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Патент USA US3024878

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March 13, 1962
3,024,868
R. M. MILTON
PURIFICATION OF REFORMER HYDROGEN BY ABSORPTION
Filed Nov. 30, 1959
3 Sheets-Sheet 1
FIG. /.
25
SODIUM ZEOLITE A
ILofDPAWbSORETsBY.NDT
SILICA GEL
LII
\
\
200
ACTIVATED ALUMINA
300
400
TEM PERATURE
500
600
700
°F
INVENTOR.
ROBERT M. MILTON
8%”
A T TORNE Y’.
March 13, 1962
R. M. MILTON
3,024,868
PURIFICATION OF REFORMER HYDROGEN BY ADSORPTION
Filed Nov. 30, 1959
3 Sheets-Sheet 2
SODIUM ZEOLITE A
:-2 2°
)\
Lu
m
0:
8
/
O
<
E
D
O
2
..J
o
9
0:
LU
LL
Q
uJ
CD
0:
l0
O
(I)
D
4 1
CE
m
a
SILICA GEL
5
/
/
‘h
______
________..
o
g-_l
//
o
0
/
7-’.
ACTIVATED ALUMlhA
.
0.2
0.4
0.6
0.8
L0
L2
L3
WATER VAPOR PRESSURE
(MM of Hg)
INVENTOR.
ROBERT M. MILTON
BY
ATTORNEY
March 13, 1962
R. M. MILTON
3,024,868
PURIFICATION OF REFORMER HYDROGEN BY ADSORPTION
Filed Nov. 30, 1959
3 Sheets-Sheet 3
FIG. 3.
23
22
.
10
V
30
/2
1/ 27 Lg,
6/
-47
/3/‘
3?
V
25
V
INVENTOR.
ROBERT M. MILTON
Biz/$43M {MM AT TORNE Y.
United States Patent 0 ” lC€
l
3 024 868
PURIFICATION on’nnironivrnn HYDROGEN
BY AD§0RPTION
Robert M. Milton, Bu?aio, N.Y., assignor to Union Car
bide Corporation, a corporation of New York
Filed Nov. 30, 1959, Ser. No. 856,281
18 tClairns. (Cl. 183-1142)
3,624,868
Patented Mar. 13, 1962
2
FIG. 3 is a schematic ?owsheet of a system for con‘
tinuously purifying reformer hydrogen, according to the
present invention.
.
This invention provides a method for purifying a mois
ture-containing reformer recycle hydrogen gas stream
wherein a bed of crystalline zeolitic molecular sieve mate
rial is provided having pore sizes less than about 4 ang
This invention relates to the puri?cation of reformer
stroms. A moisture-containing reformer hydrogen gas
hydrogen, and more speci?cally relates to an improved
feed stream is contacted with the zeolitic molecular sieve
method for removing impurities such as moisture and 10 bed, thereby adsorbing at least most of the moisture. A
sulfur-containing compounds from a reformer recycle hy
moisture-depleted reformer hydrogen gas stream is then
drogen gas stream.
discharged from the bed.
In the reforming of hydrocarbon oils with a metal oxide
The term “zeolite,” in general, refers to a group of
dehydrogenation catalyst in the presence of recycled prod
naturally occurring and synthetic hydrated metal alumino
uct gas rich in hydrogen, the activity of the catalyst is 15 silicates, many of which are crystalline in structure.
adversely affected by moisture and sulfur-containing com
There are, however, signi?cant differences between the
pounds. Since the recycled product gas, referred here
various synthetic and natural materials in chemical com
inafter as reformer hydrogen, contains moisture and
position, crystal structure and physical properties such'as
X-ray powder diffraction patterns.
sometimes a prohibitively high concentration of sulfur
compounds, the prior art has proposed and employed 20 The structure of crystalline zeolite molecular sieves
numerous methods for removing these impurities. Un
may be described as an open three-dimensional frame
fortunately all of the prior art schemes have serious limita
work of S0,; and AlO4 tetrahedra. The tetrahedra are
tions and drawbacks.
crosslinked by the sharing of oxygen atoms, so that the
Reformer hydrogen usually contains more than 50%
ratio of oxygen atoms to the total of the aluminum and
hydrogen as the major constituent, but under some condi~ 25 silicon atoms is equal to two, or O/(Al+Si)=2. The
tions where the net production of hydrogen is low it may
negative electro~valence of tetrahedra containing alumi~
num is balanced by the inclusion within the crystal of
fall to about 35% by volume. The remainder of the
reformer hydrogen stream is paraf?nic hydrocarbons rang
cations, for example, alkali metal and alkaline earth metal
ing from C1 to C9.
ions such as sodium, potassium, calcium and magnesium
The prior art has employed desiccants such as silica 30 ions. One cation may be exchanged for another by ion
exchange techniques.
gel and activated alumina to dry reformer hydrogen.
These methods of dehydration have among their disad
The zeolites may be activated by driving off substan
tially all of the water of hydration. The space remaining
vantages, low Water capacity at low vapor pressures, low
in the crystals after activation is available for adsorption
water capacity at elevated temperatures, and coadsorption
of hydrocarbons thereby lowering the capacity of the 35 of adsorbate molecules. This space is then available for
adsorption of molecules having a size, shape and energy
desiccant for water. Furthermore, desorption of the co
adsorbed hydrocarbons by heat causes extensive coking
which permits entry of the adsorbate molecules into the
thereby shortening the life of the desiccant.
pores of the molecular sieves.
The present invention is predicated on the discovery
When the reformer hydrogen also contains sulfur com
pounds such as hydrogen sul?de and mercaptans in ob 40 that water and sulfur-containing compounds are sorbed to
the substantial exclusion of saturated paraf?nic hydrocar
jectionable concentrations, the prior art has of necessity
employed a two-step arrangement to remove the impuri
bons on crystalline zeolitic molecular sieve material hav
ing a pore ‘size less than about 4 angstrom units. To
ties. Thus, moisture was removed by desiccants and sul
fur compounds by for example ethanolamine scrubbing.
one skilled in the use of molecular sieve zeolite adsorbents,
Furthermore, under normal conditions the amine system 45 the more polar nature of water and hydrogen sul?de as
will only reduce the e?‘iuent H25 concentration to approxi
compared to hydrogen and saturated hydrocarbons would
mately 0.25—1.0 grains HZS per 100 s.c.f. gas. In many
suggest that any molecular sieve zeolite having pore
reformer hydrogen puri?cation systems, this is equal to
openings large enough to accept the hydrogen sul?de
or very close to the inlet HES concentrations. Conse
molecule, about 3.6 angstron units, could be employed.
50 This is due to the fact that crystalline zeolites exhibit
quently the amine system is ineffectual in such cases.
A principal object of this invention is to provide an
a strong preference for molecules that are polar in nature.
improved method for removing moisture from a reformer
The remarkable performance of crystalline zeolites hav
hydrogen stream.
ing pore sizes less than about 4 angstroms is even more
Another object is to provide an improved method for
amazing when one considers that such zeolites are known
removing sulfur-containing compounds from a reformer 55 to adsorb the paraf?ns methane, ethane and propane, and
hydrogen stream.
these are present in appreciable concentrations in the
A further object is to provide an improved method for
reformer hydrogen. Larger pore sized molecular sieves
removing moisture and sulfur-containing compounds from
such as zeolite 5A (calcium zeolite A) and zeolite 13X
a reformer hydrocarbon stream in a single step.
are known to adsorb these compounds and their higher
Still another object is to provide an improved method 60 weight homologs, but the relative amounts of such higher
for removing moisture and sulfur-containing compounds
molecular weight materials in the feed stream would seem
from a reformer hydrocarbon stream in a single adsorp
so low that their effect would be overlooked.
tion step, without coadsorbing para?inic hydrocarbons.
Contrary to these expectations, it has been discovered
These and other objects and advantages of this inven
that molecular sieves having pore sizes larger than about
tion will be apparent from the following description and 65 4 angstroms strongly adsorb and concentrate the C4 and
accompanying drawings in which:
higher para?ins. The domination of the adsorption areas
vFliG. 1 is a graph comparing the water adsorptive ca
of the molecular sieves by these higher para?ins effec—
pacity of sodium zeolite A with conventional desiccants
tively limits the ability of the larger pore size zeolites to
at elevated adsorption temperatures;
adsorb the sulfur compounds from a reformer hydrogen
FIG. 2 is a graph comparing the water adsorptive ca 70 stream and in all probability accounts for the superiority
pacity of sodium zeolite A with conventional desiccants
of the smaller pore sized zeolites.
at low vapor pressures; and
The zeolites occur as agglomerates of ?ne crystals or
4.
are synthesized as ?ne powders and are preferably tab
leted or pelletized for large scale adsorption uses. Pel
letizing methods are known which are very satisfactory
because the sorptive character of the zeolite, both with
regard to selectivity and capacity, remains essentially un
changed.
It is to be understood that the expression “pore size,”
as used herein refers to the apparent pore size, as dis
tinguished from the effective pore diameter. The appar
> ent pore size may be de?ned as the maximum critical
dimension of the molecular species which is adsorbed by
wherein “x” is a value from zero to 1, "w” is from about
4.5 to 4.9 and “y” in the fully hydrated form is about 7.
Further characterization of zeolite D by means of X-ray
diffraction techniques is described in copending applica
tion Serial No. 680,383, ?led August 26, 1957. The pre
parative conditions for zeolite D and its ion-exchanged
derivatives and their molecular sieving properties are
also described therein.
Zeolite T is a synthetic crystalline zeolitic molecular
10 sieve whose composition may be expressed in terms of
oxide mole ratios as follows:
the Zeolitic molecular sieve in question, under normal
conditions. Maximum critical dimension may be de?ned
wherein x is any value from about 0.1 to about 0.8
as the diameter of the smallest cylinder which will ac
commodate a model of the molecule constructed using 15 and “y” is any value from about zero to about 8. Fur
ther characterization of Zeolite T by means of X-ray dif
the best available values of bond distances, bond angles,
fraction techniques is described in copending application
and Van der Waal radii. Effective pore diameter is de
Serial No. 733,819, ?led May 8, 1958, now Patent No.
?ned as the free diameter of the appropriate silicate ring
2,950,952, issued August 30, 1960.
in the zeolite structure. The apparent pore size for a
Zeolite R is described and claimed in US. patent
given zeolitic molecular sieve will always be larger than 20
application Serial No. 680,381, ?led August 26, 1957.
the effective pore diameter.
Zeolite S is described and claimed in US. patent appli
In the present method for removing both water and
cation Serial No. 724,843, ?led March 31, 1958.
hydrogen sul?de from reformer hydrogen, the naturally
Zeolite F is described and claimed in US. patent appli
occurring zeolitic molecular sieves which may be em
ployed are chabazite, gmelinite and mordenite. These are 25 cation Serial No. 681,908, ?led September 4, 1957.
adequately described in the chemical art. The suitable
synthetic zeolitic molecular sieves include types A, D,
Zeolite J is described and claimed in US. patent appli
cation Serial No. 684,843, ?led September 19, 1957.
Zeolite H is described and claimed in US. patent appli
R, S and T. These are preferably employed in their
cation Serial No. 700,736, ?led December 5, 1957.
sodium~rich cation form although they may contain some
Zeolite M is described and claimed in US. patent ap
other mono- or divalent cations provided that such cation 30
plication Serial No. 685,089, ?led September 20, 1957.
substitution does not alter the effective pore size of the
The crystalline molecular sieve sodium zeolite A has
zeolite so that it falls outside the range of about 3.6 to
been found particularly useful in the method of the pres
4.0 angstrom units.. Potassium cations have the effect of
ent invention, and the latter will be described in detail
decreasing the effective pore size below this value and to
the extent which they are present, the capacity of the ad
with respect to sodium zeolite A.
sorbent for hydrogen sul?de will be reduced. Divalent
however, that the invention is equally applicable to the
It is to be understood,
cations, exempli?ed by calcium, have the e?ect of enlarg
other previously discussed zeolites. Sodium zeolite A
ing the pore size when they are present in substantial
has a pore size of about 4 angstroms, and is preferred
quantities. In the preferred zeolitic molecular sieve type
since it substantially excludes all normal para?ins larger
A, this enlargement does not occur until more than about 40 than propane and has a larger internal adsorption area
than any other known molecular sieve Zeolite of com
25 percent of the cation sites are satis?ed by divalent
parable pore size.
calcium cations. Strontium and magnesium cations have
The pressure employed for the adsorption should be
been found to exhibit this same phenomenon.
greater than about 200 p.s.i.g., since the actual loading
When it is unnecessary to provide for the removal of
of water and sulfur compounds on the adsorbent will be
hydrogen sul?de from the reformer hydrogen, as in those
instances where the hydrocarbon feed to the reformer
prohibitively low at lower pressures. The higher the
total pressure employed during the present gas puri?ca
has been specially puri?ed or otherwise does not contain
sulfur compounds, the puri?cation can be effected using
tion method, the higher will be the actual loading of water
naturally occurring or synthetic zeolitic molecular sieves
and sulfur compounds in the molecular sieve adsorbent.
Reformer hydrogen gas streams are commonly provided
having an effective pore size less than about 4 angstroms
and even smaller than 3.6 angstroms. Suitable naturally
in the range of 200 to 1,000 p.s.i.g. and most frequently
in the range of 300 to 600 p.s.i.g.
occurring materials include erionite, chabazite, gmelinite,
The adsorption temperature should be as low as prac
mordenite, analcite, harmatome and phillipsite. Among
the synthetic zeolitic molecular sieves which may be em
tical to produce the lowest ef?uent dew point and the
ployed are: Type A in the monovalent cation forms and 55 highest purity with respect to sulfur compounds. Since
in which divalent cations may be present up to about the
the reformer hydrogen gas stream is normally provided
same 25 percent substitution described above, Types D, R,
in the range of 40 to 150° F., this range may be em
ployed. The range of 40 to 100° F . is preferred to mini
S, T, F, M, J and H.
Zeolite A is a crystalline zeolitic molecular sieve which
mize the concentration of higher boiling hydrocarbons
may be represented by the formula:
60 which effect a deactivation of the adsorbent upon heating
and also to eliminate water-icing dil?culties.
The moisture content of the reformer hydrogen feed
11
wherein M represents a metal, n is the valence of M,
and Y may have any value up to about 6. The as
synthesized zeolite A contains primarily sodium ions and
stream may vary from as high as saturation to much
lower values in some situations, as for example where
the hydrocarbon feed stream to the reformer reactor has
been specially dried. ‘Due to the fact that any water and
is designated sodium zeolite A. Zeolite A is described in
sulfur compounds entering the reforming process will tend
more ‘detail in US. Patent No. 2,882,243 issued April 14,
to accumulate in the reformer recycle hydrogen feed
1959.
stream, it is more effective to remove it there than at
Zeolite D is a crystalline zeolitic molecular sieve which
any other point in the system. The high capacity of the
is synthesized from an aqueous aluminosilicate solution 70 present molecular sieve adsorbents for water even at very
containing a mixture of both sodium and potassium
low relative humidities makes them particularly well
cations. In the as-synthesized state, Zeolite D has the
suited to the removal of water and sulfur compounds,
chemical formula:
even in those installations where the hydrocarbons feed to
, the reformer is predried..
5
3,024,868
6
In practicing the invention, it has been found that the
super?cial linear gas velocity of the reformer hydrogen
A (4A), 1A6 inch pellets and one each using calcium
zeolite (5A) and sodium zeolite X (13X), 1/16 inch pel
through the zeolitic molecular sieve bed may be any
value up to about 1.5 ft. per second. The adsorption
lets. In these designations the number refers to the ap
proximate pore size and the letter refers to the type of
front velocity is not greatly affected by such velocity but
synthetic crystalline zeolitic molecular sieve, zeolite X
being described and claimed in US. ‘Patent No. 2,882,244
higher velocities should be avoided since they cause un
desirably high pressure drop through the molecular sieve
bed.
As previously discussed, conventional desiccants such
as alumina and silica gel are very sensitive to changes in 10
gas temperatures and suffer an appreciable reduction in
issued April 14, 1959. Table I is a summary of the re
sults of these four runs.
Table I
drying ef?ciency at temperatures above 100° F. The
Molecular Sieve Type, He in. Pellets ...... ._
present molecular sieves, however, have extremely high
Run N o ____________________________ __
Super?cial Linear Velocity i'tJscc
System Pressure p.s.i.g-___________
4A
4A
1
2
3
4
-__
. ‘
575
0.85
575
0. 85
575
0. 43
575
capacity for water up to about 150° F. This property
Gas Temperature, ° F ___________________ __
is clearly illustrated in FIG. 1, which is a plot of the 15 Inlet H28 Concentration, GrS./l00 s.c.f.‘.._-__
Maximum Effluent His Concentration Grs./
amount of water adsorption per pound of dry adsorbent
100 s.c.f __________________________________ _-
versus the adsorption temperature at a vapor pressure
13X
_
88
88
88
88
0.9
0.9
0. 65
0. 83
0. 02
0.02
0. 02
0.02
Useful His Capacity—wt.-percent __________ __ 0.15
0.21
1. 3
1. 4
of 10 mm. Hg for sodium zeolite A, silica gel, and acti
vated alumina.
1Analysis indicated that approximately 30% of the total
sulfur concentration was mercaptans. However, be
Additional evidence of the suitability of the present 20 inlet
cause of inability to determine speci?c niercaptans, analysis
zeolitic molecular sieves to high temperature drying of
was calculated as if it were all H28.
reformer hydrogen was shown in a dynamic system where
In all of the above runs the inlet water concentration
the breakthrough capacity of sodium zeolite A was de
was 0.5 lbs. H2O per mm. .s.c.f. It was not possible,
creased only 33% when the temperature of the gas was
however, to obtain any weight increase, using the gravi
increased from 75 to 212° F. Both silica gel and alu 25 metric method, on the e?iuent stream up to the H28 break
mine were found to be ineffective as desiccants at 212° F.
through point. It can be seen from Table I that the
The water capacity of activated alumina and silica gel
zeolite 4A has eight to ten times greater useful capacity
is appreciably affected by the partial pressure or relative
than the types 5A and 13X. As previously discussed,
humidity. In contrast, the present molecular sieves have
this is due to the exclusion by zeolite 4A of substances
essentially the same capacity at 4.0 mm. Hg as 25 mm. Hg 30 whose molecular dimension are larger than about 4 ang
water pressure. This property illustrated in FIG. 2,
stroms. In the present puri?cation method, as the H28
which is a plot of the amount of Water adsorption per
adsorption zone moves through the bed, the HZS being
pound of dry adsorbent at 25° C., versus water vapor
adsorbed must displace whatever hydrocarbons are ad
pressure, for sodium zeolite A, silica gel, and activated
sorbed thereon. In using zeolite 4A,. only methane,
alumina. Additional evidence of the reduced sensitivity 35 ethane and very little propane are adsorbed; when em
of the present zeolitic molecular sieves to changes in rela
ploying larger pore sized zeolites as for example type
tive humidity was shown in a dynamic system where the
5A, methane, ethane, propane, butane, pentane and
breakthrough capacity of sodium zeolite A at 7% and
heavier para?ins are adsorbed. This point is illustrated
80% relative humidity was about the same.
by Table II, which shows the equilibrium capacities of
When sulfur-containing compounds such as hydrogen 40 type 4A and 5A zeolites for some of the paraiiinic hydro
sul?de and mercaptans are also present in the reformer
hydrogen feed gas, the present invention provides a
method for removing moisture and such sulfur com
pounds in one step instead of the multiple steps required
carbons.
These capacities are at 25° C. and an adsor
bate partial pressure of 500 mm. Hg. The exclusion
properties of zeolite 4A are clearly shown in the table.
by the prior art schemes. That is, crystalline zeolitic 45
Table II
molecular sieves having pore sizes between about 3.6 and
4.0 angstroms are capable of simultaneously adsorbing
Equilibrium Capaclty—
Wt. percent At 25° O.—
these impurities and at the same time excluding most of
the paraffinic hydrocarbons which would otherwise pro
vide competition at the adsorption sites, and when heated
500 mm. Hg
Hydrocarbon
Type 5A
eifect a deactivation of the molecular sieve.
When a feed gas containing two adsorbable compo
nents is fed to a bed of the present zeolitic molecular
sieve material, adsorption usually occurs in a series of
steady state mass transfer fronts or waves. These fronts
form at the feed end of the bed and progress through the
bed at different constant velocities. The more strongly
held materials will be concentrated towards the feed end
of the bed. In the case of reformer hydrogen puri?ca
Type 4A
As ‘further proof of this heavier parai?n hydrocar
bon exclusion principle, the molecular sieve vbeds used
in runs 1 and 3 of Table I were desorhed and the de
tion, there are two principal adsorbable components, 60 sorbate cold trapped for chromatographic analysis.
Table III tabulates the chromatographic analysis of the
H20 and H25. They will be adsorbed on the bed in this
desorbed materials.
order of preference, and the water will displace essen
Table 111
tially all of the H28 from a portion of the bed in which
it is adsorbed.
As previously discussed, crystalline zeolitic molecular
65
M01, percent;
sieves having pore sizes less than about 4 angstroms af
Component
__
ford unexpected advantages when compared to molecu
lar sieves of larger pore sizes, for the present gas puri
?cation method. This fact was vividly illustrated in a
series of tests using a 11/2 inch SCH. 40 x 6 ft. stainless 70
steel pipe section as the adsorption tower. The reform
er hydrogen ‘feed stream contained 86 mol-percent hy
drogen and the balance C1 through C5 parafiinic hydro
carbons.
Four runs were made, two using sodium zeolite 75
__ ___._____ _
Zeolite 5A
Zeolite 4A
Methane _______________________________ ._
Ethane
_
i3. 14
1.12
30. 1
52. 2
Propane ________________ __
13. 9O
15. 0
__.
Butane __________________________________ _-
18. 5S
Pent'me
48. 00
0. 26
2,2-Din1ethyl Butane ____________________ ._
0.07
____________ ..
1. 21.
Z-Methyl Pentane____
--_
0. 16
0 2O
n-Hexane ________________________________ __
5. 30
0. 18
3,024,868
8
7
stroke since this provides a lower linear velocity for a
given mass flow than if a lower pressure were employed.
The heatup gas leaving the adsorbent bed may be con
13% of the zeolite 5A, 1/16 inch bed desorlbate. Butane,
'veniently reduced in pressure and used as the fuel for
pentane and hexane, however, represent 72% of the zeo
lite 5A desorbate and less than 2.0% of the 4A desor 5 the heater.
In the preferred method of desorption, after the ad
bate. This, of course, is due to the exclusion of butane,
sorbent bed has reached the desired warmup temperature,
pentane and hexane by zeolite 4A.
the pressure is relieved to less than 5 atmospheres and
The data presented in Tables I-III above and Table
purging continued with the same heated gas stream until
IV below were obtained as noted on 1,56” ‘diameter pel—
It will be noted that methane and ethane represent
82% of the zeolite 4A 1/16 inch bed desorbate and only
lets of the molecular sieve. The pellet size does not ap 10 reactivation is complete. Under these conditions, re
activation will be adequate to subsequently produce a
pear to exert any controlling in?uence on the process and
pellets of 1/s" diameter have been employed with equal
success. Larger size pellets should also be suitable.
It has been found that the present method will pro
duce an effluent moisture dew point of at least -80° R,
which is considered highly satisfactory for recycle of the
hydrogen to a catalytic reformer. The following Table
IV shows the breakthrough loadings and the effluent dew
-—80° F. dew point e?luent if at least 8 pound-moles of
purge gas is employed for each 100 lbs. of adsorbent.
Following reactivation, the desorbed bed is cooled and
repressurized, using some of the puri?ed reformer hydro
gen gas from the adsorption stroke being conducted in
the alternate zeolite bed.
The previously described adsorption-desorption con
ditions are equally suitable to the sweetening and dry
relative humidity gas streams at 25 and 100° C. The 20 ing of reformer hydrogen as to the drying of reformer
hydrogen, the only difference being that when it is de
zeolite was activated before use by heating to 440° C.
sired to remove H25, the adsorption stroke is terminated
and purging with dry air. The adsorptive stroke is ter
at HZS breakthrough, which may be taken as 0.02 grain
minated at or before breakthrough of the Water adsorp
per 100 s.c.f. This is because the H28 is less strongly
tion front which can reliably be ——80° F. dew point.
25 adsorbed than the H20 at the concentrations encoun
Table IV
tered in reformer hydrogen and as a result, the HZS ad
sorption zone will precede the H20 adsorption zone.
Temperature ......................... __ 26° C._-_ 25° 0.... 100° 0.
FIG. 3 illustrates a preferred system for continuous
Relative Humidity.“
8007
7 07
2.3%
points produced by zeolite 4A when drying low and high
Linear Velocity ft/sec ................. -. 0.67..__. 1.9...... 0.65
E?duent Dew Point __________________ __ —96° F._ —l00° F. —96° F.
Break-Through Loading (lbs. H2O lbs.
adsorbent) __________________________ ..
16.4
18.5
10.5
ly purifying reformer recycle hydrogen according to the
present invention. The impurity-containing inlet stream
is introduced through conduit 10 and three-way control
valve 11 therein for ?ow through branch conduit 12 to
the ?rst zeolite molecular sieve bed 13, which for ex
The effectiveness of the present zeolitic molecular sieves
ample may be on adsorption stroke. The impurities are
in achieving the desired low e?luent dew point during
the adsorption stroke is dependent upon the complete 35 deposited from the feed stream in bed 13 and an impurity
depleted reformer hydrogen gas stream is discharged
ness of the desorption effected. The present invention
contemplates a method for continuously purifying a re
former recycle hydrogen gas stream in which at least
two beds of the aforedescribed crystalline zeolitic molec
ular sieve material are provided. The impurity~laden
reformer hydrogen feed gas stream is contacted with a
therefrom into conduit 14. At least part of the last
mentioned stream is then passed through three-way con
trol valve 15 and communicating discharge conduit 16
for subsequent use as desired, such as recycling to the
reformer unit or for ammonia synthesis.
first bed as an adsorption stroke at a pressure of at least
During the period when zeolite molecular sieve bed
200 p.s.i. and a temperature below 150“ F. As a de
sorption stroke, a second bed is heated to a temperature
13 is on adsorption stroke, a second bed 17 is on desorp
tion stroke so that a continuous supply of puri?ed re
former hydrogen gas will be available. During the ?rst
between 350° F. and 600° R, such bed having previous
ly been loaded with moisture and possibly sulfur-contain
ing compounds adsorbed from the reformer hydrogen gas
stream. The desorbed impurities are then purged from
the heated second bed by passing a heated purge gas at
low pressure therethrough. Finally, the purged second
bed is recooled and repressurized by passing at least part
of the impurity-depleted reformer hydrogen gas stream
therethrough. The ?ows between the ?rst and second
zeolitic molecular sieve beds are periodically switched so
phase of the desorption stroke, heated impurity-laden
reformer hydrogen gas is introduced through conduit
18 and three-way control valve 19 therein for flow
through communicating conduit 20 to second zeolite mo
lecular sieve bed 17. The heated impurity-laden stream
simultaneously heats and purges second bed 17 of the
impurities deposited therein during the previous adsorp
tion stroke. As previously discussed, the purge gas pref
erably flows in a direction opposite to that employed for
the feed gas during the adsorption stroke so as to effect
55
greater heatup and more complete desorption of the ef
ond bed is on adsorption stroke.
fluent end of the bed since the effectiveness of the puri
If the adsorbent is not heated to 350° F., the desorp
?cation of the product gas is largely controlled by the
tion will not be adequate to insure the desired eflluent
degree of desorption of that end of the bed. The purge
dew point on the following adsorption stroke. Tem
peratures above 600° F. tend to cause buildup of car 60 gas is discharged from second bed 17 into conduit 21
for ?ow through three-Way inlet valve 22 to discharge
bonaceous residues in the adsorbent and loss of capac
conduit 23 ‘for further processing as desired. The spent
ity thereby with likelihood of hydrolytic damage in the
purge gas stream may, for example, be conducted to the
event that a high water content purge gas is employed.
plant fuel system for recovery of its heating value.
Temperatures between 450° F. and 550° F. are preferred
During the heating phase of the desorption stroke, the
to minimize the volume of purge gas required as well as 65
that the ?rst bed is on a desorption stroke and the sec
the coking and hydrolytic degradation.
heated gas preferably passes through the impurity-laden
The heatup is preferably effected by heating a portion
of the impurity-containing reformer feed hydrogen to
550°-600° F. and then passing the heated gas through
ployed during the adsorption stroke. During. the purg
ing phase of the desorption stroke, the purge gas is pref
the adsorbent bed. The direction of ?ow is preferably
opposite to that which was employed for the adsorption
erably throttled through valve 24 to a substantially low
er pressure resulting in the removal of a proportionately
greater quantity of desorbate per unit mass of purge gas.
stroke so as to effect greater warmup and more complete
desorption of the adsorption stroke discharge end of the
bed. Also, the heatup step is preferably conducted at
adsorbent bed at about the same pressure as that em
Following the heating and purging phases of the de
sorption stroke which, for example, may be for a pre
approximately the same pressure as was the adsorption 75 determined time interval, three-way valves 19 and 22
3,024,868
9
are closed entirely, terminating flow of the heated im
purity-laden reformer hydrogen gas stream. Simultane
ously, the ports of three-Way valve 15 are reused and
control valve 25 in ‘branch conduit 26 is opened so as to
permit ?ow of the puri?ed reformer hydrogen gas from
discharge conduit 14 through branch conduit 26 and valve
25 to the feed gas inlet end of second adsorbent bed 17.
This relatively cool gas ?ows through communicating con
duit 27 to bed 17 for passage therethrough, preferably
in the same direction as the feed gas during the adsorp
tion stroke. This is to minimize shifting of the bed dur
ing repressurization. The warmed impurity-depleted re
former hydrogen gas is discharged from second bed 17
into conduit 28 after recooling. such bed, and directed
10
with the zeolitic molecular sieve bed at a temperature be
low 150° F.
5. A method according to claim 1 in which the super
?cial linear velocity of the reformer hydrogen gas stream
passing through the zeolitic molecular sieve bed is less
than about 1.5 feet per second.
6. A method according to claim 1, in which the re
former hydrogen gas stream also contains a sulfur-con
taining compound as an impurity, the crystalline zeolitic
10 molecular sieve has pore sizes between about 3.6 and 4.0
angstroms, and said sulfur-containing compound is simul~
taneously adsorbed with said moisture during contact with
said zeolitic molecular sieve bed.
7. A method according to claim 6 in which the zeolite
through three-way valve 15 to discharge conduit 16.
15 is a member selected from the group consisting of the
When the ?rst adsorbent bed 13 becomes loaded with
naturally occurring crystalline molecular sieves mor
impurities and the regenerated second adsorbent bed 17
denite, gmelinite, chabazite and erionite, and the synthetic
has been completely cooled down, the ?ows are switched
crystalline zeolitic molecular sieves A, D, R, S and T.
so that ?rst bed 13 is placed on desorption stroke and
8. A method according to claim 6 in which the zeolite
second bed 17 is placed on adsorption stroke. This is 20 is sodium zeolite A.
accomplished by reversing the ports of three-way valves
11 and 15 so that the feed gas entering conduit 10 ?ows
through branch conduit 27, second bed 17, discharge
conduit 23, three-way valve 15 and thence to discharge
9. A method for purifying a moisture and sulfur com
pound-containing reformer recycle hydrogen gas stream
comprising the steps of providing a bed of crystalline
zeolitic molecular sieve material having pore sizes be
conduit 16 as impurity-depleted reformer hydrogen gas. 25 tween about 3.6 and 4.0 angstroms; providing a moisture
Simultaneously, the ports of three~way valves 19 and 22
and sulfur compound-containing reformer hydrogen gas
are reversed so that the heated impurity-containing re
stream and contacting such stream with the zeolitic
former hydrogen stream is directed from conduit 13
molecular sieve bed at a pressure of at least 200 p.s.i.g.,
through three-way valve 19 and communicating conduit
a super?cial linear velocity of less than about 1.5 feet per
29 to ?rst bed 13, and thence through conduit 30 to 30 second and a temperature below 150° F. thereby adsorb
three-way valve 22 for discharge through conduit 23.
ing at least most ‘of said moisture and sulfur compound;
During the cooldown phase of the desorption stroke,
impurity-depleted reformer hydrogen discharged from
and discharging an impurity-depleted reformer hydrogen
gas stream from such bed.
the second zeolite molecular sieve bed 17 is diverted from
10. A method for continuously purifying a moisture
conduit 28 through communicating conduit 31 and control 35 containing reformer recycle hydrogen gas stream com
valve 32 therein to conduit 12 for passage through ?rst
prising the steps of providing at least two beds of crystal
bed 13 for cooldown and repressurization of such bed.
line zeolitic molecular sieve material having pore sizes
After cooldown has been effected, the bed may be isolated
sui?ciently large to admit moisture molecules into the
until the alternate bed has completed its adsorption stroke,
sieve and less than about 4 angstroms; providing a mois
thus conducting the adsorption stroke to the full capacity 40 ture-containing reformer hydrogen gas inlet stream and
of the adsorbent.
Although preferred embodiments of the invention have ,
been described in detail, it is contemplated that modi?ca
tions of the method may be made and that some features
as an adsorption stroke, contacting such stream with a
?rst zeolitic molecular sieve bed at a pressure of at least
200 p.s.i.g., a super?cial linear velocity of less than about
1.5 feet per second, and a temperature below 150° F.
may be employed without others, all within the spirit and 45 thereby adsorbing at least most of said moisture; dis
scope of the invention. For example, instead of effect
charging a moisture-depleted reformer hydrogen gas
ing the warmup of the zeolitic molecular sieve bed by
stream from such bed; as a desorption stroke, heating a
passing heated gas directly therethrough, such warmup
second zeolitic molecular sieve bed to a temperature be
could alternatively be obtained by passage of a heated
tween 350° F. and 600° R, such second bed having previ
fluid through coils embedded in the adsorbent beds. This 50 ously been loaded with moisture adsorbed from said re
arrangement would have the advantage of avoiding im
former hydrogen gas stream, purging the desorbed mois
purity contamination of the warmup gas, and the dis
ture from the heated second bed by passing a heated purge
advantage of the added investment by virtue of the coils.
gas therethrough, and thereafter recooling the purged
This is a continuation-in-part application of copending
second bed by passing at least part of said moisture
application Serial No. 400,385, ?led December 24, 1953 55 depleted reformer hydrogen gas stream therethrough;
periodically switching the flows between said ?rst and sec~
What is claimed is:
0nd zeolitic molecular sieve beds so that the ?rst bed is on
1. A method for purifying a moisture-containing re<
desorption stroke and the second bed is on adsorption
former recycle hydrogen gas stream comprising the steps
stroke.
of providing a bed of crystalline zeolitic molecular sieve 60
11. A method according to claim 10, in which the
material having pore sizes su?iciently large to admit
zeolitic molecular sieve beds are heated to a temperature
moisture molecules into the sieve and less than about
between 450° F. and 550° F. during said desorption
4 angstroms; providing a moisture-containing reformer
stroke.
hydrogen gas stream and contacting such stream with
12. A method according to claim 10‘ in which part of
the zeolitic molecular sieve bed, thereby absorbing at least 65
said
moisture-containing reformer hydrogen gas stream is
most of ‘said moisture; and discharging a moisture
heated and passed through said second bed at a pressure
depleted reformer hydrogen gas stream from such bed.
of at least 200 p.s.i.g. as the heating phase of said desorp
2. A method according to claim 1 in which the zeolite
is sodium zeolite A.
tion stroke, and thereafter the heated moisture-containing
in the name of R. M. Milton, now abandoned.
3. A method according to claim 1 in which the moisture 70 gas stream is throttled to a pressure below 5 atmospheres
containing reformer hydrogen gas stream is contacted
and passed through said second bed as said heated purge
with the zeolitic molecular sieve bed at a pressure of at
least 200 p.s.i.g.
4. A method according to claim 1 in which the moisture
gas.
13. A method according to claim 12, in which at least
8 pound-moles of heated, moisture-containing reformer
containing reformer hydrogen gas stream is contacted 75 hydrogen gas stream per 100 pounds of zeolitic molecu
3,024,868
11
12
lar sieve adsorbent are passed through said second bed
depleted reformer hydrogen gas stream is passed through
during the purging phase of said desorption stroke.
the purged second bed in a direction cocurrent to that
14. A method according to claim 12 in which the
reformer hydrogen gas stream also contains a sulfur
containing compound as an impurity, the crystalline zeo
litic molecular sieve has pore sizes between about 3.6
of the previously passed reformer hydrogen inlet gas
stream during the adsorption stroke.
18. A method according to claim 1 in which the zeo
lite is a member selected from the group consisting of
and 4.0 angstroms, the sulfur-containing compound is
simultaneously adsorbed with said moisture during said
the naturally occurring crystalline molecular sieves eri
adsorption stroke, and such stroke is continued until the
tome and phillipsite, and the synthetic crystalline zeo
equivalent HZS concentration in the impurity-depleted
onite, chabazite, gmelinite, mordenite, analcite, harma
10
litic molecular sieves A, D, R, S, T, F, M, J, and H.
reformer hydrogen gas stream discharged from said ?rst
' References Cited in the ?le of this patent
bed is about 0.02 gram per 100 s.c.f.
15. A method according to claim 10 in which said
heated purge gas is passed through said second zeolitic
UNITED STATES PATENTS
of the previously passed reformer hydrogen inlet gas
stream during the adsorption stroke.
2,522,426
2,699,837
2,747,681
Black _______________ __ Sept. 12, 1950
Van Note ____________ __ Jan. 18, 1955
16. A method according to claim 10 in which said
2,765,868
Parks _________________ __ Oct. 9, 1956
moisture-depleted reformer hydrogen gas stream is passed
2,880,818
Dow _________________ __ Apr. 7, 1959
molecular sieve bed in a direction countercurrent to that
through the purged second bed in a direction cocurrent 20
to that of the previously passed reformer hydrogen inlet
gas stream during the adsorption stroke,
17. A method according to claim 10‘ in which said
heated purge gas is passed through said second zeolitic
molecular sieve bed in a direction countercurrent to that
of the previously passed reformer hydrogen inlet gas
stream during the adsorption stroke, and said moisture
Schuftan et al _________ __ May 29, 1956
OTHER REFERENCES
Occlusion of Hydrocarbons by Chabazite and Analcite,
by R. M. Barrer et al., Transactions of the Faraday So
ciety (London), vol. 40, (1944), page 202.
Examine These Ways to Use Selective Adsorption,
Petroleum Re?ner, vol. 36, No. 7, July 1957, pages 136
140.
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