close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2410076

код для вставки
Oct. 29, 1946.
.
¢_ |-|_ HUGHES
. ` _
2,410,074
APPARATUS FOR PYRQLYTIGALLY TREATING HYDRocARBoNs
Filed Nov. 18, 1945
'
4 Sheets-Sheet l
M5775' GAS
`
uw
?, 5111-4
BY
a. @Säumn
ATTORNEY
»
Oct. 29, 1946.
. Q_ H_ HUGHES
ì
‘
2,410,074
APPARATUS FOR PYROLYTICALLY TREATING HYDROCARBONS
Fíled‘NQV. 18, 1945
'4 SheètS-Sheet
INVEN'ToR
CHA fPL Es, HH uc; Hfs
`
'
.
ATTORNEY
Oct. 29,- 1946.
, C. H. HUGHES
2,410,074
.ÀPPARATUS’FOR PYROLYTICALLY TREATING HYDROCARBONS
Filed NOV. 18, 1945
.
4 Sheets-Sheet 4
l BYG" @t
ATTORNEY
2,410,074
Patented Oct. 29, 1946
UNITED STATES PATENT OFFICE
2,410,074
APPARATUS FOR PYROLYTICALLY
TREATING HYDROCARBONS
Charles H. Hughes, Glen Ridge, N. J., assignor to
Hughes By-Product Coke Oven Corporation,
New York, N. Y., a corporation of New York
Application November 18, 1943, Serial No. 510,760
'7 Claims.
(Cl. 19E-104)
2
1
It is an object of the present invention to pro
vide a method for the pyrolytic conversion of hy
drocarbons commercially and on an industrial
scale with yields high enough to makev it econom
ical to carry the process into practice on a com
The present invention relates to a method of
pyrolytically treating hydrocarbons to cause the
conversion thereof, and, more particularly, to a
method of pyrolytically treating in a broad crack
ing and coking oven straight chain hydrocarbons,
mercial scale. with resulting benefits to the public
generally and to industry specifically.
It is another object, of the invention to provide
like paraffin hydrocarbons occurring in petroleum
and the like, to convert them into aromatic hy
drocarbons, such as benzol, toluol, Xylol, naph
thalene,V anthracene, and the like, While evolving
vapors containing straightl chain hydrocarbons
a process for the cracking of straight chain hy
drocarbons and their conversion into aromatic
hydrocarbons with high enough yields to Warrant
industrial operation.
Furthermore, the invention contemplates the
from a- fluid hydrocarbon mass and carbonizing
the residue thereof into coke, and to an improved
cracking and coking oven to carry the aforesaid
methods into practice.
Heretofore, various methods have been used
in converting one hydrocarbon into another.
Generally speaking, such conversions were con
ducted ina variety of metal equipment, includ
ing stills, cracking units, etc., etc.
provision of a vapor cracking oven having a spe
cial structure which is capable of heating a fluid
hydrocarbon mass to evolve hydrocarbon vapors
therefrom and to carbonize the residue into coke,
thereby effecting the pyrolytic treatment of the
In recent
years, attempts have been made to conduct the 20
evolved vaporsy containing straight chain hydro
carbons and their conversion into aromatic hy
pyrolytic conversion of hydrocarbons in ovens,
drocarbons, such as benzol, toluol, Xylol, naph
such vas coking ovens oi’ the broad type. Various
thalene and anthracene, and the like. _
diiiiculties were encountered and unsuccessful re
Moreover, the invention likewise contemplates
the provision of a cracking and broad coking
oven in which the tar and carbon resulting from
the pyrolytic treatment of hydrocarbons can be
made into a high carbon coke having a true spe
cific gravity of 2 plus and suitable for the manu
facturing of carbon electrodes.
suits Were obtained, including failures in certain
instances. The most serious diñiculties were the
choking-up of channels and conduits with carbon,
soot, and the like, the production of lovv- yields of
aromatic hydrocarbons, the poor coking of the
residue of fluid hydrocarbon masses, and the 10W
grade and bad quality of coke which was pro->
duced. In attempts at actual commercial opera
tions of the pyrolytic conversion of hydrocarbons
It is still a further object of the invention to
provide a cracking and coking oven of novel and
improved design providing a heating system for
the distillation of heavy Ipetroleum and also a
separate heating system within the same oven
on a commercial scale, the results were so bad
that the operations were given up as commercial
ly unadvisable and were considered as industrial” 35
failures. Although various endeavors were made
to overcome the foregoing difficulties, none, so far
as I am aware, has been wholly satisfactory for
commercial operation conducted on an industrial
scale.
'
f .40
The present invention involves the discovery
that in cracking-hydrocarbon vapors evolved dur
structure for the cracking of ' the oil vapors
ing the coking of petroleum residues, fory instance,
for the production of aromatic hydrocarbons, it`
vapors in such a manner as to cause the oil va
and the pyrolysis of parafñns for the production
of aromatic oils and` other aromatic hydrocar
bons.
It is also an object of the invention to provide
an improved broad cracking and coking oven hav
ing the Walls of the vapor flues constructed with
uneven surfaces to produce turbulence of the cil
pors to contact the hot wall surfaces, whereby
is necessary to control not only the direction ofi 4.5 eiîective pyrolytic treatment of hydrocarbons can
be conducted.
flow of the vapors and» the temperature of the
4 ItV is Within the contemplation of the inven
cracking fluids, but also the space velocity'and the
turbulence of the vapors. It has likewise been
discovered that a cracking oven, having a special
structure, must be provided in order to properly` »
tion to provide a cracking and coking oven of
novel and improved character providing an in
creased and positive control of the flow and ve
carry out the pyrolytic conversion of hydrocar
bons while at the same time heating fluid hydro
carbon masses tc evolve hydrocarbon vaporsL and
to carbonize the 'residue into good coke having
locity oi the oil vapors' through the vapor ?lues,
an increased and positive control of the air to
be preheated and of the Waste gas from the oven,
and an arrangement of structural elements
acceptable qualities and properties.
55 capable of >causing the air Which‘is' being heated
2,410,074
3
4
to ascend and of causing the waste gas which is
in said vapor ilues for controlling the ilow of
the vapors;
Fig. 3 is a sectional View taken on the line 3-3
being cooled to descend, whereby uniformity of
ñow and an effective change of temperature of
the different streams are obtained.
of Fig. 2 showing the series flue heating system
The invention also provides a broad cracking
and coking oven having a series o-f interdepend
ent and interconnected heating ñues extending in
a single continuous, serpentine character under
located directly under the door of the oven;
the entire sole of the oven to afford a continuous
Fig. 4. is a sectional View taken on the line
@-4 of Fig. 2 illustrating the longitudinal uneven
walls forming the ilues through which the vapors
flow and are heat treated and cracked;
Fig. 5 is a sectional view taken on the line 5-5
stream of the heating gases throughout the whole 10
of Fig. 2 and shows the upper transverse heating
sole flue heating system and having a multi
system located above the coking chamber and
plicity of ,burners in the series fiues to furnish
directly under the vapor iiues, shown in Fig. fi;
a continuous flow of hot gases throughout where
Fig. 6 is a plan section of the nues taken on
by uniform heating conditions in all parts of
15 the line 6_5 of Fig. 2 directly below the regenera
the oil charge are obtained.
tor checker-brick to show the iiow of waste gas
Another object of the invention is to provide
and incoming air to and from the vertical re»
an improved cracking and coking oven having
a system of heating flues so designed as to con
generators;
vious to the infiltration of oil or tar, such as re
upper part of the oven is a cracking chamber
Fig. 7 is a perspective showing a line diagram
duct the products of combustion to each succeed
of
the upper and lower heating systems, regener
20
ing flue _in series for the purpose of using said
ators, gas piping, stacks and the Isley system for
waste products to prevent high heats or hot
reversing the air through the regenerators and
spots in the vicinity of the fuel burners and to
lower heating iiues and the travel of the exit
lengthen the name by means of the increased
waste gases through the Isley ejector to the at
velocity necessary for proper heat transfer, the
increased velocity being due to the increased 25 mosphere; and
Fig. 8 is a sectional view -of the special L and
volume of gases constantly circulating through
orifice provided for the regulation of fuel gas.
all heating flues.
Broadly stated, the present invention contem
A further object of the invention is to provide
plates
the pyrolytic conversion of hydrocarbons,
a cracking and coking oven in which the direc
such
as
the production of aromatic hydrocarbons
30
tion of ñow of the hot gases through the heating
from hydrocarbon vapors evolved from the heat
flue system can be reversed, thereby insuring' ,
ing of petroleum residues and the like. By con
uniform heating over the entire floor of the oven.
trolling the direction of flow of the vapors in the
The invention likewise contemplates the pro
oven and through the cracking chamber and the
vision of an arrangement of gas burners in the
control of temperatures in the cracking chamber
new cracking and coking ovens in such positions 35
while at the same time controlling the space
that the flames, which burn constantly and at
velocity and turbulence of the vapors, relatively
both ends of the oven at the same time, will
high yields of aromatic hydrocarbons, such as
change direction with the reversal of gases
benzol, toluol, and Xylol, are accomplished. In
through the heating ñues, moving back and forth 40 carrying the foregoing operation into practice,
from one heating flue to another adjacent flue.
large quantities of gases are produced from the
Still further objects of the invention are the
petroleum residue or the like, under treatment,
provision of an independent upper `heating sys»,
as Well as tar and carbon, which are converted
tem associated with the roof of the oven and
into useful coke. All of the foregoing operations
consisting of a multiplicity of separate heating 45 are conducted in a single structure having coop
flues disposed horizontally, transverse to the
erating elements which reduces the cost of man
oven and oil vapor flues, for providing the con
ufacture and eliminates the operating difficulties
trolled heat required for pyrolytically treating
of prior operations. Good results and high yields
the hydrocarbons in the oil vapors flowing
of aromatic hydrocarbons and electrode coke can
through the super-imposed vapor flues; of a gas 50 be obtained from the processing of, for instance,
or oil burner at the end of each separate ilue so
a low grade A. P. I. cracked petroleum residue
as to control the transfer of heat to the oil
which is charged into the cracking oven at 700°
vapors as required in various sections of the
F. The single structure involves abroad crack
vapor cracking flues; and of refractory mate
ing and coking oven with a heating system adapt
rials best suited for rapid heat transfer, such as 55 ed to operate with either rich fuel gas, such as
silicon carbide, for the ñocr of the overland the
coke oven gas, oil gas, or with liquid fuels, such
ñoor of the oil vapor flues and other super-duty
as fuel oils, tars, and the like, combined with a
high temperature refractory materials imper
heat regenerative system. Housed within the
fractories made of diaspore, mullite, cyanite, or 60 provided with an independent heating system
the like.
.
Other objects and advantages will become ap
parent from the following description taken in
conjunction with the accompanying drawings, in
65
.
Fig. 1 illustrates a vertical cross-sectional View
of one oven showing the vertical regenerators,
lower and upper heating systems, flues in which
the oil vapors are cracked, the gas and air supply
manifolds and piping to the upper transverse 70
which:
heating system and the air and oil ports leading
into the oven;
Fig. 2 depicts a vertical longitudinal sectional
which can be so controlled as to obtain the de
sired temperature in the walls of the cracking
oven. The entire brick work can be encased in
a metal shell, such as a welded or riveted steel
casing, whereby the interior of the oven can be
put under pressure or under vacuum as desired.
Generally speaking, the oven heating system
preferably consists of an uneven number of sole
nues, say three, ñve, seven, or nine intercon
nected in series and arranged longitudinally of
the oven to support and heat the floor of said
oven. These heating flues are connected to
damper controlled ports or openings, located at
opposite ends of the series, with two sets of ver
heating flues, vapor flues and regulating dampers 75 tical regenerators located below and parallel to
view of one oven, regenerators, lower and upper
»2,410,074
5
6
are similarly connected with ñue l and transverse
ilue C»-2> and by-passages P-lf' to P-22 in-A
elusive. Flues C+! and C--Z are preferably lo- y
the» heating ilues and ovens.A The two setsï of
vertical regeneratoîrs are alternately used- to sup
ply pre-heated air to opposite ends of the series
flue heating system and to receive the hot waste
products of combustion. The regenerators, of
which I prefer to employ three, are connected "in
series in each’set, have spacious, chamber-like
cated on the same horizontal level as the regen
They are
adapted to serve as' manifolds for'air to be pre
heated in the regenerators or for waste gas to be .
keratorsY and separate the tw'o sets.
discharged to the stack through the Isley system.
passages both above and belowr the che'ckerbrick,
The alternate flow of air and waste gas and
mushroom out before passing through and thus 10 >the circulation through the heating ñues, regen
erators and said common transverse'r ilues are
increasing the time of contact and affording
giving4 the gases an opportunity to spread or y
controlled by reversing and plate dempers of the
more effective heat transfer. Ea'ch set of regen
erators communicates with one or two ?lues which
are located transversely of `the oven below the
Isley system connected with flues C-2 and C-l,
which are connected with heating flues l and 5,
respectively, by passages P~-l2 and P-l leading
to regenerators R-ll and R-l, respectively, vas
will- be more fully explained hereinafter.
heating ilues and preferably between the two sets
of regenerators.
Means associated with the
transverse iiues are» provided outside the oven
structure for the purpose of reversing the ilow
Passages 13_2, PL-B, P-ill, and P-lä, P-VI'P,
through the heating system in each oven'. An
and P--2l, which lie above the checkerbricl: in
upper transverse flue heating system in the oven 20 R--i, Rw?, Re~3, and R-'ll, R-ë, R-ä, respec
tively (see Fig. 7 andv Fig. `2) are spacious and
roof, is used not for heating the oven, but ‘for
chamber-like and, when these regenerators are
cracking and heat treating the vapors for theL
being used for waste combustion products, they
production of aromatics and for the conversion
are adapted to give these Waste gases an oppor
of hydrocarbons.
f
'
tunity to spread or mushroom out before passing
For the purpose of giving those skilled in the ‘
downwardly through said regenerators. »Simi
art a better understanding of the invention, a de
larly, passages P-S, P-l, P-ll and _i3-«lt
tailed description will be given in conjunction
P-i t, P--`22, which lie below the checkerbricl: in
with the drawings.
'
.
said respective regenerators, are also spacious
Referring now more particularly to Figures l
to 6, it is Vreadily observed that the cracking and 30 and chambenlike and are adapted to furnish an
opportunity for air flowing to the regenerators
colring oven embodying my invention is a domed
to spread and mushroom out before its upward
rectangular broad coking chamberv l-I-l, in which
passage through said regenerators.
the fluid hydrocarbon mass, such as oil residue,
The terminal ñues, 5 and ihof the series hue
tar or the like, is treated and is disti‘led.
heating system are connected through P-l and
superimposed upon the chamber are flues I-I-?l
’i3-l2, respectively, with-regenerators R-l and
in which vapors from the mass of fluid hydro~
R-4. The openings or ports V-~i and V-2 from
carbons, such as hot oil residue or tar, are
treated.
said fines, respectively, into said .passages are re
The hot oil or hot tar is charged
spectively controlled by dampers D-l and D,-l?,
into the coking chamber H-~l, through charg
ing hole ports H-2, in both sides of side
walls of the oven.
adapted to slide over said ports and to effect par
tial or complete closure, thus providing regulation
rThe oil vapors pass from
the coking chamber H-l, 'through olf-take
duct D, into the vapor heat treating> ?lues H-lL
of the draft in each individual oven.
'
‘Fuel gas manifolds F-l and F-2 (see Fig. 2)
run the entire length of one or more ovens on op
and out of the oven structure through flue
lil-5 to ley-product recovery apparatus; In cer
instances, it may be desirable to take off the
posite sides thereof and are adapted tosupply
burners B-l, B--2, B-k-îl, and B-d of each oven
with rich fuel gas under moderate
constant
uncracked vapors `through offftake flue H-ß,
is provided with a damper D-S, similar
pressure. Riser pipes G--l andCi-ä from the
to' D-~5, which is shown in Fig. vl and is illus-»
trated diagrammatically in Fig.' 7. The coking 50
mber l-l-l is adapted to be sealed against
the admission of air by oven doors K--l, which
‘e provided at the pusher end and the discharge
'supply manifolds to the burners are provided, and
a special L
orifice are also furnished for the
regulation of the fuel gas conducted there«
through. This L, depicted in Fig. S, is equipped
with a plug T--l and a removable orifice T-2,
which is adapted to be replaced by other similar
`
Beneath each colring chamber and running 55 members having larger or smaller orifices as re»
end of the oven.
¿land 5 are preferably >arranged in horizontal
quired. Valves ‘lí-3, V-éil, V-li and V-li (see
7 and 2'), located the riser pipes from the
position and are preferably series-connected.
manifolds to burners B-l , B-_2, B-3 and B-ll,
parallel to the length thereof, heatingñues l, 2,
The flues are separated from each other by 1on
gitudinal partition walls alternately spaced from
opposite ends of the ovens to form a turn between
adjacent flues. The interconnected heating flues
are provided at said turns with burning means,
such as gas burners B~-~!. B-f, B-3 and B-eâ,
which can be supplied with fuel, as will be de
scribed hereinafter.
f
Below the heating ilues of each cracking» and
coking oven are located two series-connected sets
of regenerators R?-i, R-Z, Re?, and R-e?l,
idf-5, R--6. The regenerators are huilt of stand
ard checkerbrick or special checkerbrick> in a con
ventional manner. Regenerators R-l, BMZ and
R-3 are connected with flue 5 and transverse
ñue C-L lay-passages P-l to PY-~-ll inclusive
(see Fig. 7). Regenerators R415-, 1%;5, and R-lì
respectivelyare adapted to shut olf the gas sup
60 ply entirely.
l
For certain conditions, an auxiliary fuel sup
ply can be easily added by the use ofv pipe lines
>L-I and L--2 (seeFigï), adapted for carrying
fuel oil or tar, also run the length of the oven or
'ovens Von opposite sides thereof. They are con~
nected with burners B»-l, 3_2, B-3 and B-e
through'valves V-`l, V-ß, V---9 and V--l@, re
spectively, said valves being adapted to atomize
the oil or tar. Air lines lr-S and L_-Ll running
the length of the oven yin association with the
pipe lines are also provided
connect with
valves V-l, V-B, VMS and V-l§, through air
regulating valves V-~i_l, V--i2, V-ES and V-M,
respectively, and are adapted to furnish air for
said atomization.
'2,410,074
7
8
The foregoing description of the lower half of
the entire unit is used primarily for the distilla
'air-,and waste gas, are communicably connected
with the Isley induced draft system; >dampers,
ejectors and air fans being provided for coopera
tion of oil or tar. The following description
covers the upper part of the oven in which the
oil or tar vapors are cracked` and where the 5
method of pyroiytically treating hydrocarbons for
the production of aromatic oils takes place. The
two oven sections form and are operated as one
unit.
The upper section of the oven structure em
bodies a heating system and oil vapor cracking,
heat-treating fiues,
`
The heat treating flues H-íi (see Figs. 2, Äl, and
‘7) which may consist of any number of flues as
tion with each other, as shown in Fig. 7.
The circulation is as follows: Dampers D-l I
in pipe L-5, D-I2 in pipe L-â, are open, damp
ers D--IIL in pipe L-S, D-iû in pipe L-iû are
closed, `as is damper D`-I3 in stack S-Z; damp
ers D-ß in pipe L--9 and D-i) in s-tack S-i are
10 open. With the dampers in this position, air from
blower BnFl flows through pipes L-5, L--iì
through ejector E-Z into flue C-Z to flue P-ZZ
through regenerators R-S, R-5, R-li and the
interconnecting flues to oven heating flue I, the
required lto handle the volume and velocity of the 115 waste gases pass out through valve V-i into flue
oil vapors, are arranged in a horizontal position
P-i, regenerators R-í, R~-«2, R-3 and the in
and are separated from each other by longitudinal
terconnecting ilues to ñue C-I .
partition Walls W.
Each wall has »a multiplicity
of projections W-l. The purpose of îthe projec
tions is to cause turbulence of the oil vapors,
causing them to contact the hot wall surfaces.
Each vapor flue H~-c is provided with regulat
ing dampers D-3 and D-d (see Figs. l, 2, and 4)
for the purpose of controlling the volume of gas
The waste gas is drawn from the oven through
ejector E-l by means of blower B-FZ, air enters
pipes L--’l, L-9, then around ejector E-I to
stack S-i, thence to atmosphere» The air swiftly
passing around ejector E--i flows 4upward
through stack S-I carrying the waste products
to the atmosphere. The dampers are reversed
from duct D to exit ñue H--5~ Beneath the vapor 25 by a conventional clock mechanism at fixed in
tervals and the circulation of air then passes to
flues H-4 (see Figs. 2, 5, and 7) and located
transversely to ñues H--li are heating iiues 5.
These heating flues 6 are single and separated by
the oven through flue C-l, regenerators R-L
R---2, Pif-3, and the interconnecting fiues to heat
partition walls W-Z.
ing nue 5.
Y
Each heating flue has a separate gas burner
B-E supplied with fuel gas from gas manifold
F-3 (see Figs. l and 5). The air for combustion
is supplied from air manifold pipe F--S through
air pipes F-l. The products of combustion from
all of the heating ñues 6 discharge into ñue 'l
(see Figs. l and 5) and to the stack through
flue 8.
When oil and tar vapors from the charge have
The Waste gas passing downward
through regenerators R---¿i, R-E, R-S and the
interconnecting i‘lues to ejector E~-2 to atmos~
.phere via stack S-Z.
The improved method embodying the present
invention can be carried into practice in any oon-'
vem'ent‘manner, but it is preferred to conduct the
operations of the novel method in the cracking
and `coking oven described hereinabove.
The following is a brief description of the op
eration of this invention when heat treating 8.5
all been evolved and there are no vapors to heat
treatin fiues H-ß, then the carbonaceous residue 40 degree A. P. I. Dubbs cracked residuum oil for
has been thoroughly coli-.ed and the coke is ready
the production of electrode coke from the carbon
content of the heavy oil While heat treating the
to be calcined for the purpose of improving the
true speciñc gravity of the coke Ito meet electrode
oil vapors for the recovery of aromatic oils, such
specifications, if so required.
as benzol, toluol, and Xylol.
Coke is calcined by means of forcing either hot 45 The heavy oil or oil tar is preferably first pre
heated to about '700° F. At this temperature the
or cold air in and- around the coke to produce
oil is continuously sprayed into the coking cham
limited combustion which burns all remaining oil,
Vber and immediately covers the entire or sub
volatile matter and loose carbon particles. The
stantially _the entire hot oven ñoor or the carbon
local combustion produces a hard dense cell wail
ized residue thereon. The gasifying of the hot
structure which increases the specific gravity of
oil starts immediately (i. e. volatilizing hydrocar
the coke from an average specific gravity of about
1.8 to about 2 plus.
‘
In my invention I have discovered that pre
heated air reduces the time of calcining the coke.
bon vapors, etc.), as well as the coking process
' (i. e; carbonizing the residue, etc.). An eight
hour operating cycle divided as follows is pre
I preferably preheat the air for calcining in ñues 55 ferred. v(The oven is said to be “on stream”
whenV oil is being continuously charged into the
H-ß (see Figs. l, 2,5 and '7).
Damper D-5 located between vapor flues H-4
oven). Oven on stream, continuously about five
and the by-p-roduct recovery equipment is closed.
and one-half hours, coking time required includ
Damper D-eß in air pipe 9 is opened. The lair
ing the time on stream, about seven hours, cal
to be preheated hows through pipe 9 into the 50 oining the coked or carbonized residue about
distributing flue H-5y then through vapor flues
thirty minutes, pushing coke from the oven and
H-li, where it is preheated from heating ilues E.
luting or sealing the oven doors and burning car~
The preheated air for combustion enters the
bon, thirty minutes, thus completing the eight
oven H-l through duct D.
The small volume
hour cycle. In practice operating three “eight
of products of combustion resulting from the pre 65 hour cycles” each twenty-four hours can be ef
heated air burning some of the coke, then enter
fected.
duct H-'l (see Figs. 2, 5, and 7) and pass to a
'The control of oven floor temperature is neces
stack through open damper D-l.
sary in order not to produce cracking of the oil
During the coking of tar, some carbon is de
vapors when oil, tar, or the like is continuously
posited over certain areas of the oven ñoor; to 70 sprayed over the floor surface. After the calcin
burn this carbon air as required is introduced
ing of the coke in the oven before pushing the
(see TE‘igs. l and 2) lthrough air ports H-3 from
coke, the entire ñoor area is overheated due to
pipe F-S into oven chamber CEI-I.
the combustion of so-me of the coke. The pro«
The transverse flues C-I and C-2, referred
cedure preferably used ,is as follows: All gas to
to in the foregoing as being used alternately for 75 the burners in the heating ?lues under the oven
2,410,0741
1”.'0
,
.
for the conversion of straight chain hydrocar
bons to aromatics, such as benZol, toluol vand Xylol.
For the purpose of evolving hydrocarbon vapors
floor is'shut off and the floor temperature is re
duced from an average temperature of about
2000° F. to about 1350° F. This quick drop in
temperature is induced by the cold air forced into
the oven through ports I~I-3, while scurñng the
small amount- of surface floor carbon.
As the oil covers the iioor, the gas is then
turned on and the burners in the heating flues
ignited from the stored heat in the brick walls.
from oil residues, tar and the like in the oven, a
. controlled amount of heat is supplied. by the
heating flue system which preferably has an odd
number of nues in series, such, for example, as
ñve 'as shown in the drawing. 'I‘he velocity of
flow in the fiues is preferably about thirty to
As the coke increases in depth over the floor sur
face, more gas is used at the burners to raise the
about thirty-five feet per second.
temperature as required for coking the incoming
the heating system, each fiue has a cross-section
of about one hundred square inches; whereas
When a rich
fuel, such as oil or coke oven gas, is burned in
Y oil on stream which is being deposited over the
ever increasing depth of coke until at the end oi'
when a lean gas is used, each flue has a cross
the oil input, when the coke bed is about 7 inches
section of about one hundred and thirty square
thick on an average, then the temperature in the
inches. Each set of regenerators (Rf-I, Rf-2
heating flues is raised to an average temperature
and R--S or R-IS, R-ä and lit-6) has a vvolume
of about 2750° F., which is necessary to complete
of about 600 cubic feet and is capable of han
the coking of the oil carbon residue on the top
dling about 800 cubic feet of outgoing hot waste
surface of the coke.
20 gas or incoming air per minute vwhich means that
The foregoing description covers the distilla
the temperature Aof vthe Waste gas is preferably
tion of the oil in the broad oven, whereas the
reduced from about 2750° F. to about 550° F. and
next one relating to an important feature of this
the air is preheated from about 70° F. to about
invention concerns the production of aromatic
1700° F. As is custo-mary, the valves of the Isley
hydrocarbons from straight chain hydrocarbons
system have to be reversed from time to time
evolved in the oven. It has been found that the
and, as a general rule, the interval of reversal
exothermic reaction temperature relating to the f
is preferably about 15 minutes. With the afore
conversion of straight chain hydrocarbons to
said arrangement, about 130 cubic feet of gas
aromatic hydrocarbons will average about 1350°
per minute (75,000 B. t. u.’s) or one half of one
F., and also that Contact of the oil vapors with 30 gallon of oil (75,000 B. t. u.’s) are burned in the
hot surfaces of the cracking and heat treating
main heating flues under the oven whereas about
chamber is required to bring about the reaction
50 cubic feet of gas (28,500 B. t. u.’s) are burned
in the oil vapors, to wit: the conversion of
in the auxiliary heating flues whereby electrode
straight'chain hydrocarbons to aromatic hydro
coke, gas, aromatics and other -by-products are
produced in the novel cracking and coking oven.
It is to be observed that the present invention
contemplates not only a‘single oven but a plu
rality of such ovens. Due to the unique combi
carbons. To insure the contact of the hot hy`
drocarbon vapors with hot cracking and heat
treating surfaces, meansfor providing turbulence
of the Yhot vapors has been provided. I have
found that radiated heat of a temperature higher
than 1350° F. will not release the aromatic light
nation of structural elements in the present
cracking and coking oven, it is possible to con
struct and operate a single oven or two, three,
four, five or more ovens in contradistinction to
the large slot ovens which require the building
of large numbers of ovens in order to make the
structure practical, economical and commercial.
When a plurality of ovens similar to the one
illustrated in Fig. 1 are yto be constructed then
the steel work and buck stays are removed to the
end of the battery of ovens and the pipes sup
piying air and fuel are incorporated directly in
the brick work. Of course, the conventional aux
oils from the oil vapors. In other words, I have
discovered that it is necessary to cause the hy
drocarbon vapors to contact the hot surfaces in
order to effect ~the conversion of hydrocarbons
and the formation of aro-matics from straightl
chain hydrocarbons.
The upper heating system as previously de
scribed with superimposed vapor cracking nues
has been especially incorporated in the oven
structure as a means for producing vapor tur
bulence and surface contact as required for theA
production or aromatic oils.
The present invention provides a novel crack
ing and coking oven which in actual practice is
preferably about forty feet long inside oven doors
K-l, about nine feet in width throughout from
iliaries are employed.
As these are well known
and understood by those skilled in the art, the
conventional auxiliaries have not been illustrated
and described. Reference to any appropriate
publication will give the illustration of the aux
iliaries and a description. Thus, for instance,
reference may `be had to the following textbooks:
the pusher-end door to the discharge-end doo-r,
and about two and one half feet in height or
depth. Associated with the roof of the oven
is a cracking chamber constituted of a plurality (30 Coal Carbonization, flo-y Horace C. Porter (The
Chemical Catalog Company, Inc., New York,
of ñues, preferably eight, each of which has a
New York)
i
free cross-sectional area of about one hundred
square inches. Although the cracking lchamber
H-d is heated in part from th-e heat coming from
oven H--|, the independent heating iiues 6 pro
vide additional heat required for cracking and
heat treating the hydrocarbon vapors. Each
separate heating íiue preferably has a cross-sec
Coal Carbonization, by John Roberts (Pittmanl
Si Sons, New York, New York)
(i5
.
International Handbook of the~ By-Product Coke
Industry, by Dr. W. Gluud, translated by D. L.
Jacobson (The> Chemical Catalog Company,
New York, New York) ~
‘
Petroleum Technology Scientific Principles, by
tional area of about sixty to about one hundred
Leo Gurwitsch and Harold Moore (D.~ Van
square inches depending upon the volume of oil 70
Nostrand C‘o., Inc., New York, New York)
vapor and has a control for the a-mount of fuel
to be burned and thus the amount of heat evolved
Furthermore, the present inventionv provides a
and the temperature attained. »tis preferred vto
control the heat and to maintain a wall tempera
ture of about 1800° E’. in the cracking chamber
method of p'yrolytically treating hydrocarbons
to cause a conversion thereof and the provision
of a broad cracking and coking oven in which the
2,410,074”
aforesaid method can be carried into practica'
including the cracking of straight chain hydro
carbons like parafñns occurring in petroleum and
the like, to lconvert them into aromatic hydro
12
rectangular type being broader than it is high
and adapted to receive carbonaceous material
capable of evolving upon being heated volatile
vapors including straight chain hydrocarbon va
pors and a residue capable of being carbonized
and coked, and a main heating system located
under substantially the entire sole of said oven
from a fluid hydrocarbon mass and canbonizing
to eiîect a substantially uniform heating of sub
the residue thereof into coke. In the new crack
stantially the entire sole whereby vapors are
ing and coking oven the main heating flues are 10 evolved from carbonaceous material in said oven
located under the sole or ñoor of the oven which
and some heat is supplied to said cracking cham
provides the heat for evolving the vapors from
ber, for pyrolytically treating carbonaceous ma
the fluid hydrocarbon mass in the oven, for the
terial including fluid hydrocarbon masses such
coking of the residue of said mass, and for sup
as petroleum, heavy oil, oil residue, tar, and the
plying a part of vthe heat for the cracking .cham 15 like to evolve vapors containing straight chain
-ber superimposed above and associated with the
hydrocarbons such as paraffin hydrocarbons and
roof of the oven, Whereas the auxiliary heat nues
then
cracking said straight chain hydrocarbons
are provided directly under the cracking chamber
and converting them into aromatic hydrocar
for the purpose of controlling the heat treatment
of the hydrocarbon vapors coming from the oven 20 bons such as benzol, toluol and xylol while car
bonizing the residue into good coke having ac
and passing through the channels or flues of the
ceptable qualities and properties, the improve
cracking chamber, whereby the hydrocarbons are
ment
which comprises a refractory cracking
converted, particularly the straight chain or par
chamber superimposed above and associated with
afiin hydrocarbons, into aromatic hydrocarbons.
The theory underlying the pyrolysis of hydro 25 said oven for cracking and heat treating said hy
drocarbon vapors to effect pyrolysis therein and
carbons is not completely understood at the pres
conversion of straight chain hydrocarbons into
ent time and the mechanism of the chemical re
aromatic hydrocarbons, said cracking chamber
actions involved is very complex. In the con
being divided into a plurality of longitudinally
version of hydrocarbons, a variety of reactions
extending Zones by means of partitions extending
occurs including decomposition, polymerization, `
longitudinally thereof, each of said partitions
and side reactions. The aforesaid reactions in
clude those of the endothermic type as well as
' having a multiplicity of projections for producing
those of the exothermic type. Generally speak
turbulence in said hydrocarbon vapors, means
ing, the decomposition of hydrocarbons belongs
connecting said coking oven with said cracking
carbons, such as benzol, toluol, xylol, naphtha
lene, anthracene, and the like, while evolving
vapors containing straight chain hydrocarbons
to the endothermic type, whereas those relating
to polymerization belong to the exothermic type.
. chamber to conduct the volatile vapors including
In the conversion of straight chain hydrocarbons
to aromatic hydrocarbons it appears that the first
reactions are of the decomposition variety and
are subsequently followed by those of a polymer
izing variety which may also be accompanied
with various side reactions. Although many fac
top of said oven and the bottom of said cracking
chamber for supplying the rest of the heat re
tors are involved, it appears that the more im
portant are temperature, time or space velocity,
turbulence of the vapors, pressure, concentration,
contacting surfaces and catalysts. Under cer
tainconditions, such products as butadiene may
be formed. By controlling the conditions in the
cracking and heat treating chamber a variety of
products can be produced. It is understood,
however, that the present invention is not to be
restricted to and dependent upon any theory in
cluding the foregoing.
Although the present invention has been dis
closed in connection with a preferred embodiment
thereof, variations and modiñcations mayV be re
sorted to by those skilled in the art without de
parting from the true spirit and scope of the
invention as disclosed in the foregoing specifica
straight chain hydrocarbon vapors evolved in said
coking oven to said cracking chamber, and an
auxiliary heating system interposed between the
quired in said chamber, said auxiliary heating
system having independent control whereby the
temperature in the cracking chamber may be
independently controlled relative to that of the
coking oven and desired aromatic temperatures
may be maintained within said cracking chamber
to effect the desired pyrolysis of vapors therein
including the conversion of straight chain hy
50 drocarbon vapors into aromatic hydrocarbon va
pors.
2. In a refractory cracking and coking oven
of the broad rectangular sole-fired type having a
broad refractory coking oven of the long rectan
gular type being broader than it is high and
adapted to receive carbonaceous material includ
ing fluid hydrocarbon masses such as petroleum,
heavy oil, cil residues, tar and the like capable of
evolving volatile vapors including straight chain
tion and defined by the appended claims. Thus, 60 hydrocarbons upon being heated, a door provided
at each end of the oven for sealing the same
for instance, the present method and coking and
against the admission of air, and a main heating
cracking oven can be used for coking and d_is
tilling coal tar and coal tar pitches, for the re
system located underneath the sole of said oven
for providing suñicient heat to evolve said vapors
covery of a variety of compounds including .creo
sote and tar acids. The novel method may like 65 from the said carbonaceous material and to coke
the residue thereof and for providing substan
Wise be used for the treatment of peat for the
tially uniform heat throughout the sole of said
recovery of volatile products including volatile
oven without cracking straight chain hydrocar
oils. Moreover the novel process and oven can
bons therein and without overcoking residue in
be used for heating of oil shales for the recovery
of various icy-products including oil and fractions 70 one part and undercoking residue in another part
of the oven, for pyrolyticaly treating carbona
thereof.
ceous material including nuid hydrocarbon
I claim:
masses such as petroleum, heavy oil, oil residue,
l, In a refractory cracking and coking oven of
tar, and the like to evolve vapors containing
the broad rectangular sole-fired type having a
straight chain hydrocarbons such as parafiin hy
sealable broad refractory coking oven of a long
2,410,074 Y
14
drocarbons and then cracking said straight chain ,
2..
hydrocarbons and converting them into aromatic
hydrocarbons such as benzol, toluol and xylol
while carboniaing the residue into’good coke hav
ing acceptablequalities and properties, the im
provement which comprises a refractory crack
ing chamber superimposed above and V_associated
with the roof of said coking oven, said cracking
chamber beiner divided into a plurality of longi
tudinally extending zones by means of partitions
extending longitudinally thereof, each of said
partitions having a multiplicity of projections for
producing turbulence in said hydrocarbon vapors,
and said partitions being in heat conducting rela
tionship with the heated bottom of the cracking
chamber, whereby heat is transmitted to the
cracking zones by the walls thereof as well as by
the bottom thereof, a flue connecting said oven
with said cracking chamber for conducting va
pors >from said oven toisaid chamber, and an
ture in the cracking chamber may be independ
ently controlled relative to >that of the coking
oven and desired aromatic cracking tempera
tures may be maintained Within said cracking
chamber to effect the desired pyrolysis of vapors
» therein including the conversion of straight chain
hydrocarbon vapors into aromatic hydrocarbon
vapors, and independent burners disposed in the
' flues' or the auxiliary heating system whereby
the temperature' in the cracking chamber> may
be independently controlled relative to that of
the coke oven.>
4. In a refractory cracking and coking oven
of the broad rectangular sole-fired type having
a scalable broad refractory coking‘oven of a long
rectangular type being broader than it is high
and adapted to receive» carbonaceous material
capable of evolving upon being heated volatile
vapors including straight ‘chain hydrocarbon
vapors and a residue capable of being carbonized
auxiliary lheating system located underneath said
and coked, and a main heating system located
cracking chamber and above the roof of said
Arudder substantially the entire sole of said oven
to effect a substantially uniform heating of sub
stantially the entire sole whereby vapors are
evolved from carbonaceous material in said oven
and some heat is supplied to said cracking cham
ber forpyrolytically treating carbonaceous ma
tcrial including kfluid hydrocarbon masses such
coking oven for supplying a desired and con
trolled amount of heat to establish predeter
mined thermal conditions Within said cracking
chamber> to cause the conversion of straight
chain hydrocarbons to aromatic hydrocarbons in
cluding benzol, toluol, and xylol whereby the tern
perature in theV cracking chamber may be in
as petroleum, heavy oil, oil residue, tar, and the
dependently controlled relativev to that of the 30 like t0 evolve vapors containing straight chainy
coking
oven.v
'
‘
hydrocarbons such as parafñn hydrocarbons and
3. In a refractory cracking and coking oven
of the broad rectangular sole-fired type having
a scalable broad refractory coking oven of a long
rectangular type being broader than it is high 35
then cracking said straight chain hydrocarbons
and converting them into aromatic hydrocarbons
such as benzol, toluol and Xylol while carbonizing
the residue into >good coke having acceptable
and adapted to >receive carbonaceous material
capable of evolving upon being heated volatile
vapors including straight chain hydrocarbon
qualities and properties, the improvement which '
comprises a refractory cracking chamber super
imposed above and associated with said oven
for cracking and heat treating said hydrocarbon
bonized and-coked, anda main heating system 40 vapors to effect pyrolysis therein and conversion
located under substantially the entire sole of said
of straight chain hydrocarbons into aromatic
oven to effect a substantially uniform heating- of
vided
hydrocarbons,
into a plurality
said cracking
of vaporchamber
cracking being
and heat
substantially the entire sole whereby vapors are
evolved from carbonaceous material in said oven
treating flues by meansvof partitions capable of
and some heat is supplied to said'cracking cham 45 producing turbulence in said hydrocarbon vapors,
ber, for pyrolytically treating carbonaceous ma
means` connecting >said coking oven with said
terial including- fluid hydrocarbon masses ysuch
, cracking chamber to conduct the volatile vapors
including straight chain hydrocarbon vapors
as petroleum, heavy oil, oil residue, -tar, and the
like to evolve vapors containing straight chain
evolved` in said coking oven to said cracking
hydrocarbons such as parañin hydrocarbons and 50 chamber, and an auxiliary heating system inter
then' cracking said straight chain hydrocarbons
posed between thetop of 'said oven and the bot
and converting them into yaromatic hydrocarbons
tom of said cracking chamber forA supplying the'
such as benzol, toluol and xylol While carbcnizing
rest >of the .heat'required in said chamber,v said’
the residue into good coke having acceptable
auxiliary `heating, system having independent
qualities and propertiesthe improvement which 55 control whereby the temperature in the cracking
comprises a refractory cracking chamber super
chamber may be independently controlled rela-1;
imposed above and associated with said oven for
tive to that of Vthe coking oven and- desired
cracking and heat treating said `hydrocarbon
aromatic cracking temperatures may7 be main
vapors to eilect pyrolysis therein and conversio-n
tained' within said cracking chamber to effect
of straight chain hydrocarbons into aromatic hy 60 the desired' pyrolysis of vapors therein including
drocarbons, said cracldng chamber being divided
the conversion of straight chain hydrocarbon
into a plurality 0f` longitudinally extending Zones
vapors into aromatic hydrocarbon vapors.
`
by means ci“ partitions extending longitudinally
5. In a refractory cracking and coking oven of
thereof, eachof said partitions having a multi
the-broad rectangular sole-ñred type having a
plicity of projections for producing turbulence 65 broad refractory coking oven of the long rec
in said hydrocarbon vapors, means connecting
tangular type being broader than, it is high and
said coking oven with said cracking chamber to
adapted to receive carbonacecus material includ
conduct the volatile vapors including straight
ing iiuid hydrocarbon masses such as petroleum, ~
chain hydrocarbon vapors evolved-in said'coking
heavy oil, oil residues, tar and‘the'like capable
oven to said cracking chamber, and an auxiliary 70 of evolving volatile vapors including' straight
heating system interposed between the top> of said
chain'hydrocarbons upon being heated, a door
oven and the bottom of said cracking chamber
provided at- each endof the oven forsealing the
_for supplying the rest of the heat required
same against the admission of air. and amain
said chamber, said auxiliaryheating system hav
heating system located underneath the sole of
ing independent control whereby the tempera-ï
saidbven for providing sufñci‘ent heat tov evolve
vapors and a residue lcapable of f being~ car
16?k
said vapors from the said carbonaceous material
and to coke the residue thereof and for providing
substantially uniform heat throughout the sole
of said oven without cracking straight chain hy
drocarbons therein and Without overcoking resi
due in one part and undercoking residue in an
other part oi the oven and for pyrolytically treat
ing carbonaceous material including fluid hy
drocarbon masses such as petroleum, heavy oil,
oil residue, tar, and the liketo evolve vapors con
taining straight chain hydrocarbons such as par
afñn hydrocarbons and then cracking said
straight chain hydrocarbons and converting them
into aromatic hydrocarbons such as benzol, toluol
and Xylol while carbonizing the residue into good
coke having acceptable qualities and properties,
posed above and associated with said oven for
cracking and heat treating said hydrocarbon va
pors to efîectpyrolysis therein and conversion of
_ straight chain hydrocarbons into aromatic hy
drocarbons, said cracking chamber being divided
into a plurality oí vapor cracking and heat treat
ing ?lues by means of partitions capable of pro
ducing turbulence in said hydrocarbon vapors,
means connecting said ccking oven with said
cracking chamber to conduct the volatile vapors
including straight chain hydrocarbon vapors
evolved in said coking oven to said cracking
chamber, an auxiliary heating system interposed
between the top of said oven and the bottom of
f said cracking chamber for supplying the rest of
the heat required in said chamber, said auxiliary
heating system having independent control
the improvement which -comprises a refractory
whereby the temperature in the cracking cham
cracking chamber superimposed above and as
ber may be independently controlled relative to
sociated with the roof of said coking oven, means
connecting said coking oven> with said cracking 20 that of the coking oven and desired aromatic
cracking temperatures may be maintained within
chamber for conducting vapors from said oven
said cracking chamber to eiïect the desired DY
to said chamber, said cracking chamber contain
rolysis of vapors therein including the conver
ing at least one vapor cracking and heat treat
sion of straight chain hydrocarbon vapors into
ing iiue made by means of partitions in heat
conducting relationship with the heated bottom 25 aromatic hydrocarbon vapors, and independent
burners disposed in the nues of lthe auxiliary
of the cracking chamber whereby heat is trans
heating system whereby the _temperature in the
mitted to the cracking Íiue by the walls thereof
cracking chamber may be independently con
as Well as by the bottom thereof, and an auxil
trolled relative to that of the coke oven.
iary heating system located underneath said
7. In a refractory cracking and coking oven of
cracking chamber and above the roof of said 30
the broad rectangular sole-ñred type having a
coking -oven for supplying a desired and con
sealabie broad. refractory coking oven of a loner
trolled amount of heat to establish predetermined
rectangular type being broader than it is high
thermal conditions within said cracking cham
and adapted to receive carbonaceous material
ber to cause the conversion of straight chain hy
drocarbons to aromatic hydrocarbons including
benZol, toluol, and xylol whereby the tempera
ture in the cracking chamber may be independ
ently controlled relative to that of the coking
capable of evolving upon being heated volatile
vapors including straight chain hydrocarbon va
pors and a residue capable of being carbonized
and ccked, and a main heating system located
under the soie of said oven for providing suffi
.
6. ïn a refractory‘cracking and coking oven of 40 cient heat to evolve said vapors from said carbo
lnaceous material in said o-ven and to coke the
the broad rectangular sole-iired type having a
residue thereof and i'or‘ providing substantially
scalable broad refractory coking oven of a long
uni-form heat throughout the sole ofA said oven
rectangular type being broader than it is high
oven.
without cracking and without overcoking residue
and adapted to receive carbonaceous material
capable of evolving upon being heated volatile 45 in one part and undercoking residue in another
part of the oven and for pyrolytically treating
vapors including straight chainv hydrocarbon va
carbonaceous material including fluid hydrocar
pors and a residue capable of being carbonized
bon masses such as petroleum, heavy oil, oil resi
and coked, and a main heating system located
due, tar», and the like to evolve vapors containing
under the sole of said oven for providing sufíi
cient heat to evolve said vapors-from said car to straight chain hydrocarbons therein such as par
añin hydrocarbons and then cracking said
bonaceous material in said oven and to coke the
straight chain hydrocarbons and converting them
residue thereof and for providing substantially
into aromatic hydrocarbons such as benzol, tolu
uniform heat throughout the sole of said oven
ol and Xylol while carbonizing the residue into
without »cracking’and without overcoking residue
good coke having acceptable qualities and prop
in one part and undercoking residue in another
erties, a chimney system for conducting hot waste
part of the oven and for pyrolytically treating
products of combustion from said main heating
carbonaceous material including fluid hydrocar
system to the atmosphere, and a heat regenera
bon masses such as petroleum, heavy cil, oil
tive system interposed between said main heat
residue, tar, and the like to evolve vapors con
taining straight chain hydrocarbons therein such 60 ing system and said chimney system for exchang
ing heat from the hot waste products of combus
as paraiiin hydrocarbons and then cracking said
tion coming from said heating system to preheat
straight chain hydrocarbons and converting them
incoming air and/or gas going to said heating
into aromatic hydrocarbons such as benZol,
system, the improvement which comprises a re
toluol and Xylol while carbonizing theresidue
into good coke having acceptable qualities and 65 fractory cracking chamber superimposed above
and associated with said oven for cracking and
properties, a chimneysystem for conductinghot
heat treating said hydrocarbon vapors to effect
waste products of combustion from said/main
pyroylsis therein and conversion of straight chain
heating system to the atmospheregand a heat‘
hydrocarbons into aromatic hydrocarbons, said
exchange system interposed between said main
heating system and said chimney system for ex 70 cracking chamber being divided into a plurality
of vapor cracking and heat treating ñues by
changing heat from the hot waste products of
means of partitions' capable of producing turbu
combustion coming from said heating system to
lence in said hydrocarbon vapors and extending `
preheat incoming air -and/or gas going to said
substantially from one end of said oven to sub
heating system, the improvement which com
prises a refractory cracking chamber superim.. 75 stantially the other end, means connecting said
2,410,074
17
18
coking oven With said cracking chamber to con
duct the volatile vapors including straight chain
hydrocarbon vapors evolved in said coking oven
to said cracking chamber, an auxiliaryrheating
system interposed between the top of said oven
and the bottom of said cracking chamber for
and desired aromatic cracking temperatures may
be maintained Within said cracking chamber to
eiîect the desired pyrclysis of vapors therein in
cluding the conversion of straight chain hydro
carbon vapors into aromatic hydrocarbon vapors,
a multiplicity of projections in said flues for pro
supplying the rest of the heat required in said
ducing turbulence in said hydrocarbon vapors,
chamber, said auxiliary heating system compris
and independent burners disposed in the flues of
ing a plurality of ñues extending underneath sub
the auxiliary heating system whereby the tem
stantially the entire cracking chamber and hav 10 perature in the cracking chamber may be inde
ing independent control whereby the temperature
pendently controlled relative to that of the coke
in the cracking chamber may be independently
oven.
controlled relative to that of the coking oven
CHARLES H. HUGHES.
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 841 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа