~h-psid. desiccant stream;
17. The process of claim 1, Wherein the permeate stream (v) WithdraWing from the permeate side a permeate
has a total organic compound concentration of less than stream comprising Water vapor.
about 500 ppmv. 27. The process of claim 26, Wherein the desiccant
18. The process of claim 1, Wherein the permeate stream comprises glycol.
has a total organic compound concentration of less than 28. The process of claim 26, further comprising heating
about 200 ppmv. the spent desiccant before step (b)(ii).
19. The process of claim 1, Wherein the permeate stream 29. The process of claim 26, Wherein the residue desiccant
has a total organic compound concentration of less than 25 stream contains less than about 1 Wt % Water.
about 100 ppmv. 30. The process of claim 26, further comprising recircu
20. The process of claim 1, Wherein the dehydrated lating at least a portion of the residue desiccant stream to
natural gas stream has a Water vapor deW point of less than step (a)(i).
about 10 C. 31. The process of claim 26, Wherein the inorganic
21. The process of claim 1, Wherein the dehydrated membrane comprises a silica membrane.
natural gas stream has a Water vapor deW point of less than 32. The process of claim 26, Wherein the inorganic
about 20 C. membrane comprises a Zeolite membrane.
22. The process of claim 1, Wherein the dehydrated 33. The process of claim 26, further comprising passing a
natural gas stream has a Water vapor deW point of less than sWeep gas across the permeate side.
about 40 C. 35 34. The process of claim 26, Wherein the inorganic
23. The process of claim 1, Wherein the natural gas stream membrane, When in use in the process, exhibits a vapor
has a ?rst Water vapor deW point and the dehydrated natural pressure-normaliZed Water ?uX of at least about 10
gas stream has a second Water vapor deW point and the g/m2~h~psid.
second Water vapor deW point is at least 50 C. loWer than 35. The process of claim 26, Wherein the gas stream has
the ?rst Water vapor deW point. 40 a ?rst Water vapor deW point and the dehydrated gas stream
24. The process of claim 1, Wherein the natural gas stream has a second Water vapor deW point and the second Water
has a ?rst Water vapor deW point and the dehydrated natural vapor deW point is at least 50 C. loWer than the ?rst Water
gas stream has a second Water vapor deW point and the vapor deW point.
second Water vapor deW point is at least 70 C. loWer than 36. The process of claim 26, Wherein the gas stream
the ?rst Water vapor deW point. 45 further comprises a volatile organic component, and Wherein
25. The process of claim 1, Wherein the permeate stream the inorganic membrane exhibits a pervaporation separation
is discharged to the atmosphere. factor of at least about 100 in favor of Water over the volatile
26. A process for dehydrating a gas stream, comprising: organic component.
(a) subjecting the gas stream to an absorption step, 37. The process of claim 26, Wherein the permeate stream
comprising the steps of: contains less than about 200 ppmv of organic components.
(i) contacting the gas stream With a liquid desiccant in 38. The process of claim 26, Wherein the permeate stream
an absorber; is discharged to the atmosphere.
(ii) WithdraWing from the absorber a dehydrated gas
stream;