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Патент USA US2120296

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June 14, 1938. -
M. PIER E1‘ AL
-
2,120,296
HEATING UPVICARBONACEOUS MATERIAL
Filed Nov. 27, 1955
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Patented June 14, 1938
2,120,296‘
UNITEDSTATES PATENT OFFICE.
_
2,120,296
Mathias
HEATING
Pier,UP
Heidelberg,
CARBONACEOUS
and Eugen Anthea, and
Ludwigshateu
- on - the
Hanna Schappert,
Rhine, Germany, assignors to I'. G. Farbeniu
dustrie Aktiengesellschatt, Frankiort-on-the
v Main, Germany
’ Application November 27, 1935, Serial No. 51,826
In Germany December 1, 1934
5 Claims.
The present invention relates to improvements
in the heating. up of carbonaceous materials.
The drawing is diagrammatic in form and
(Cl. 196-63)
itself proceeds with great evolution of heat, the
preheater has only to serve the single purpose of
bringing the whole system at the beginning of the '
operation to the necessary temperature. When
the reaction has been initiated, the preheater
The destructive hydrogenation of carbonaceous. then usually is idle since the heat regeneration
materials of the nature of coals, tars, mineral by means of the heat-exchanger brings the initial
materials to a su?iciently high temperature but
oils and the like usually proceeds with consid
illustrates a method by which the present inven
tion may be carried into practice.
erable evolution of heat.
'
-
From a certain size of
plant upwards, the heat set free is greater than
the heat losses, the latter being composed of two
the preheater still ‘consumes, heat and tails in
pressure. If, by means of a by-pass, the pre 10
heater is short-circuited, there is then the danger
that the residues of products remaining in the
ent on the surface area of the apparatus and tubes will coke and render the preheater useless.
(3) Most preheaters, whether heated by gas,
the temperature of the radiating surfaces, and‘
1 losses in the heat-exchanger employed in the electricity or otherwise, transfer the heat to be
supplied through a relatively small surface for
. usual manner for imparting the heat of the re
action products to the initial ‘materials because the reasons already mentioned. _The outer ?lm
the products issuing from the heat-exchanger oi the initial materials which transfers the heat
always carry away a certain amount, 0! heat in to the inner parts of the materials is therefore
practice. vAll these losses can be reduced to a usually-at a higher temperature than is desirable
minimum, but in spite of this it is still necessary for the initial materials, and even if overheating
to supply heat from outside to plants of medium can be reduced by employing special precautions,
size and it is only with quite large units that the such as regulating the supply of heat, ribbed tubes
heat of reaction preponderates. Even in this of different circuits, there still remain the said
case, the whole plant must ?rst be brought to the > drawbacks of pressure difference and bad degree
operating temperature. The time necessary for of efilciency. Even by heating one of the initial
this purpose depends on the mass of iron-tobe materials, as for example the gas, and then mix-.
brought to operating temperatures, the strength ing it with the colder initial material in order
of the available source of energy and the radia- ' to ‘produce the desired reaction temperature, a
3 6 tion of the preheating system.
temporary marked exceeding of the initial re
.
In the priorheating arrangements, the necese action temperature desired to be set up cannot
‘ sary heat has usually been supplied to the initial always be avoided in practice because the equali
materials in tubular preheating apparatus which zation of the mixture proceeds in wave-like ?uc-J
is heated by gas or fed from a source of electric tuations in temperature. This is also true in the
3 GI current.
casewhen the [necessary heat is supplied by an
parts namely radiation losseswhich are depend
15
20
,
25
30
'
'
35
The drawbacks of such a heating ‘up are as , additional exothermic reaction, as for example of
(1) The naturally high speed of the initial ma
terial in the preheater which is necessary for the
the reaction CO+3H2=CH4+H2O.
We have now found that thesaid drawbacks are
avoided by directly or indirectly supplying to the
transference of heat causes a loss in pressure
still hot products having left thereaction cham 40
follows:—
'
,
~
which must be continuously obviated by the gas
circulation pump. If the heating up of the ini
tial materials takes places in a preheater in front
of the reaction chamber, it is impossible to avoid
45 the pressure prevailing in the reaction chamber
from being lower than the pressure set up by
the pump to an extent corresponding to the re
sistance of this preheater.
_
(2) The preheater is very expensive in opera
60 tion because in the case of gas-heated preheaters
the degree of thermal ef?ciency is usually very
bad by reason of the high temperatures (as for
example more than 400° C.) and electrical energy
on the other hand is not. cheap.
55
‘
Very frequently, especially when the reaction
ber further heat, by means of a medium heated
outside the system, advantageously by means of
a vaporized normally liquid medium having a
high heat of vaporization, preferably a heat of
vaporization of at least 500 kilocalories per kilo
gram the initial materials ?owing towards the
reaction chamber being heated by means of the
products thus heated. The said heating medium
cannot only be brought into indirect heat ex
change relation with the reaction products as
soon as the latter leave the reaction chamber but
also some time after their issue from this cham
ber provided the said reaction products are still
in heat-exchange relation with the initial mate
rials to be heated.
e
45
2'
p
_
_
when the supply of heat is effected by ‘means
of a liquid, the latter'is preferably heated out
side the system by any of the‘known methods in
a separate heating device, preferably a heating
device simultaneously used for several systems.
The burden of‘the resistance of this heating de
and which latter material at first is still cold, the
said chamber thus being slowly heated up by
means of a medium outside the system. It has
the advantage that especially with an exothermic \
course of the reaction the supply of heat can be
' vice does not fall on the system and moreover it
readily interrupted when the operation requires
117,; ‘when working with the usual preheatcrs this is
‘is very. small. Furthermore, only a small ex
‘practically impossible in a satisfactory manner as
penditureof energy is necessary'i'or heating, es
10 pecially as compared with a. preheater arranged
in circulation.
The heating device for the heating medium
works at a very high degree of ei?ciency because
its‘ inlet temperature is low. Since the heat-sup
15 plied, for example when using water as the heat
ing medium, is utilized for the greater part as
heat of vaporization, the heat of condensation
supplied in the regeneration increases the degree
of eiliciency of the latter very considerably.
or Not only water, but also other media may be
employed as heating media, as for example oils
‘or gases. It is especially advantageous, however,
to employ condensing steam because it has very
good heat-transferring properties and the heat
- g5 transit value of the regeneration surfaces is in
creased to no small extent. Care should always
be taken not to supply to the eiiluent substances
so much heat that iniurious overheating takes
. place.
so
The thermal reaction may be initialed by heat
ing the ?rst charge of initial material by pre
heaters preheated with gas. The further charges
‘of initial material are then heated according to
the present invention.
_
The process according to this invention allows
of an easy adjustment of the supply of heat by
regulation of the amount or temperature of the
heating medium or both. It offers further greater
advantages, for example, when working in the so- .
40 called sump phase, that is the phase in which
the initial materials are present either as a liq
uid or as a pasty dispersion of solids in liquids.
for example ‘in the destructive hydrogenation
, of coals even when in the separator directly at
45 tached to the reaction chamber large amounts
of liquid products are obtained the heat content
of which is lost as far as the regeneration is con
cerned because these products are usually fur
ther worked up at the temperature which they
so have in the separator, since in such case the re
maining vaporous constituents, if not further
heated, do not contain amounts of heat suiiicient
for heating by regeneration the initial materials
substantially to the reaction temperature.
A further advantage of the operation accord
55
ing to the present invention consists in ‘the fact
that the heating medium need not be brought
into ‘ heat exchange with the products vhaving
left the reaction space at a place at which these
products have the highest temperature; thus, for
example, ifthree heat regenerators arranged in
‘series are employed the said heating medium
may also be brought into heat exchange with the
‘ products passing- through the second heat regen
65 erator. In this case the heating medium need not
be brought to a temperature’ as; high as is neces
sary when bringing -it into heat exchange with
the products directly after their issue from the
reaction space and nevertheless the necessary
70 amount of heat is imparted to the products.
' The said kind of preheating may also be used
with special advantagefor setting apparatus in
operation. The initial material is thereby pre
heated in a cautious manner by heat exchange
75 with the material leaving the reaction chamber
already pointed out.
‘
'
p
‘
10
Example
20 tons per hour of a tar are pumped together
with 30,000 cubic meters per hour of hydrogen
through two heat regenerators arranged in series
and are‘then introduced while at the reaction
temperature of 425° G. into the first of two reac
tion vessels; they leave the second vessel while
at 450° C. From the adjacent separator two tons
per hour of high boiling constituents are removed.
To the mixture of vapors and gases leaving the
separator 1 ton of steam superheated to 450° C.
and maintained under superatmospheric pressure
is then supplied before its entrance into the heat
regenerators, the initial materials being in heat
exchange with the said mixture of vapors and
gases thus being heated to 425° C. before enter 25'
ing the first reaction vessel. Without the said
operation a preheater would be necessary for the
complete heating up to the reaction temperature
which supplies the still lacking heat amounting
80
to about 600,000 kilocalories per hour.
.The process according to the present invention
is not only applicable to all varieties of destruc
tive hydrogenation as for example aromatiza
tion, hydrofining or the usual splitting hydro
genation under pressure; but also with other heat 85
treatments of carbonaceous materials in the pres
ence or absence of hydrogen or steam or other
gases, such as cracking or non-splitting hydro
genation, the necessary heat may be supplied with ‘
40
advantage in the ai’oredescribed manner.
The foregoing example further illustrates the
nature of this invention but the invention is not
restricted to this example.
~
In the drawing numeral i designates the feed
line by-which the hydrocarbon material to be 45
hydrogenated is fed. Pump 2 forces the mate
rial through the line I and through heat exchang
ers 4 and 5. Hydrogen is forced into the line 3
by pipe 6. From the heat exchangers the heated
mixture of hydrogen and hydrocarbon passes by
a line ‘I into the reaction vessels 8 and 9 which
are shown in series. I'hese vessels are adapted tov
withstand the high pressure and temperature re‘
quiredfor the reaction and the reacted materials
flow through a valved line ll into a separator II,
from which any unvaporized material may be re
moved- by a pipe II. The vaporized materials
pass through a pipe it. If desired, a portion of
the material from the second reaction vessel 8
may be passed directly into the pipe I! by a
valved pipe ll. Steam at high temperature and
pressure is also passed into the line II by means
of a pipe I! and the mixture of the reaction
product and steam then passes through the heat
exchangers 5 and 4, in the order mentioned, by
the pipes i6 and I1 and issues from the pipe i8
into a separator is. The lique?ed products are
taken from ‘the separator by a pipe 20 and gas
by a pipe 2|.
'
‘
70 ,
What we claim is:
1. In the thermal conversion of distillable car
bonaceous materials in one or more reactors the
step of heating up the initial carbonaceous mate“
rials to the temperature requiredfor the sat? ‘
2,120,290
3
thermal conversion by indirect heat exchange re
4. In the process asclaimed in claim I adjust
lation with at least part of a prior charge of still ing the temperature desired for the thermal con
hot reactants to which after issue from the last version by supplying regulated amounts of heat
reactor a higher temperature has been imparted ing medium and regulating the temperature of
than they had in the said conversion, by a me this heating medium.
‘
dium ‘which has been heated by a foreign source
b. In the process as claimed in claim 1 heat
of heat to a higher temperature than these re
ing up the initial carbonaceous materials by indi
actants have at the place at which the said me
rect heat_exchange relation with the constituents
dium is supplied.
-
of the still hot reactants issuing as vapors from
the last reactor and to which a higher tempera 10
ture than they have in the conversion has been
terials having undergone the thermal conversion‘ imparted by a foreign source- of heat.
a vaporized normally liquid medium having a
2. In the process as claimed in claim 1 supply
ing to the still hot distillable carbonaceous ma
high heat of vaporization.
3. In the process as claimed in claim 1 supply
ing superheated steam to the still hot distilla
ble carbonaceous materials having undergone the
- thermal conversion.
MATHIAS PIER.
EUGEN ANTI-IE8.
HANNS SCHAPPERT.
16
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