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Патент USA US3069260

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United States Patent O??ce
3,069,250
Patented Dec. 18, 1962
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3,069,250
value of the mixed gas increased considerably without
thereby exceeding the density of coke-oven gas.
Other and further objects will become apparent from
PROCESS FOR THE CONVERSION OF GAS PRO
DUCED BY PRESSURE GASIFICATION
Hellmuth Weitt-enhiller, Essen-Bredeney, Franz Bieger,
Dorsten, Harry Scho?, Essen-Margarethenhohe, Wil
5
high-boiling hydrocarbons, tars and pitches as well as
gases which have been ‘freed to a great extent from the
helm Herbert, Frankfurt am Main, Oskar Dorschner,
Bad Homburg-Gonzenheim, and HansIWerner Gross,
Buchschlag, Kreis O?enbach, Germany, assignors to
Metallgesellschaft Aktiengesellschaft, Frankfurt am
Main, Germany, a German corporation
No Drawing. Filed June 6, 1960, Ser. No. 33,956
Claims priority, application Germany June 9, 1959
13 Claims. (Cl. 48-197)
the study of the within speci?cation.
It is already known that both crude gases containing
high-‘boiling hydrocarbons, tars and pitches and which
have been obtained by a gasi?cation reaction effected
10 without pressure, can be converted with steam in the
presence of suitable, non-sensitive catalysts to produce a
gas with richer combustibles content. However, the
catalysts, whose activity is not strongly diminished, i.e.
This invention relates to improved gaseous fuels ap
which are only slightly sensitive to contact with crude
plicable for industrial and residential use by both munici 15 gases ‘containing high-boiling hydrocarbons, tars and
pal and long-distance distribution and, more particularly,
pitches, are characterized in that, in the presence of the
relates to a process by which long-distance fuel gas may
. high carbon dioxide content of the pressure-generated
be produced from crude fuel gases having a relatively
. gas, they effect an insufficient transformation of the gas
high content of carbon monoxide and other impurities,
during the conversion.
,
and which have been pro-treated to remove only that 20
Furthermore, it has been found that even slightly sensi
part of these impurities which is injurious to the con
tive catalysts, when ‘the conversion reaction is carried
version catalyst.
out under pressure, allow only low volumetric velocities
By subjecting carbon-containing liquid or solid fuels,
and have a very limited life ‘with respect to duration of
activity.
such as coal or mixtures thereof, to oxygen or oxygen
containing gases and steam treatment under pressure, 25
gaseous fuel products which are suitable for industrial
or residential purposes may be recovered. The gas pro
duced in the pressure treatment generally has a relatively
high content of carbon dioxide of about ‘25-30%. Upon
reducing the undesirable carbon dioxide present to a
content of only about 2% by volume by scrubbing tech
niques, the heating value of the resulting fuel gas is be
tween 3700 and 45100 kcal. per m.3, depending on the
particular fuel originally charged. The density of the
It has now been discovered that this failure of the
catalyst to give desirable conversion yields is due to the
fact that the pressure gasi?cation gas contains substances
which considerably reduce or completely destroy the ac
tivity of the conversion catalyst. These substances are
30 in particular reactive asphalt materials, such as unstable
tar components, resin-forming impurities, carbon dioxide,
hydrogen sul?de, organic sulfur compounds, ammonia,
hydrocyanic acid, as well as such compounds as styrol,
diole?ns, nitric oxide, etc.
gaseous fuels after scrubbing to remove carbon dioxide 35
According to the invention, the crude hot-pressure
is higher than that of coke-oven gas.
The carbon monoxide content of these pressure-formed
generated gas, substantially at the pressure of the gasi?
cation, may be treated to remove a portion of these solid,
gases can be varied between the range of about 18 and
liquid and resin-forming attendant impurities in such a
40% by volume, depending on the quantity of steam
manner that the major portion of the oil and tar com
used in the gas formation. Generally, the higher the 40 ponents, which do not injuriously a?ect the catalyst, re
rate of steam addition, the lower will be the carbon
main in the gas. The conversion of the partially puri?ed
crude gas is then carried out under pressure in the pres
ence of a conversion catalyst, wherein the unused steam
most uneconomical, in that, when large quantities of
present is utilized to produce a richer combustible con
steam are ‘added, the gasi?cation temperatures are rela 45 tent. The converted gas is thereafter cooled and puri?ed
tively low and the conversion is not extensively effected.
in any known manner.
Additionally, where a large quantity of ‘fresh steam is
Under these circumstances, not only can the pressure
added to the reaction zone, the solid fuel ash does not
conversion of the gas be carried out without impairing,
sinter, but accumulates as a powder instead, which can
and thereby diminishing the activity, of the catalysts,
only be removed with great di?iculty from the ash sluice. 50 but it is possible at the same time to improve the hydro
It is an object of this invention to provide a process
carbon, oil and tar constituents remaining in the gas.
for the production of a fuel gas’ low in carbon monoxide
The steam content and the vaporous oil and tar con
and substantially free from undesirable impurities, which
stituents of the gas can be increased by adding water,
may be admixed with‘ gases having higher calori?c values
steam or oil to 'the gas before it reaches the conversion
55
to form a long-distance fuel gas.
stage. At the same time it is possible to use any unused
It is a further object of the invention to provide a
steam and additionally the heat which is contained in the
crude gas, so that little or no steam or heat is wasted in
process for the production of a fuel gas with a desirably
the overall process, thereby decreasing the cost of con-'
low carbon monoxide content under technically and
economically favorable reaction conditions, which gas 60 ducting the same.
The partial puri?cation and removal from the hot
can then be admixed with gases having higher calori?c
crude gas on its exit from the pressure gasi?cation zone of
values to form a mixture having the calori?c value nec
the disturbing and interfering substances, which not only
essary for long-distance fuel gas, without exceeding the
monoxide content. A large addition of steam during
the pressure gasi?cation can, however, render the method
density of coke-oven gas.
‘
detrimentally affect the catalysts but also form 'incrusta
It is a still further object of the invention to provide a 65 tions and deposits on the walls of the heat-exchanger and‘
heater in which the gas is heated to conversion tempera
process for the production of a fuel gas low in carbon
ture, can be effected by treating the hot gas passing out
monoxide and substantially free from other undesirable
from the pressure gasi?cation zone with a Washing agent,
impurities without sacri?cing the major portion of the
such as water, oil, tar or a mixture thereof. Accordingly,
oil and tar components of the gas by conversion of a gas
the crude gas upon its exit from the pressure gasi?cation
70
produced by pressure gasi?cation, which can thereafter,
by the addition of certain gases thereto, have the calori?c
zone is treated with water, oil or tar, or a mixture of
water with oil and/or tar, whereby the gas is cooled and‘
its content of vapors of water and/ or oil 'and/ or tar is
increased. The gas is now cooled further to such an ex
tent that the condensates separate out in the desired quan
tities. By this cooling, the high-boiling products, resin
forming impurities and dust, including tars and oil drop
A.
stances by cooling and removal thereof, the crude gas is
reheated to the temperature, as for example via suitable
heat-exchange means, which is required for the conversion.
These hot gases are then conducted over a conversion
catalyst in a conversion reaction zone to convert a sub
lets, are separated out in the condensate, all of which
may be removed therefrom, as for example by suitable
cyclone means. Any mist and/or liquid droplets still
stantial part of the carbon monoxide present with a stoi
chiometric quantity of the unused steam present to carbon
are caused chie?y by the cracking of the mist and liquid
Surprisingly, this conversion takes place at conditions
almost completely corresponding to those of equilibrium,
in spite of the impurities contained in the crude gas, such
dioxide and hydrogen. In this way, little or no steam
is wasted in the overall process, and the quantity of gas
remaining in the gas can be removed from the gas by
such known means as baf?e separators, ?lters or the like. 10 liquors from which water must be recovered is decreased,
thereby decreasing the cost of such water recovery.
The deposits and incrustations on the walls of the heater
droplets which were permitted to remain in the gas and
to settle out on the walls of the heater. In order to fur
ther ensure against such formations, the baffle separators
as carbon dioxide, hydrogen sul?de, organic sulfur com
and ?lters can be heated to temperatures at which the mist
pounds, ammonia, hydrocyanic acid, resin-forming im
and liquid formation can no longer take place. The
cooled, crude gas, puri?ed in this manner, is then re
poisons.
heated, as for example via suitable heat-exchange means,
by the hot pure gases emanating from the subsequent con
version and brought to the conversion temperature. In
this process, any cooling of the gas between the ?lter and
heater, which might again lead to the formation of mist
and liquid droplets in the gas, is carefully avoided.
The condensate formed from the gas, enriched with
steam, can be conducted through conventional waste heat
stearn boilers or similar heat exchangers, and the con
centrate thereby recovered can be used as washing liquid.
The high-boiling oil and petroleum fractions are prefer
purities and the like, which are recognized catalyst
According to another embodiment of the invention, the
attendant impurities, which impair the activity of the
conversion catalyst, are removed from the gas employing
therefor surface-active substances, such as coals and
cokes having suf?cient surface activity, silica gel, active
argillaceous earth or by ?ssion catalysts such as chromium
oxide catalysts on active carrier substances. In this em
bodiment, a cooling agent, such as oil, tar or water or
steam, is introduced into the hot crude gas by suitable
injection means in such quantity that the temperature of
the crude gas leaving the pressure gasi?cation zone is only
reduced to that value which is suitable for the conversion
ably returned into the gasi?cation reaction zone in order
reaction without any considerable separation ?rst taking
to form therein as the upper layers thereof a ?lter layer
place by the condensation of high-boiling tar or pitch
on the solid fuel wetted by these substances and preventing
constituents. The introduction of any cooling agent can
the entrainment of any solid fuel particles, because the
be dispensed with if the gas coming from the gas generator
same, being a wetted loose layer, has a ?ltering effect.
Further in this manner, the interfering impurities are at 35 is already at the conversion temperature.
The removal of the disturbing substances is then e?fected
the same time partially destroyed in the gasi?cation zone.
by using the surface-active solid substances, which possess
If the hot gas is treated by washing with an oil or tar,
the property of holding the disturbing substances on their
an increase in its content of oil and tar vapors takes place.
surface, or converting them into harmless compounds.
At the same time, when the gas is treated by washing with
an oil or tar, a more or less extensive cooling of the gas
These surface-active materials can at the same time have
is brought about. As the oil and tar washing mixtures
effect a particularly extensive removal of the impurities,
i.e. disturbing substances, from the gas, it is not neces
sary to cool the gas exiting from the pressure gasi?ca
a certain catalytic effect in the sense of the conversion
reaction to be effected. The determining factor in their
tion zone to the low temperatures which are required
when aqueous liquids are employed as washing agents to
separate out the high-boiling, resin-forming impurities
regeneration in an easy and simple ‘manner, for example
by oxidation of the disturbing substances collected on
their surfaces with gases containing oxygen.
which may be present. The advantage is thereby at
tained that the gas, after being washed with an oil or tar,
The surface-active substances are used in heaped-up
?xed-bed form or as a ?uidized bed, in which the crude
or mixture thereof, can be conducted at a suitably high '
temperature through the ba?le separator or ?lter into the
conversion reaction stage without the vaporous oils and/ or
selection is, however, their lasting effectiveness for remov
ing the disturbing substances or their being capable of
gas to be puri?ed or, during the period of regeneration,
the gases containing oxygen constitute the suspension gas.
The surface-active substances can additionally also be
guided in circulation between two reaction chambers, in
tars being condensed out and with only small quantities
of tar condensate being separated out. The heat-exchange
means-for reheating the gas to the temperature required
for the conversion becomes entirely or partially super
?uous, which represents a considerable advantage of this
embodiment of the invention.
The extent to which the partial separation of the dis
conducted into the second reaction chamber to be regen
erated, after which they are returned to the ?rst reaction
chamber.
After the disturbing substances have been separated out
turbing impurities is effected is regulated according to
by the surface-active materials, the preliminarily cleansed
the extent to which the vaporous tar and oil gas com
ponents are or are not injurious to the conversion catalyst
over a relatively long period of time. On account of the
the ?rst of which they effect the removal of the disturbing
substances from the crude gas, after which they are then
gas is also ?ltered, if necessary, in order to remove any
particles separated from the surface-actve materials, and
then passed directly to the conversion reaction stage. The
improvement resuling from the hydrocarbons remaining
gas contains a large quantity of carbonic acid as well as
in or added to the gas, it is advantageous to limit as far
carbon monoxide, hydrogen sul?de, organic sulfur com
pounds, ammonia and hydrocyanic acid, and tar vapors,
that is, all components of the crude gas, with the excep
tion of the disturbing substances, resini?ed or held by the
as possible the quantity of components which are sepa
rated out.
It has also been found in accordance with the invention
that the quantity of substances separated out can be
lowered if care is taken to eliminate any possible forma
tion of the very ?ne separated droplets of oil and tars.
surface-active solid substances as well as, in the case where
steam is introduced, an increased steam content as com
pared with the crude gas. As has already been mentioned,
the gas is at conversion temperature. By carrying out
Consequently, it is ‘advantageous to employ as separator,
i.e. cyclone, etc., an arrangement having a high degree of
the conversion reaction following the pre-treatment of the I
efficiency.
crude gas as described, the ‘following advantages unex
After limited partial separation of the disturbing sub 75 pectedly become apparent.
5
3,069,260
The pretreatment allows the use also of very active con
version catalysts, whose activity can be maintained for a
very long period of time with a high volumetric velocity
of about 500 to 2500 m? of gas, preferably 700 to 1000
1115*‘ per m5‘ of catalyst an hour.
Under the action of the conversion catalysts, in addi
tion the oil and tar vapors contained in the gas undergo
6
are subjected several times to the re?ning action of the
conversion catalyst, and the quality of the re?ned products
is improved.
In addition, inherent or foreign hydrocarbons, for ex
ample mixtures of water and hydrocarbons, can be intro
duced for vaporization and conversion by the catalyst
at any point between the gas outlet from the pressure gas
a considerable improvement and stabilization. Thus, for
generator and the gas inlet to the catalyst, providing these
example, the quantity of benzine contained in‘ the crude
hydrocarbons do not come into contact with the catalyst
gas is substantially doubled, while the aromatic substances 10 in the form of droplets, but only in vaporous state. By
'in the benzine increase considerably, the ole?n content
this measure, liquid or solid disturbing substances are
drops and the content of saturated hydrocarbons rises.
reliably prevented from reaching the catalyst and thereby
Q
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l
x
s
At the same time, the content of water-soluble phenols in
causing damage. At the same time and under all cir
creases. Moreover, the content of sulfur compounds in
cumstances, it is important that the arrangement be such
both the oil and tar decreases. The content of acid oils 15 that also in the heating devices thermic decomposition of
in the light and medium oils is also considerably lessened,
the hydrocarbons or the like, contained in the gas, cannot
which shows that the higher molecular, less desirable
take place. Therefore, it is advisable to introduce the
phenol constituents have been converted into water-solu
heating medium into the heating devices in counter-?ow to
ble phenols. In the gas itself, the hydrocyanic acid con
the gas.
tent and the content of organic sulfur compounds have di 20
After leaving the conversion reaction zone, the convert
minished to fractional parts of that which they were
ed gas may be cooled through heat-exchange means, re
originally.
leasing the major part of its heat to the gas entering the
It has also been found that the partial cleaning of the
conversion reaction zone and its residual heat through
crude gas, according to the invention, likewise allows ad
heat-exhange means to a waste heat boiler for the produc
vantageously the use of conversion catalysts which at the 25 tion of steam. Thereafter, direct or indirect cooling
same time have a hydrogenating effect and further con
means may be employed for ?nal cooling of the gas
tribute to the improvement of the oil and tar constituents
‘freed from carbon dioxide and hydrogen sul?de, as for
of the crude gas. This can be carried so far that the light
example by suitable conventional scrubbing techniques.
ends obtained during the preparation of the gas after the
Upon drying, the puri?ed gas may be used as a synthesis
conversion reaction require no further ?nishing by, for 30 gas or directly as an industrial or residential gas via long
example, hydrogenating re?ning, but whereby a motor fuel
distance or local distribution.
is obtained directly solely by distillation separation from
The puri?ed gas obtained in accordance with the proc
the light and medium oils and, if necessary, washing out
ess of the invention normally contains only about 4 to
the phenols.
:
8% carbon monoxide, and its tensity is ordinarily below
p The catalytic conversion may be carried out, employing 35 that of coke-oven gas. However, if desired, for speci?c
as conversion catalyst, for example, iron oxide catalysts
purposes the gas may be made to have a higher carbon
activated with chromium oxide. However, other less ex
pensive materials may be used advantageously, such as
bog iron ores or similar iron oxide hydrates. In place
monoxide content than 8% and a higher density as well by
effecting a less complete transformation in the conversion
reaction zone or by mixing non-converted gas with the
of iron oxide catalysts, catalysts containing oxides or sul 40 puri?ed converted gas.
.
?des of metals of the 6th group of the periodic system,
The advantage of the process in accordance with the
particularly molybdenum and tungsten as effective metal,
invention is increased by the advantages resulting from
may be used with good results. These catalysts have at
the use of the converted gas thereby obtained. The
the same time a more or less distinct hydrating effect,
pressure-produced gas obtained, for example, from pit
especially when they are admixed with sul?des or oxides 45 coal has a calori?c value below 4000 kcal. per in.3 after
of metals of the 8th group of the periodic system, such
the separation of the carbon dioxide. To increase this,
as cobalt or nickel. A catalyst formed of active alumina
with 3.4% cobaltous oxide and 9.6% molybdenum tri
oxide has, for example proved highly suitable.
it can be mixed with natural gas, but then the density rises
above that of the coke-oven gas. This, however, hinders
or prevents the use of the mixed gas for long-distance gas
The two embodiments for preliminary puri?cation ac 50 supply. If, on the other hand, the pressure-produced gas
cording to the invention can also be used jointly. This
is converted and completely or partially freed from car
is advantageous, for example, when, by partial separation
of the high-boiling tar or pitch components by cooling,
bon dioxide, its density drops considerably. Therefore,
by adding gases having a high calori?c value, such as for
example natural gas, re?nery gas, propane, butane, it can
removed, but not the other interfering and disturbing sub 55 easily be brought to the calori?c value necessary for long
stances, such as styrol, diole?ns or nitric oxide, which are
distance gas supply, for example 4600 kcal. per m.3, with
present in the gas and which may occur alone or jointly
out exceeding the density of coke-oven gas. By this
in the resini?cation reactions which attack the conversion
measure, breakdowns in manufacturing works, using long
catalyst and considerably impair its high activity. In this
distance supply gas and the burners of which frequently,
instance, the treatment described with surface-active solid 60 react very sensitively, are avoided. Furthermore, the
substances is carried out after the partial separation of
density of the gas produced can be adjusted by the addition
the highdboiling tar or pitch constituents by cooling before
of other gases having a higher density, such as nitrogen,
or after the gases have been heated to conversion tem
carbon dioxide, ?ue gases or the like.
perature, and only thereafter is the gas conducted over
Also, the pressure gasi?cation itself can be performed
the disturbing tar constituents of the crude gas have been
the conversion catalyst.
65 in a very favorable manner according to the instant
It has also proved advantageous, before treating the gas
invention. The carbon monoxide content of the pres
with surface-active substances in the preliminary cleaning
sure-generated gas can, as is known, be varied between
operation, to introduce again and vaporize the whole or a
about 10 and 40% of the pure gas, inthat the gasi?cation
portion of the tar constituents obtained from the gas in
of the fuel is carried out with larger or smaller quantities
re?ned state after the conversion reaction, for example, 70 of steam. It is now possible, according to the invention,
in fractions, possibly also with aqueous concentrates, at
to work advantageously with a small addition of steam
those points where a cooling of the gases occurs for the
and thus‘ already obtain considerable economic advantages.
partial separation of the high-boiling tar and pitch constit-‘
But also for technical reasons, this smaller addition of
uents or for attaining the conversion temperature. In this
steam is of importance, because, even in the case ofdi?‘L,
manner, the tar constituents capable of being improved 75 cult fuels, it produces an ash which is light and easy to
3,089,250
7
remove from the pressure gas generator; an operation
which frequently presents difficulties in the case of the
addition of large quantities of live steam.
The invention is further illustrated by the following ex
amples, but it is to be understood that it is not to be
liydrocyanic acid of the gas is decreased, as for example
from 170 to 4 mg./rn.3, and the content of organically
bound sulfur is decreased, for example, from 300 to 25
limited thereby.
cordance with the invention that the gas throughput can be
between about 500 and 2500 m.3 of gas per m9 of catalyst
mg./m.3.
In addition, it is important for the procedure in ac
Example 1
an hour and that the process is conducted at catalyst
The gas generator is operated under a pressure of 23
atmospheres and with oxygen and steam in the ratio
of about 1. m.3 oxygen:4.5-6.5 kgs. of steam as gasifying
agents. The gas thus obtained leaves the gas generator
temperatures of about 240-660” C., preferably 400
in the case of open-burning coal at a temperature of about
500—600° C. It is cooled in a washing cooler to a temper
The production of a standard, long-distance supply gas,
starting with a pressure-produced gas converted accord
ing to the process of the invention, takes place as follows:
500° C.
Example 2
ature of about 190-210° C., preferably 195-—200° C.,
whereby any liquid produced in the cooling process, as
The converted gas employed has, for example, a car
for example aqueous condensate, is advantageously used
bon monoxide content of 6%. Its density, after the car
as washing agent. High-boiling products and dust, in—
bon dioxide has been washed out to a residue content of,
cluding pitch, tar and oil droplets, separate out in the
for example, 2—3%, amounts to about 0.25 to 0.3, relative
washing cooler. The gas takes up the water from the
to air=1. 2580 111.3 of this converted pressure-produced
washing agent in the ‘form of vapor. The water absorbed 20 gas, which, after cleaning to 3% carbon dioxide, consists
depends upon the temperature conditions and the dew
of 1670 m3 pure gas, are mixed with 860 m.3 of natural
point of the gas entering the washing cooler. The gas
gas and 500 m.3 of nitrogen to form 3030 m.3 of standard
passes into the washing cooler with a dew point of, for
long-distance supply gas.
example, 178° C. and leaves the washing cooler with a
We claim:
dew point of about 195° C. The gas can be further
1. Process for the production of a puri?ed fuel gas
cooled to a temperature of about 160-l70° C. in a waste
having a low carbon monoxide content from hot crude
heat boiler, whereby an aqueous condensate is produced
fuel gas high in carbon monoxide and attendant impurities
which contains considerable quantities of nitrogen. The
obtained by pressure gasi?cation of solid carbon-contain
condensate is advantageously circulated as Washing agent
30 ing fuels with steam and oxygen, which comprises cooling
through the Washing cooler. On leaving the Waste-heat
said hot crude gas to a temperature of about 190 to 210°
boiler, the gas has the following composition, based on
C. by contacting the hot crude gas under pressure with
dry gas:
a member selected from the group consisting of steam, oil,
‘Percent
tar, and mixtures thereof, whereby the high boiling prod
CO2
_____________________________________ .... 26.5
C0
______________________________________ __ 23
H2
____..
..
35
39
CH; _____________________________________ __ 10
N2 ______________________________________ __ 1
H28 _____________________________________ __
0.5
The gas contains 240~270 mg./m.3 of organically
bound sulfur and a Water vapor content according to
the dew point, that is, about 0.3 to 0.4 kg./m.3 of gas,
ucts, reactive asphaltic materials, resin-forming impurities,
water, tars, pitches, and like materials form a condensate,
conducting the crude gas after separation therefrom of
said condensate at the conversion temperature and at sub
stantially the same pressure as the pressure of the starting
hot crude gas over a conversion catalyst to thereby con
vert the high content of carbon monoxide and steam un—
used in the pressure gasi?cation contained in said crude
gas to carbon dioxide and‘ hydrogen, and thereafter re
covering the low carbon monoxide content fuel gas.
also 100 to 200 mg./m.3 of hydrocyanic acid, varying
2. Process according to claim 1, which comprises heat
quantities of gaseous hydrocarbons and 15 to 100 g./m.3 45
ing said crude gas after removal of the condensate there
of condensable hydrocarbons, according to the kind of
from to said conversion temperature prior to conducting
coal gasi?ed.
If this mixture of gas and vapor is now converted
after being passed through a baf?e separator, it is found
that in spite of a high CO2 and water vapor content a '
the crude gas over said conversion catalyst.
3. Process according to claim 2, wherein the heat of
the gas recovered from the conversion is utilized to effect
said heating of said crude gas.
4. Process according to claim 1, which comprises re
change in the condensable and gaseous hydrocarbons takes
place, in that the gas-benzine is about doubled and the
cycling said condensate to said pressure gasi?cation.
quantity of aromatic substances contained therein in
5. Process according to claim 4, which comprises em
creased considerably, being in many cases doubled, with
ploying said condensate as a wetting agent for said solid
the result that the density of the gas-benzine is greater,
fuel to be gasi?ed.
the bromine number dropping to about 1A of the original
6. Process according to claim 1, in which said con
value, as for example from 47 to 12, and the ole?n content
version catalyst additionally exerts a hydrogenating effect.
dropping correspondingly, as for example from 20% by
7. Process according to claim 1, wherein said crude gas
volume to 6% by volume. The content of saturated hy
drocarbons is increased, as for example from 12% by 60 is conducted over said conversion catalyst at a throughput
rate of from 500 to 2500 m.3 per m.3 catalyst an hour.
volume to 29% by volume. The content of water-solu
8. Process for the production of a puri?ed fuel gas
ble phenols is increased, as for example from 2 g. per
liter to 10 g. per liter, and also the total sulfur content
of the gas-benzine is decreased, as for example from
0.81% by weight to 0.15% by weight.
After the conversion reaction, the gas-benzine is re
covered in the known manner, as for example by a wash
ing with oil after high-boiling benzine and oil constituents,
which are contained in the converted gas, have been sepa
rated out by condensation. These are speci?cally lighter
after passing through the catalyst than they were before.
Their content of acid oils is considerably less, as for
example decreased from 36% by volume to 13% by
volume. The sulfur content has dropped similarly to the
gaS-benzine content. At .the same time, the content of 75
having a low carbon monoxide content from hot crude
fuel gas high in carbon monoxide and attendant impurities
obtained by pressure gasi?cation of solid carbon-contain—
ing fuels with steam and oxygen, which comprises cooling
said hot crude gas to the temperature required for the
conversion of the carbon monoxide and steam content in
said crude gas to carbon dioxide and hydrogen by con
tacting the hot crude gas under pressure with a member
selected from the group consisting of steam, oil, tar, and
mixtures thereof, thereafter passing said partially cooled
crude gas in contact with a surface-active solid substance
capable of removing the high boiling products, reactive
asphaltic materials, resin-forming impurities, water, tars,
‘3,069,250
19
pitches, and like materials present in said gas, conducting
the crude gas after separation therefrom of said materials
gas to carbon dioxide and hydrogen, recovering the low
carbon monoxide content fuel gas, thereafter cooling
at the conversion temperature and at substantially the
and scrubbing the converted gas to remove therefrom
same pressure as the pressure of the starting hot crude
gas over a conversion catalyst to thereby convert the
further impurities such as hydrogen sul?de, organic sul
fur compounds, ammonia, hydrocy-anic acid and nitric
acid, admixing said puri?ed gas with gases having higher
calori?c values than such puri?ed gas to thereby form a
long-distance fuel gas having a condensate below that of
high content of carbon monoxide vand steam unused in the
pressure gasi?cation contained in said crude gas to carbon
dioxide and hydrogen, and thereafter recovering the low
carbon monoxide content fuel gas.
coke oven gas.
9. Process according to claim 8, wherein said surface 10
12. Process according to claim 11, wherein said gas
active solid substance is a member selected from the group
having a high calori?c value is a member selected from
consisting of surface-active carbons, silica gels, argil
the group consisting of natural gas, a re?nery gas, propane,
laceous earths, and ?ssion catalysts.
butane and mixtures thereof.
10. Process according to claim 8, wherein said contact
13. Process according to claim 12, which comprises
ing with said solid surface-active substance is eifected at 15 additionally adding to said puri?ed gas a member selected
a temperature of between 240 and 660° C.
from the group consisting of nitrogen, carbon dioxide,
11. Process for reproducing long-distance fuel gas,
?ue gas ‘and mixtures thereof.
which comprises cooling hot crude fuel gas high in carbon
monoxide and attendant impurities obtained'by pressure
gasi?cation of solid carbon-containing fuels with steam 20
and oxygen to a temperature of 190 to 210° C. by con
tacting the same under pressure with a member selected
from the group consisting of steam, oil, tar, and mix
tures thereof, whereby the high boiling products, reactive
\asphaltic materials, resin-forming impurities, Water, tars, 25
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,918,254
1,926,170
2,134,548
2,671,718
pitches, and like materials form a condensate, conducting
used in the pressure gasi?cation contained in said crude
1933
1933
1938
1954
FOREIGN PATENTS
the crude gas after separation therefrom of said con
densate at the conversion temperature and at substan
tially the same pressure as the pressure of the starting
hot crude gas over a conversion catalyst to thereby con
vert the high content of carbon monoxide and steam un
Faber _______________ __ July 18,
Oberfell et al _________ __ Sept. 12,
D-anulat _____________ __ Oct. 25,
De Coriolis __________ __ Mar. 9,
739,752
30
Great Britain _________ __ Nov. 2, 1955
OTHER REFERENCES
Hassler: Active Carbon, pp. 277-282, Chemical Pub
lishing 00., Brooklyn, N.Y., 1951
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