U.S. patent number 3,655,518 [Application Number 04/877,996] was granted by the patent office on 1972-04-11 for retort system for oil shales and the like.
This patent grant is currently assigned to Metallgesellschaft Aktiengesellschaft, Ruhrgas Aktiengesellschaft. Invention is credited to Heinrich Janssen, Paul Schmalfeld, Hans Sommers.
United States Patent |
3,655,518 |
Schmalfeld , et al. |
April 11, 1972 |
RETORT SYSTEM FOR OIL SHALES AND THE LIKE
Abstract
In apparatus for retorting oil shale, oil sands and similar
materials wherein finely divided solids residue is used as a heat
carrier and is heated in a vertical pneumatic conveyor-burner,
mixed with fresh finely divided solid feed, product distillation
vapors are removed from the mixture, and the solid distillation
residue is returned to the conveyor-burner, the improvement whereby
the propellant gas is introduced axially to the bottom of the
conveyor-burner and the cool heat carrier is introduced thereinto
from a concentric annular chamber thereabout through slits or
openings in the propellant gas conduit by means of a flow of a
control gas. Other specific improvements of portions of the
retorting apparatus and solids circulating system are examplified
and claimed, especially a screw conveyor-mixer retorting
chamber.
Inventors: |
Schmalfeld; Paul (Bad Homburg,
DT), Sommers; Hans (Essen, DT), Janssen;
Heinrich (Hanau, DT) |
Assignee: |
Metallgesellschaft
Aktiengesellschaft (Frankfurt, DT)
Ruhrgas Aktiengesellschaft (Essen, DT)
|
Family
ID: |
5713797 |
Appl.
No.: |
04/877,996 |
Filed: |
November 19, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Nov 20, 1968 [DT] |
|
|
P 18 09 874.3 |
|
Current U.S.
Class: |
202/108; 201/20;
202/118; 201/12; 201/39; 202/230 |
Current CPC
Class: |
C10B
49/20 (20130101); C10G 1/02 (20130101) |
Current International
Class: |
C10G
1/02 (20060101); C10G 1/00 (20060101); C10b
001/06 (); C10b 007/10 (); C10b 047/20 () |
Field of
Search: |
;196/123,126,127,129
;202/121,117,118,108,119,133 ;201/31,32,33,12,20 ;55/435
;208/11 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Edwards; David
Claims
What is claimed is:
1. In an apparatus for the dry distillation of finely divided solid
hydrocarbonaceous material by admixing therewith in a distillation
retort a hot finely divided heat carrier taken from the solid
distillation residue of said dry distillation, which heat carrier
is thereafter separated from the vaporous distillation product and
conveyed pneumatically, separated from the conveying gas and after
reheating is recycled to said distillation retort, said apparatus
comprising
a. said distillation retort having an elongated casing with a feed
end portion and a discharge end portion, and a pair of rotating
worms in said elongated casing,
b. a feed conduit for said hydrocarbonaceous material and
c. a separator containing said hot heat carrier connected to the
feed end of said distillation retort,
d. a product recovery and cooling system adapted to receive
vaporous distillation product,
e. an intermediate hopper adapted to receive solid distillation
residue connected to the discharge end of said distillation retort,
and
f. a vertical pneumatic conveyor connecting said intermediate
hopper and said separator, the improvement comprising
I. inlet conduit means for introducing a free oxygen containing
propellant gas upwardly through the lower end of said vertical
pneumatic conveyor to burn at least a part of the carbonaceous
material in said carrier material to heat it by combustion, and a
concentric annular chamber about said inlet conduit means adapted
to receive said carrier material to be heated from said
intermediate hopper, said inlet conduit means having openings
communicating with said annular chamber, and controlled gas
introduction means communicating with said openings so as to
regulate the amount of said heat carrier material passing
therethrough,
Ii. a first separator to receive the hot carrier material from the
upper end of said vertical pneumatic conveyor comprising in its
upper portion two chambers separated by a downwardly directed wall,
one of said chambers communicating directly with the upper
discharge end of said vertical pneumatic conveyor, the other
chamber having an outlet for gaseous combustion products, a solids
reservoir in the lower portion common to said upper two chambers to
collect hot heat carrier material, and a discharge conduit
connecting said reservoir and the inlet of said distillation
retort,
Iii. a second separator to receive gaseous combustion products from
said first separator to separate entrained dust therefrom,
Iv. indirect heat exchange means connected to said second
separator, to transfer heat from said hot gaseous combustion
products to said free oxygen containing propellant gas for
introduction to said lower end of the vertical pneumatic conveyor,
and
V. conduit means adapted to remove solid distillation residues from
said two separators and said intermediate hopper connected to a
mixing device for cooling and quenching with water said solid
distillation residues for disposal.
2. The apparatus of claim 1 wherein said first separator has a
cross-sectional area in the range of 5 to 20 times the average
cross-section of said vertical pneumatic conveyor and the distance
from the discharge end of said conveyor to the top of said first
separator in the range of 3 to 10 m.
3. The apparatus of claim 1 wherein at least two of said conveyors
operate in parallel and commonly discharge into said first
separator.
4. The apparatus of claim 1 including valve means in said solids
discharge conduit from said first separator and in said conduit
between said intermediate hopper and said annular chamber, said
valve means permitting the build-up of solids in the conduits and
said intermediate hopper.
5. The apparatus of claim 1 wherein said product recovery and
cooling system comprises three scrubbers adapted to progressively
cool said distillation vapors by contact in each with cooled liquid
condensate.
6. The apparatus of claim 1, wherein said mixing device for water
quenching the discharged solids is connected to said product
recovery and cooling system so as to receive condensed water
therefrom.
7. The apparatus of claim 1, including a dust gas separator
connected to said distillation chamber and to the intermediate
hopper so as to receive distillation vapors from said distillation
chamber and to discharge dust recovered therefrom to the
intermediate hopper.
Description
PRIOR ART
Portions of the retorting system of this invention are similar to
apparatus disclosed in U.S. Pat. Nos. 2,788,314; 3,056,248 and
2,983,653.
PREAMBLE
Recently there has been an intensification of efforts to
dry-distill solid hydrocarbonaceous materials such as bituminous
coals, oil shales, oil sands and the like to produced oils, which
may be further converted by hydrogenation and conventional refining
to products similar to natural petroleum products, e.g. gasoline.
Such efforts are being carried on particularly in countries that do
not have a cheap and adequate supply of petroleum, but do have
large, easily workable deposits of coal, oil shale, or oil sand. In
order for an "artificial petroleum" of this kind to be able to
compete with natural petroleum, the content of bitumen or oil in
the starting material must be relatively high, and if possible
should be at least 8 percent, and preferably more than 10 percent.
The starting material should also be able to be mined at moderate
investment and operating costs.
The distillation apparatus used for this purpose should desirably
be able to handle quite large quantities of material in a single
unit. It should yield a high quantity of liquid oil with little
gas, and the apparatus should make the distillation vapors
available for further processing free from admixture with
combustion gases or large amounts of recycled higher distillation
gases. The expenditure of heat and the power requirements of the
distillation process must be low.
Shaft furnaces or retort furnaces are not suitable for a
distillation of such hydrocarbonaceous material, because the
residence time of the distillate vapors in such units is usually
too long and accordingly the formation of gas and residual coke is
too great. Shaft furnaces operating with scavenging or stripping
gas heating or by internal combustion are not suitable either,
because they, require that the starting material be in lumps, and
because the distillate vapors produced in them are diluted by the
scavenging gas or combustion gas.
Neither can the known methods for the dry distillation of a finely
granular starting material in one-stage or multi-stage fluidized
beds be used, because the distillate vapors are diluted by the
fluidizing gas. If the fluidizing gas is produced by the partial
combustion of the starting material or by the admixture of hot flue
gases, the distillation gas then contains nitrogen. This
necessitates a considerable enlargement of the condensation
apparatus and diminishes the value of the distillation gas by
making it unusable directly as a pipeline (e.g. public utility)
gas, as a source of hydrogen for hydrogenating, or as a synthesis
gas.
It is known to carry out the dry distillation of bituminous and
petroliferous materials by means of circulating heat carriers.
Ceramic balls or steel balls are used as the heat carriers, whose
heat is transferred to the material to be distilled by direct
mixing and contact therewith, as in a rotating tube. This procedure
has been known for some time, but it has not been widely used
because the heating and transport of the heat carrier balls through
the heater and the rotating tube or kiln is complicated and
expensive.
The use of finely divided heat carrying agents offers important
advantages, especially if the solid residue from the distillation
of the finely granular starting material can be used as the heat
carrier. Processes and apparatus are known which heat finely
granular heat carriers in a pneumatic conveyor or in a fluidized
bed.
Processes and apparatus are also know in which the heat carrier and
the raw hydrocarbonacous material are mixed by feeding them
together into a shaft retort, thereby heating the starting material
and distilling it. The vapors and gases that are released support
the fluidization and the mixing together of the heat carriers and
the raw material. But this method of effecting mixing in a shaft
furnace is not satisfactory when the quantities of raw material and
heat carrier to be processed are great. This retorting method also
causes increased formation of coke and gas, thereby resulting in
considerable losses in the yield of recoverable oils.
The heating of very large quantities of circulating finely granular
heat carriers in a fluidized bed requires a large capital
investment and frequently results in unsafe operation. Heating in a
pneumatic conveyor is therefore to be preferred.
THIS INVENTION
The invention is directed to an apparatus for the dry distillation
of bituminous or petroleum-containing materials such as coal,
lignite, oil shale, oil sand or the like in a finely granular state
and the winning of a distillate therefrom. The material to be
distilled is heated by means of being thoroughly mechanically mixed
with a circulating, finely divided heat carrier which is thereafter
separated from the distillation vapors along with the solid
distillation residue, heated in a pneumatic conveyor, and returned
to the distillation apparatus.
The requirements for a high oil yield with a low formation of coke
and gas, a rapid and uniform heating of the starting material and a
rapid removal of the distillate vapors from the distillation zone
are effectively met by this invention.
The apparatus according to this invention consists of a vertical
pneumatic conveying and heating unit for the particulate heat
carrier to the bottom end of which a free-oxygen containing gaseous
propellant is fed axially as through a venturi tube and finely
granular thermal carrier is introduced thereinto from a concentric
annular chamber thereabout through slits by means of a flow of a
control gas.
A separator at the upper end of the conveyor is divided by a wall
extending downward from the top into a separating chamber and a
secondary chamber containing the discharge for the propelling gas
and products of combustion, and a bottom solids collecting chamber
that is common to both.
A distillation chamber is connected at its input end to the heat
carrier discharged from the separator. It also receives the raw
material or feed that is to be distilled. At its discharge end, one
conduit carries away the hot mixture of thermal carrier and fresh
solid distillation residue and another conduit carries away the
distillate vapors. The distillation chamber has a screw conveyor or
the like to force and mix the solids along the length thereof.
An intermediate reservoir or hopper is connected at one end to the
distillation chamber and at the other end to the annular chamber at
the bottom of the conveyor.
A dust gas separator is used to remove fines from the distillation
vapors after which they are condensed in a product recovery system
in which the vapors are condensed by spraying them with previously
separated and cooled condensate.
Another dust separator cleans the products of combustion discharged
from the conveyor-separator and the gas is then utilized in heat
exchange to heat the incoming propellant gas and/or in a waste heat
boiler.
The particulate solids removed from the process are cooled,
preferably with water, in a solids cooler.
The finely divided solid distillation residue which serves as the
heat carrier is carried and simultaneously heated in a vertical
pneumatic conveying and heating unit and then is separated from the
combustion gases by free fall and inertial ejection in a separating
chamber, and delivered to a mechanical mixer in the distillation
chamber. In the mixer the thermal carrier, heated to 700.degree.
C., for example, is combined with the finely granulated starting
material that is to be distilled, e.g., coal, oil shale, oil sand
or the like, and blended intensely therewith within seconds. A very
rapid transfer of heat from the thermal carrier to the finely
granulated starting material takes place. This heat quickly brings
the starting material to the desired distillation temperature,
usually between 450.degree. and 650.degree. C., breaks down the
bitumen, and/or drives out in vapor form the oils contained in or
developing from the raw material, together with water vapor formed
from the moisture and from chemically bound water. The formation of
light cracked gases while this is taking place is extremely
slight.
The mixture of thermal carrier and fresh distillation residue flows
from the distillation chamber into an intermediate reservoir or
hopper for the after-distillation of the feed material and for the
driving of hydrocarbon vapors from the interstices and pores of the
solids as by the injection of water vapor returned light
distillation gases into the mixture. The solids are then fed back
into the bottom part of the pneumatic conveying and heating unit,
thereby completing the cycle of the thermal carrier through the
heating and distillation steps.
The apparatus of this invention permits an effective and simple
distillation of finely granulated oil-bearing materials, the
condensation of the distillation vapors, and a good recovery of
heat from the waste gas from the heating of the thermal carrier.
The distillation vapors from the mixer-distilling chamber are
processed in a cooling system providing for several stages of
contact of the distillate vapors with their own cooled condensate,
while the cooling of gases from the heater-conveyor is performed in
an air preheater and/or a waste-heat boiler.
The specific investment costs of large units embodying this
invention are low. The consumption of heat and power by such units
is also low.
THE DRAWINGS
FIG. 1 is a flow diagram of an installation according to the
invention;
FIG. 2 is a sectional view in elevation of the distillation chamber
taken along the axis thereof and showing in particular the
mixer-screw conveyors;
FIG. 3 is a sectional view of the distillation chamber taken
perpendicular to the axis thereof; and
FIG. 4 is a horizontal sectional view of the conveyor-solids
separator in one alternative embodiment of this invention.
DESCRIPTION
FIG. 1, is the vertical pneumatic conveying and heating unit, 2 is
the conveyor-separator for the separation of the thermal carrier
from the combustion gases, 3 is the mechanical mixer-distillation
chamber and 4 is the intermediate reservoir when the solids are
finally stripped of hydrocarbon gases.
Separator 2 and the retort-mixer 3 are connected by the feed line
5, which in its lower portion has a closing and flow regulating
slide valve 17, thereby permitting a dense, gas-blocking
accumulation of solids in line 5 above the valve. In like manner,
the intermediate reservoir 4 and the conveyor-burner unit 1 are
connected by a feed line 7, which has a closing and flow regulating
slide valve 25 in its lower portion, thus also creating a dense,
gas-blocking accumulation of the solids above the valve 25. These
blocking accumulations in the lines 5 and 7 separate the
retort-mixer 3 and the intermediate reservoir 4, in which the
distillate vapors and a gas of high heat value flow, from the
bottom portion of the conveyor-burner unit 1 in which there is air,
and from the separator 2 in which combustion gases are flowing.
The combination conveyor and heating unit 1 is constricted in its
bottom portion where the mixture enters through slits or openings 9
into the conveying tube 1 which is constricted into venture at its
entrance at the openings 9. Propellant air, which is preferably
preheated is introduced from the bottom by conduit 10 from which it
flows upward, taking with it the mixture flowing in through the
openings 9, burning the carbon contained in or attached to the
mixture and thereby heating the mixture to the desired temperature
of, for example, 700.degree. C. If the mixture should not contain
enough carbon to heat it sufficiently, additional fuel is
introduced into the propellant air through line 65 and nozzle 66,
in the form, for example, of gas, waste oil or coat dust in a
proportioned amount.
The combustion takes place very rapidly and the heat that is
released is immediately transferred to a great extent to the solids
of the mixture. Overheating or great temperature differences
between the combustion gases and the solids does not occur. This
rapid temperature eqalization also makes it possible to preheat the
propellant gas to a high temperature, so that excess air can be
reduced to a minimum. The rate of flow of air and the rate of flow
of any fuel that may be added are adjusted so that no more than the
required heating of the mixture is achieved in the conveying unit
1.
Conveying unit 1 is generally 20 to 40 m. long and it is desirable
that it flare from the bottom to the top, either at a constant rate
or in a step-wise manner. In the bottom part the velocity of the
air or combustion gases must be higher, e.g., 30 to 40 m./sec., in
order to accelerate the mixture and in the upper part the velocity
can drop to 15 to 25 m./sec.
The solids from reservoir 4 and feed line 7 run from the annular
chamber 11 surrounding the conveyor unit 1 to the openings 9 in the
latter. It is desirable for each opening or slit to receive a
controlled feed of secondary propellant-control air through the
nozzle 53 to drive the mixture in as well as control, by its rate
of flow, the amount of mixture which it injects. In this manner the
mixture is introduced around the entire periphery of the conveyor
unit and charges it evenly, which is especially important where the
diameter of the conveyor is great, e.g., 1 meter or more. Since the
rate of flow of the propellant air is individually adjustable at
each slit, the recirculated material can be introduced in
relatively greater amounts at the individual slits, if this becomes
necessary.
It is very important to separate the conveyed and hot solids from
the propellant gas in such a manner as to prevent abrasion of the
apparatus walls and the formation of any large amount of fine
debris. This requirement is met by the arrangement of the
conveyor-separator 2. The vertical conveyor unit empties into a
greatly expanded separating chamber 13 of unit 2, which has from 5
to 20 times, and preferably 7 to 12 times the cross-sectional area
of the conveyor. The velocity of the propellant gases drops greatly
in this chamber. The flow of gas is obliged to pass around a
vertical partition wall 12 which extends downward from the cover,
so that the solids are ejected from it because of the abrupt change
in direction. The gas thus separated flows upwardly through the
adjacent chamber 14 of unit 2 to an outlet 60.
Separator 2 is designed in its lower portion so as to serve
simultaneously as a collecting reservoir or hopper 15 for the hot
solids. Hopper 15 communicates with both the large separating
chamber 13 and with the smaller adjacent chamber 14. Chamber 14 can
be made larger or smaller by varying the position of the partition
12. This may be important because the upward velocity of the hot
combustion gases in chamber 14 is determined by the cross section
of this chamber. This upward velocity, in turn, is what determines
the amount of the finely divided solids that are separated or fall
out into hopper 15.
The distance between the cover of the separating chamber 13 and the
top edge of the vertical conveyor 1 amounts, according to the
invention, to from 3 to 10 m., and preferably 5 to 7 m. At this
distance practically no wear is observed in the cover of the
separator. The separator is preferably provided with a
wear-resistant ceramic lining.
A cyclone separator can be used instead of the separator 2, to the
bottom of which a collecting hopper can be connected. In this case
the upper end of the conveyor is turned 90.degree. to the
horizontal and connected to the cyclone separator.
A narrow feed line 5 runs from the lower portion or collecting
hopper 15 to the input of the mechanical mixer-retort 3. In the
lower portion of line 5 is a slide valve 17 by which control can be
exercised over the amount of heated solids that are continuously
fed to the mixing mechanism. Valve 17 provides for the formation of
dense accumulation of the solids above the valve. To accommodate
thermal expansion, it is desirable for feed line which is
preferably ceramically lined to have an expansion joint 16 above
valve 17 which joint can also be equipped with a feed line 18 for
an auxiliary gas, such as water vapor.
The finely granular feed to be distilled, e.g. tar, sand, oil
shale, or asphalt is fed from the hopper 19 through line 20 into
the distillation chamber 3, in which it is rapidly and
energetically mixed with hot solids from conduit 5. Within a few
seconds the finely granular raw material is raised by rapid heat
transfer to a prescribed temperature between 450.degree. and
650.degree. C., so that the bitumen is decomposed and the oils are
released in vapor form by dry distillation. At the same time the
moisture and the chemically bonded water in the solid feed are
released in vapor form. In addition, a small amount of distillation
gas develops, amounting to about 5 to 100 standard cubic meters,
and usually to 10 to 40 standard cubic meters per ton of starting
material.
The mixer-retort 3 is illustrated in longitudinal section in FIG. 2
and in cross section in FIG. 3. It has two shafts 21 which rotate
in the same direction, each bearing two vanes 22. The vanes of the
two shafts are 90.degree. out of phase and interplay with one
another and carry the material being mixed around the two shafts.
This circulation is produced by the fact that one vane of the
mixing shaft strips the material being mixed from the other mixing
shaft, carries it around the shaft in its own area of movement, and
yields it back to the other mixing shaft. In the stripping action
the space filled with the material being mixed constantly changes
its form, the material in the marginal portions being pushed to the
interior and the material in the inner portions being pushed to the
margin.
The vanes 22 are preferably mounted on the shafts in a spiral or
worm manner and thus also advance the mixture forward, axially
along the shafts. The spiral shape of the vanes also promotes a
more uniform stressing of the mixing shafts and of the transmission
that drives them. The forward movement of the mixture can be aided
by tilting the mixing shafts downward from the horizontal by
5.degree. to 45.degree., preferably 20.degree. to 30.degree.. The
interplay of the vanes of the two shafts produces a mutual cleaning
of the shafts on all but a lens-shaped cross section around the two
vanes of each shaft. If deposits in this lens-shaped cross section
cause trouble, the vanes themselves can be bent or curved
accordingly. The vanes of the two shafts additionally clean the
mixer housing in the areas of their movements.
The vanes 22 are best welded directly onto the mixing shafts 21. It
is advantageous to avoid making them continuous so as to prevent
damage by thermal expansion. The vanes are therefore interrupted by
by gaps of 1 to 10 mm., preferably 2 to 5 mm., at intervals of 100
to 500 mm., preferably 150 to 300 mm. Continuous vanes can also be
interrupted by notches extending nearly to the welding seam and can
be made more elastic. The vanes and mixing shafts are exposed to
only slight wear, and can be made of ordinary steel or from a
material of slightly higher wear resistance. It is important,
however, to equip the edges of the vanes with a highly wear
resistant deposit as by welding material, or to make them of hard
steel inserts that are replaceable and can be fastened on by
screws, clamping or welding.
Distillation chamber 3 has to handle material with an average
temperature of 450.degree. to 650.degree. C., and only in
exceptional cases does it come in contact with heated solids of a
temperature of up to 750.degree. C. To cool shafts 21, it is
desirable to use hollow shafts to which a coolant is fed through a
pipe extending all the way to the end of the bore in the hollow
shaft, returning it through a bore around the infeed pipe. Water is
normally used as the coolant. To keep the heat loss because of the
cooling of the mixer shafts to a minimum, circulating oil can be
used having a temperature around 200.degree. to 250.degree. C., or
some what similar coolant suitable for high temperatures can be
used. It is best to leave the other parts of the mixer
uncooled.
The mixer shafts 21 equipped with the spiral vanes 22
advantageously have short spiral sections 54 at the inlet, so as to
positively feed the solids. The spiral sections 54 and the vanes 22
of the mixer shafts 21 are connected to one another by transitional
pieces of appropriate shape. The raw feed can also be blown in
together with returned light distillation gases. These gases can
also be used for the purpose of more rapidly removing the vapors
and gases formed in the mixer.
The housing 55 of the mixer 3 is preferably insulated and equipped
with a masonry lining in the bottom part and in the side parts, and
is given an external covering of metal plate welded to form a
hermetic seal. The cover is also preferably insulated. The cover
plate, however, can also be welded on without inside insulation, or
it can be at least partially attached by screws, so as to be easily
removed for inspection of the interior of the mixing mechanism. The
cover plate as illustrated is externally insulated.
Between the area of movement of the mixer shafts 21 and the cover
plate, a free gas collecting chamber 56 is left so as to permit a
more ready passage of the vapors and gases formed in the mixer.
This chamber 56 is enlarged at the outlet end of the retort 3 to
form a dome 50 to draw off the vapors and gases to the condensation
apparatus. This suppresses the entrainment of dust into the
condensation apparatus. Chamber 56 is advantageously constructed in
such a manner that the velocity of the vapors and gases does not
exceed 10 m./sec., if possible, while it can increase to 20 m./sec.
and more in the pipe 51 leading to the condensation or product
recovery apparatus. The velocity in chamber 56 must also not be too
low, because a long residence time of the vapors favors secondary
reaction, particularly of the high-boiling hydrocarbons.
Distillation gas fed back into mixture-retort 3 supports the rapid
removal of the vapors and gases and suppresses secondary
reactions.
The mechanical mixer-retort 3 with the two mixer shafts 21
revolving in the same direction permits the rapid and intense
mixing of the solids even at high throughput, and permits
distillation within a few seconds when large amounts of finely
granular heat carrier. The abrupt heating achieved prevents the
extensive decomposition of the oil vapors and makes possible an
optimum yield of liquid hydrocarbons from the starting
material.
Pneumatic mixing systems have proved impractical at high flow rates
because large amounts of steam or returned distillation gases are
required for the pneumatic propulsion. This places an unnecessary
burden on the condensation apparatus. Mechanical mixers of other
kinds do not mix rapidly or intensely enough, and they excessively
comminute the material and are not self-cleaning.
The present invention, however, is not necessarily directed to the
use of a mixer having 2 mixer shafts revolving in the same
direction, and in some cases simpler mixers using vertical mixer
shafts can be used.
The starting material is substantially completely distilled in the
distillation chamber 3 and, still mixed with the heat carrier, it
flows down through line 23 at the end of the mixer into an
intermediate hopper 4, where the mixture accumulates, the transfer
of heat from the heat carriers to the starting material is
completed, and the distillation of the starting material is
completed.
The solids are continuously drawn from hopper 4 through conduit 7
to the annular chamber 11 of the vertical conveyor-burner 1. In the
bottom part of the conduit 7 there is provided a slide valve 25
with which the rate of flow of the mixture into the annular chamber
11 is controlled. Valve 25 brings about the formation of a dense
accumulation of the solids above the valve and up into the
intermediate hopper 4.
The intermediate hopper 4 tapers towards conduit 7. In this tapered
portion it is desirable to install a diffuser 26, in the form, for
example, of a tubular ring with outlet orifices, so that steam or
returned light distillation gas can be fed through line 27 and
distributed by means of the diffuser 26 into the solids. The steam
or gas introduced in this manner drives hydrocarbon vapors out of
the interstices and pores of the solids. According to the
invention, the time of stay of the solids in the intermediate
hopper for post-distillation, the driving out of hydrocarbon vapors
and the compensation of certain irregularities that may occur in
the circulation of the solids is about 0.5 to 5 minutes, preferably
1 to 2 minutes. The size of the free gas space in hopper 4 is
desirably at lease equivalent to a possible detention time of the
solids of 1 to 2 minutes, to permit accumulation thereof in case of
a process interruption. Hence, the hydrocarbon vapors would
normally flow only slowly through the free gas space in the
intermediate hopper, and could be decomposed by secondary
reactions. Consequently it is desirable to introduce steam or
distillation gas in such a quantity that the detention time of the
hydrocarbon vapors in the free gas space of the intermediate hopper
does not exceed 1 to 2 seconds.
The hydrocarbonaceous feed material has a particle size of less
than 6 mm., and preferably less than 4 mm. If the grains
decrepitate easily, a feed grain size of up to 2 mm. can be used.
The maximum particle size is determined by the requirement of
performing the distillation all the way to the center of the grains
during the short time of stay in mixer-retort 3, so as to achieve a
high yield of oils.
The solid residue remaining after the distillation of the starting
material is preferably used as the heat carrier. Depending on the
starting material, the size of the grains of this residue remains
approximately equal to the particle size of the starting material,
or it may shrink or swell slightly. In many cases, it may tend to
crumble.
The residue that serves as the heat carrier preferably has a
particle size greater than 0.2 mm., so that the separation in
separator 2 can be effected readily with only small quantities of
inder dust being carried into the condensation apparatus by the
vapors and gases. The recirculation of the heat carriers produces a
constant attrition creating dust, most of which is carried out of
the circulating system with the combustion gases.
A rather large amount of particulate solid residue is freshly
formed continuously by the distillation process, and this is
removed from the circulation system as by conduit 61 connected to
intermediate hopper 4. At this point, however, there is a portion
of freshly distilled residue which has not yet passed through the
conveying and heating unit 1 and has therefore a carbon content. To
enable the solids residue to be free of carbon when brought into
contace with the air, excess residue can be removed by line 28 from
hopper 15 of the separator through a cooler 43 to the dump.
The vapors and gases liberated in the distillation are collected at
the discharge end of the mixer-retort 3 in the enlarged gas dome
50, to which the vapors and gases formed in the intermediate hopper
4 are also passed, and from there they are fed through conduit 51
to a dry dust gas separator 29. The gas separator 29 is preferably
in the form of one or more cyclone separators in parallel or
series. The dust that is removed is fed through line 30 into the
bottom portion of the intermediate hopper 4 or into line 7, and
thence to the conveyor-burner.
The vapors and gases flow from dust gas separator 29 through
conduit 68 into a cooling or product recovery system 69, in which
they are scrubbed and cooled by means of cooled condensate. This
treatment is best performed in a plurality of stages, three for
example. In the first stage 30, the heavy oil condensed is used for
the cooling of the vapors and gases. The heavy oil practically
completely absorbs from the vapors and gases any dust that has not
been eliminated by the dry dust separator. The recirculated oil can
be cooled in a heat exchanger 31 by water, air or the like, or the
cooling can also be brought about by the production of low-pressure
steam. If the utilization of the waste heat is not considered
important, one simple solution is to spray water into the scrubber
30 and evaporate it. The amount of water is then so proportioned
and the temperature of the vapors and gases so adjusted that as
much heavy oil condenses in the scrubber as is necessary to keep
the heavy oil with its dust content satisfactorily fluid and
pumpable. The vapors and gases are in this case cooled to a
temperature between 200.degree. and 300.degree. C. The temperature
can, however, be reduced still further in order to make more oil
condense and to obtain a more greatly diluted heavy oil.
In the second stage of the cooling system, in the scrubber 33, the
gases and vapors are cooled by recirculated medium oil to such an
extent that the oil vapors condense substantially, but no water
vapor precipitates. This is the case when the temperature of the
vapors and gases at the discharge of scrubber 33 is slightly above
100.degree. C. The circulating medium oil is recooled for this
purpose in a heat exchanger 34 by water, air or the like. The
injection and evaporation of water is impractical in scrubber 33,
because it is difficult to completely vaporize the water at the low
temperatures and thus keep the circulating oil free of water. The
excess medium oil taken from the circulation is practically free of
dust and water and can be used directly for further processing or
can be delivered to the storage tank.
In an additional stage of the cooling system 69, the
scrubber-cooler 35, the remaining mixture of gases and vapors is
chilled to about 30.degree. C. by sprinkling with their own
condensate and water. This recirculated water is best cooled by air
in a first cooler 59 and indirectly in a second cooler 62. The
condensed light oils and the gasoline are separated from the
process water in a separating tank 36. In this cooling stage the
light oils, gasoline and water vapor condense. At this point an
indirect cooler with cooling surfaces can also be used. The
distillation gas which is saturated with water vapor and gasoline
vapors at the cooling temperature, is left behind. The gasoline
vapors still contained therein can be recovered by scrubbing with
light oil, by compression of the gases and then cooling them, or
also by intense cooling. A portion of the light distillation gas is
fed back as scaventing gas to the mechanical mixer 3 and the
intermediate hopper 4.
The light distillation gases have a high content of C.sub.1 to
C.sub.3 hydrocarbons, and furthermore contain hydrogen, carbon
monoxide and often carbon dioxide, too. They have a high heat value
and are practically free of nitrogen. They can be sold as a public
utility gas or can be processed to yield synthesis gas or
hydrogen.
The combustion gases which have heated and driven the circulating
heat carrier upward in the conveyor-burner unit 1 and have been
separated from the carriers in the separator 2 pass from the
chamber 14 through conduit 60 into a cyclone 37 in which the
entrained dust is substantially separated from the gases. This dust
can be fed back through line 38 into the feed line 5 or directly to
the mechanical mixer-retort 3. Preferably, this dust is ejected
from the process, e.g., through conduit 39, in order to keep the
percentage of dust in the circulating solids low.
It is desirable to connect to cyclone 37 an air preheater 40 and a
waste heat boiler 41 with a steam collector 64 for the production
of steam, so as to utilize the waste heat from the waste gases. In
some cases it might be better to place the waste heat boiler 41
first and the air preheater 40 second in the waste gas line.
In air preheater 40 air is compressed in blower 63, that is needed
for the conveyor-burner 1 and is preheated. It is advantageous to
design the air preheater 40 and the waste heat boiler 41 in such a
manner that the heat of the waste gases is substantially utilized,
but the temperature should not be lowered below the dewpoint if the
gases contain sulfor dioxide.
After the heat of the waste gases has been utilized, dust must be
thoroughly removed from them before they can be passed through a
smokestack into the open air. A mechanical or electrical dust
remover 42 or a conbination of both can be used. This dust remover
can also be connected to a wet scrubber if the circumstances
require it. Since the apparatus according to the invention is used
in large units of high output and consequently very large amounts
of waste gases have to be released into the atmosphere, their
content of fine dust must be very low. This can only be achieved in
may cases by an electrical fine cleaning in the final stage. Wet
scrubbing is involved when the waste gases are rich in SO.sub.2 and
the SO.sub.2 is to be recovered.
The dust drawn from cyclone 37 through conduit 39 and from the dust
removers 42 through pipe 67 has to be cooled and moistened so that
it can be handled, transported and dumped without creating a
nuisance by producing great clouds of dust. All of the solid
residue that is to be dumped can be introduced into cooler 43. The
cooling and moistening of the hot residue is performed preferably
in a mixer 43 which, like mixer 3, contains two mixer shafts
rotating in the same direction and equipped with spirally curved
vanes. At the point where the dust is fed in, a line 44 is
connected which carries water, preferably condensate produced in
the process. By the spraying in and evaporation of the water the
dust is cooled to a temperature below 100.degree. C. and can be
brought to a moisture content either of 24 - 4 percent, for
example, or as high as 10 to 20 percent, if desired.
If the apparatus according to the invention is used for the
distillation of coals, large quantities of coke are produced in
addition to tar. This coke is used as the circulating heat carrier
and is consumed in small quantity to supply the fuel requirement in
the conveying and heating unit 1. The large mass of the coke
ejected from the circuit can be burned in a power plant or, if it
is possible and profitable, it can be used as a sintering fuel, as
a leaning material in coking works, or as a tar-free reducing fuel
in dust form. This residue coke can also be briquetted and the
briquettes can be treated to serve for house heating purposes or as
blast-furnace coke. In the distillation of coal, experience
dictates the maintenance of a temperature between 550.degree. and
650.degree. C. at the discharge of the mixer-retort 3 and in the
intermediate hopper 4 in order to obtain a maximum yield of tar.
Experience shows that this yield amounts to about 100 to 170
percent, depending on the type of coal, of the tar content that can
be detected in the starting coal by the low-temperature
carbonization analysis according to Fischer and Schrader. The
apparatus is suitable for use both with coking and with non-coking
coals.
Oil shale has an oil content of 2 to better than 30 percent by
weight, depending on its source. Oil shales of different types and
origins can be processed in the apparatus according to the
invention. Experience shows, however, that the oil content should
not be less than 8 percent, and preferably not less than 10
percent, in order to make it sufficiently profitable to work. In
detail, profitability depends on the cose of decomposing the oil
shale, the region in which the oil shale is located, and the price
of natural petroleum at the point of use of the shale oil. A
special economic advantage is had when the oil-shale residue can be
used in whole or in part for special purposes and does not have to
be simply wasted by dumping it. Depending on the composition of the
residue, it can be used as a hydraulic binder, as raw material for
the manufacture of cement, for the production of bricks, or for the
recovery of aluminum oxide, uranium oxide or the like.
Oil shale having an oil content of more than 20 percent is often
plastic by nature, or becomes plastic upon passing through a
certain temperature range. The apparatus according to the invention
can be operated without any trouble even with oil shales that
behave plastically in the cold or hot state.
The oil yield from oil shale differs according to its character. In
comparison with the oil production that can be achieved in the
Fischer analysis, yields between 95 and 110 percent by weight are
achieved in the apparatus according to the invention.
Oil sands are often hard to work, because they may become plastic
even at temperatures of around 20.degree. C. and tend to cake up.
By the use of appropriate mechanical crushers, especially toothed
roller mills, a crushing to under 10 mm. can be achieved. If the
broken material has an undesirable tendency to cake up before its
introduction into the mechanical mixer-retort 3, it is advantageous
to add finely granular residue from the distillation of the oil
sand to the crushed material immediately after it is crushed, thus
keeping it from sticking together. Often the oil sand has a
tendency to stick undesirably to the walls of the crushers and
transporting means. This sticking can be completely prevented if
the walls are heated by low-pressure steam or the like.
In oil sand, the oil is present in petroleum form. The same is the
case with oil shale. In the case of distillation in the apparatus
according to the invention, an oil yield of 95 percent of the oil
content determinable by extraction can be achieved if the proper
distillation temperature is maintained and the residence time of
the oil vapors in the hot part of the apparatus is kept short. By
using a somewhat higher distillation temperature, the character of
the overall oil production can be improved, with a lower overall
yield.
The apparatus according to the invention can be made in large units
of high output capable of distilling 200 to 400 metric tons per
hour of coal, oil shale, oil sand or the like. If a total oil yield
of 10 percent by weight is assumed, 20 to 40 metric tons of oils
can be produced per hour in one unit, corresponding to 160,000 to
320,000 tons of oil per year. The inside diameter of the conveying
and heating unit 1 should not be much greater than 1,500 mm., on
the basis of past experience. For high throughputs, therefore, 2 to
4 conveying units can be connected in parallel to one sifter 2.
FIG. 4 indicates how, in an apparatus having a plurality of
parallel conveying units, the separating chamber 13 of the sifter 2
is subdivided by cross partitions 44, so that if one conveying unit
fails it will not be packed full by the others that are in
operation.
The capacity of the mechanical mixer-retort 3 is also limited. In
the case of a temperature difference of 100.degree. - 150.degree.
C. between the hot heat carrier flowing into the distillation
chamber 3 and the solids emerging from the intermediate hopper 4,
the amount of circulating solids that is required is normally 4 to
8 times the weight of the starting material that has to be
distilled. Consequently the distillation of 200 to 400 tons of
starting material per hour requires 800 to 3,200 tons of
circulating solids per hour. The mixing together of these great
quantities is advantageously divided among a plurality, preferably
two to four mixer-retorts 3, which are disposed and operated in
parallel underneath a common separator 2. Whether to associate a
separate intermediate hopper with each mixer-retort 3 must be
decided from case to case. FIG. 4 is a top view of a cross section
through the apparatus 2 with the openings of three parallel
conveying and heating units 1 in the separating chamber 13 equipped
with the partition and the two cross-partitions 44. Two mixers 3
and one intermediate hopper 4 underneath the apparatus 2 are
indicated by broken lines.
* * * * *