Process and Apparatus for Making Coke and Saving By-products.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
Process and Apparatus for Making Coke and Saving By-products.
PAUL NAEF, Doctor of Philosophy, Chemical Engineer, 15, 3rd Avenue,
New Brighton, S.T., New York, U.S.A., do hereby declare the nature of this
invention to be as follows: :―
This invention relates to a process and apparatus for the manufacture of coke,
gas, ammonia and by-products from carbonaceous fuel, producing at the same
time cyanides or ammonia by the action of atmospheric nitrogen on the coke in
the presence of an alkali.
Objects of the invention are, to provide a process and apparatus to produce
coke in a single apparatus in much larger quantities than has been done hereto-
fore, and on a scale commensurate with the requirements of a blast furnace, to
obtain a favourable condition and a sufficiently high temperature for the combi-
nation of the nitrogen of the atmosphere with carbon and an alkali to form a
cyanide.
Further objects are, to utilize the nitrogenous compounds which are with ordi-
nary coking processes left in the coke (and which represent usually 50 per cent of
the nitrogen contents of the coal) for the production of ammonia by the action
of incandescent steam and also of alkali and alkaline earth metals on the red hot
coke; to provide a process and apparatus to produce coke and the by-products of
coal without waste of heat, so that the heat units required for the distillation
only, are consumed, the remaining heat units being contained in the coke and
gas; to utilize the heat of the incandescent coke for producing steam and super-
heating the same; to make the coking of coal and the cooling and loading of the
coke wholly automatic; to manufacture,fuel and illuminating gases, as well as
tar, ammonia, and coke; to reduce the cost of plant investment and repairs per ton
of coke; and to effect great economies in the cost of production and in the utiliza-
tion of the by-products.
The coke ovens heretofore used for coking coal to recover or utilize the by-
products, have the disadvantage in that they are very costly, requiring consider-
able repair and producing a very limited amount of coke per oven.
My process and apparatus is designed to, obviate all these disadvantages,. and
to obtain the results hereinbefore stated, by a new method of supplying all or a

page_text: part of the heat necessary for the distillation of the coal, by passing incandescent
gases through the coking material. These gases are produced by injecting air
previously heated to as high a temperature as possible into the coking material;
part of the heat necessary for the coking is thus supplied by the preheated air,
the rest by combustion of a small percentage of the coke. By preheating the air
a smaller volume of it is required for the coking, consequently the gas produced
is richer and less diluted with nitrogen. A still further reduction in the per-
centage of nitrogen in the gas is effected by transmitting heat through fire brick
tiles in the walls of the apparatus.
The incandescent gases pass through a column of coking material of consider-
able height. They escape from the top of the apparatus carrying tar and
ammonia and at a temperature not much higher than is necessary to prevent con-
densation of tar.
As the coke is subjected to considerable pressure during its formation, this pro-
cess is adapted for the manufacture of metallurgical coke.
The invention also relates to the apparatus for carrying out the process. As
the hot air is forced into the coking column under pressure, it is an important
feature to have an apparatus from which the coke can be withdrawn without
escape of gas or steam. This can be achieved by injecting the hot air at such a
height in the apparatus, that the resistance offered to the passage of the gas is
nearly the same in a downward as in an upward direction, as specially described
in another application of even date.
In this case it is advisable, that iron doors should be used between the upper
and lower chambers.
Other important features of the apparatus are:-that the coke is automatically
discharged, and is crushed screened and loaded into railway cars without manual
labor.
It is an important feature, that by applying my process, blast furnaces already
built, can be utilized for the production of coke, tar, gas and ammonia. The
changes which are necessary for such utilization, are to introduce the blast at a
higher level and to rebuild the bottom part of the furnace as shown in the
drawings.
The process is intended for a production of up to 200 or more tons of coke per
day in a single apparatus, while the coke ovens now in use furnish only from 3 to
5 tons per oven per day.
In the accompanying drawings forming part of the application:-Fig. 1 is a
in part sectional view showing a complete plant. Fig. 2, is a cross section of
the apparatus and stoves in Fig. 1. Fig. 3, is an enlarged vertical section of the
coking apparatus.
Referring to the figures, the coking apparatus is composed of a coking or upper
chamber, 1, having a suitable mechanical feed, 2, on the top, which may be con-
nected with an elevator, and a bottom cooling chamber, 3, in communication with
the coking chamber. At the juncture of the coking and cooling chambers the wall
of the apparatus is contracted, or rather the cross section of the apparatus is re-
duced, and the walls of the apparatus form an incline, 4, for the passage of the
material readily down through the contraction and into the cooling chamber. The
cooling chamber, 3, is supplied with steam pipes, 5, Fig. 3 and water pipes 6,
Fig. 3 for cooling the coke, and to recover or produce ammonia from the nitro-
genous compounds contained in the coke; as it passes on down to the bottom
delivery slopes, 7, from whence it is discharged through chute doors, 8. A hood, 9,
extends out over the doors, 8, and is connected by a pipe, 10, with a pump, 11,
for carrying off the steam and gases which may escape when drawing the coke.
Through the contracted portion of the apparatus extend horizontal shafts, 12.
operated from the outside of the apparatus, and upon which shafts are secured
doors, 13, to support the body of the coke as well as to separate the two chambers.
The coking chamber is lined with hollow tiles, 14, forming a series of vertical
flues, 15 which open at the bottom upon the outside of the chamber wall, and at

page_text: the top they open into an annular flue, 16, which has a stack, 17, for carrying off
the products of combustion.
A gas pipe, 18, encircles the exterior of the coking chamber and is provided
with a series of branch pipes, 19, the ends of which extend into the said open
ends of the wall flues, where the gas burns, the products of combustion passing
up through the series of flues into the annular flue, and thence to the chimney by
pipe, 17. A circular chamber or flue 20, surrounds the contracted portion of the
apparatus and is connected with the coking chamber by a radial series of ducts 21,
leading in just above the doors, 13. Hot air is supplied to the flue 20, and thence
to the coking chamber by a pipe, 22, and the hot air blasts entering through the
ducts, 21, are driven well in towards the centre of the charge of coke & then pass
up through the column of coking material in the coking chamber, and discharge
along with all the volatile products of the coal through the pipe 23, at a tempera-
ture not much higher than is necessary to prevent condensation of tar. The pipe 23
conducts the volatile products and gases to a suitable washing apparatus, 24, to
remove the tar, and thence through a similar apparatus, 25, to remove the
ammonia, the said washers being connected by a pipe, 26, and a pipe, 27, con-
ducts the gas from the washer, 25, to a gasholder not shown.
For heating the air blast to a high temperature there is shown in Figs. 1 and
2 a pair of heating stoves, 28 and 29, with the induction pipes, 30 and 31 lead-
ing from the air pump, 11, and the delivery pipes, 32, and 33, connected with the
hot air flue 20, of the apparatus. The pump, 11, as before stated sucks from
under the hood, 9, above the coke discharging doors, 8, so as to remove and dis-
pose of any gases escaping during the drawing of the coke. Pipe connections for
gas, for heating the stoves are shown at 34, and the chimney flue, 35, therefor.
Suitable valves, 36, allow for the alternate use of the stoves, one heating up with
gas, whilst air for the hot blast is being forced through the other.
The operation of the coking apparatus is as follows:-Coal elevated into the
feed hopper of the coking chamber, is discharged thereinto and as the charge
works downward, reaching a higher and higher temperature in its descent, through
heat from the gas heated flues in the chamber walls, and through the hot air
blasts until it finally reaches the maximum temperature at a point just above the
doors and within the zone of the converging air blasts, at which point all traces
of volatile matter are removed. As the doors are at intervals partially opened the
incandescent coke drops down into the lower chamber, where it meets the jets of
steam, and lower down is cooled by sprays of water; the steam thus, being super-
heated and decomposed in its passage through the hot coke, setting free ammonia
and also cooling the coke. The coke is from time to time discharged through the
doors at the bottom of the cooling chamber, sliding down over the sloping floor
thereof. Gas and all volatile products pass out through the pipe 23, and are con-
ducted to the washers for removing the tar and ammonia.
י
If ammonia is to be produced from the atmospheric nitrogen during the coking
process, an oxide or carbonate of an alkali or alkaline earth metal is intimately
mixed with the coking material, which is to be coked. The mixing of the coking
material and alkali can be effected by grinding the two materials together, or by
introducing the alkali as a solution into the top part of the apparatus through
spray nozzles, 23, Fig. 3. As the volatile matter is driven off from the coking
material, coke is produced holding the alkali in a very fine state of division. At
a red heat the alkali will set free, ammonia from the nitrogenous compounds of
the coking material. As the coke reaches the zone of the tuyeres for the entrance
of the hot blast, which is heated as high as possible, a temperature is reached
sufficiently high for the formation of cyanides by combination of nitrogen, carbon
and alkali. The conditions for this reaction are more favourable than in most of
the numerous processes proposed for the manufacture of cyanides. As the alkali
and the coking material have been coked together, the former is in extremely fine
distribution, and as coke is always more or less porous an enormous surface is
offered to the nitrogen gas to act upon. This is considered of more importance by

page_text: the inventor than the point, that the nitrogen must not be diluted with other
gases, on which great stress has been laid by some authorities. The large body of
coke acts further as an equalizer of temperature; it prevents great variation in
temperature and irregularities in the working of the apparatus. Most of the
cyanide rises in the chamber as vapor and is decomposed by 'introducing. steam
after the gas has passed about half the height of the apparatus, as indicated by
the dotted lines 38 in Fig. 3.
I
Alkali is recovered by the reaction: —;
2NaCN + 3H20=2NH3 + Na2O + 200.
which is again carried to the lower part of the apparatus and converted into
cyanide. It will thus be seen that only a small amount of alkali has to be added
to the coking material, which will in no way deteriorate the quality of the coke.
Any cyanide in the coke is decomposed by steam in the cooling chamber. The
steam from this chamber is conducted to a washing apparatus through a pipe 37,,
to recover ammonia, or it is conducted into the coking chamber at a higher level,
shown by the dotted pipe 38, where the temperature is not sufficiently high to
destroy ammonia.
It has been observed before in ordinary gas retorts, that oxides of alkaline
earth metals, act on the nitrogenous compounds of the coal, setting free ammonia..
As in the present case the temperature is much higher, such action takes place to
a greater extent.
If cyanide as such is to be manufactured, no steam is introduced into the upper
part of the coking apparatus. The cyanide is recovered from the gases leaving
the coking apparatus by similar methods as are used in some gasworks. Cyanide
can also be recovered from the coke, in which case no steam is used in the cooling
chamber. The cyanide can be lixiviated with water from the coke, after the coke
has been discharged; or the water lute shown in another application of even date
can be used. When using the water lute, as much cold solution as possible is
passed through it to prevent decomposition of the cyanide by steam.
Dated 25th March 1898.
COMPLETE
SPECIFICATION.
Process and Apparatus for Making Coke and Saving By-products.
PAUL NAEF, Ph.D., Chemical Engineer, 15, 3rd Avenue, New Brighton, S.T.,
New York, U.S.A., do hereby declare the nature of this invention and in what
manner the same is to be performed, to be particularly described and ascertained
in 'and by the following statement:-
This invention relates to a process and apparatus for the manufacture of coke,
gas, ammonia and by-products from carbonaceous fuel, producing at the same.
time cyanide or ammonia by the action of atmospheric nitrogen on the coke in
the presence of an alkali.
Objects of this invention are to provide a process and apparatus, to produce
coke in a single apparatus, in much larger quantities than has been done hereto-
fore, to obtain a favourable condition and a sufficiently high temperature for the
combination of the nitrogen of the atmosphere with carbon and an alkali to form
a cyanide.
Further objects are, to utilize the nitrogenous compounds, which are with ordi-
nary coking processes left in the coke (and which represent usually 50 per cent of

page_text: the nitrogen contents of the coal) for the production of ammonia by the action of
superheated steam, and also by the action of alkali and alkaline earth metals on
the red hot coke; to provide a process and apparatus to produce coke and the by-
products of coal, with a small waste of heat, so that the heat units required for
the distillation only, are consumed, the remaining heat units being contained in
the coke and gas; to utilize the heat of the incandescent coke for producing steam
and superheating the same, to make the coking of coal, and the cooling and load-
ing of the coke wholly automatic; to manufacture fuel and illuminating gases as
well as tar, ammonia and coke.
The coke ovens heretofore used for coking coal, to recover or utilize the by-
products, have the disadvantage in that they are very costly, requiring consider-
able repair and producing only a very limited amount of coke ner oven.
My process and apparatus is designed to obviate these disadvantages, and to
obtain the results hereinbefore stated, by a new method of supplying all or a
part of the heat necessary for the distillation of the coal, by passing incandescent
gases through the coking material. These gases are produced by injecting air
previously heated to as high a temperature as possible, into the coking material;
part of the heat necessary for the coking is thus supplied by the preheated air.
the rest by combustion of a small percentage of the coke. By preheating the air
a smaller volume of it is required for the coking, consequently the gas produced
is richer and less diluted with nitrogen. A still further reduction in the per-
centage of the nitrogen in the gas is effected by transmitting heat through the
fire-brick tiles, in the walls of the apparatus.
The incandescent gases pass through a column of coking material of consider-
able height. They escape from the top of the apparatus, carrying tar and ammonia,
and at a temperature not much higher than is necessary to prevent condensation
of tar.
As the coke is subjected to considerable pressure during its formation, caused
by the hight of the coking column, this process is adapted for the manufacture of
metallurgical coke.
This invention also relates to the apparatus for carrying out the process. As.
the hot air is forced into the coking column under pressure, it is an important
feature to have an apparatus from which the coke can be withdrawn without loss
of gas or steam. This can be achieved by injecting the hot air at such a height
in the apparatus, that the resistance offered to the passage of the gas is nearly
the same in a downward as in an upward direction, as especially described in a.
special application of even date, (7951/98, date under International Convention
7 Sept. 97.
In this case it is advisable that iron doors, should be used between the upper
and lower chambers.
Other important features of the apparatus are that the coke is automatically
discharged, and is crushed, screened and loaded into railway cars, without manual
labour.
It is an important feature, that by applying my process, blast furnaces, already
built, can be utilized for the production of coke, tar, gas and ammonia. The
changes, which are necessary for such a utilization, are to introduce the blast
at a higher level, and to rebuild the bottom part of the furnace as shown in the
drawings.
The process is intended for a production of up to 200 tons or more of coke per
day in a single apparatus, while the coke ovens now in use furnish only from 3.
to 5 tons, per oven, per day.
In the accompanying drawings, filed with my Provisional Specification, form-
ing part of the application:-Fig. 1 is a in part sectional view showing a com-
plete plant. Fig. 2 is a cross section of the apparatus and stoves in Fig. 1.
Fig: 3 is an enlarged vertical section of the coking apparatus..
Referring to the figures, the coking apparatus is composed of a coking or upper
chamber.1, having a suitable mechanical feed 2, in the top, which may be con-

page_text: nected with an elevator and a bottom cooling chamber 3, in communication with
the coking chamber. At the juncture of the coking and cooling chambers, the
wall of the apparatus is contracted, or rather the cross-section of the apparatus
is reduced, and the walls of the apparatus form an incline 4 for the passage of the
material readily down through the contraction and into the cooling chamber. The
cooling chamber 3, is supplied with steam pipes 5, and water pipes for cooling
the coke and to recover or produce ammonia from the nitrogenous compounds
contained in the coke as it passes on down to the bottom delivery slope 7, from
whence it is discharged through chute-doors 8. A hood 9, extends out over the
doors 8, and is connected by a pipe 10, with a pump 11, for carrying off the steam
and gases, which may escape whilst drawing off the coke. Through the con-
tracted portion of the apparatus extend horizontal shafts 12, operated from the
outside of the apparatus, and upon which shafts are secured doors 13, to support
the body of the coke as well as to separate the two chambers. The coking chamber
is lined with hollow tiles forming a series of vertical flues 15, which open at the
bottom upon the outside of the chamber wall, and at the top they open into an
annular flue 16, which has a stack 17, for carrying off the products of combustion.
A gas pipe 18, encircles the exterior of the coking chamber and is provided
with a series of branch pipes 19, the ends of which extend into the said open
ends of the wall flues, where the gas burns, the products of combustion passing
up through the series of flues into the annular flue 16 and thence to the chimney
hy pipe 17. A circular chamber or flue 20, surrounds the apparatus, and is com-
municated with the coking chamber by a radial series of ducts 21. Hot air is
supplied to the flue 20, and thence to the coking chamber by a pipe 22, and the
hot air blasts entering through the duct 21 are driven well in towards the centre
of the charge of coke, and then pass up through the column of coking material
in the coking chamber, and discharge along with all the volatile products of the
coal,, through the pipe 23.
The pipes 23, conducts the volatile products and gases to a suitable washing
apparatus 24, to remove the tar, and thence through a similar apparatus 25, to
remove the ammonia, the said washers being connected by a pipe 26; and a pipe 27,
conducts the gas from the washer 25, to a gas holder-not shown.
For heating the air blast to a high temperature there is shown in Figs. 1 and 2,
a pair of heating stoves 28 and 29, with the induction pipes 30 and 31 leading
from the air pump 11, and the delivery pipes 32 and 33, connected with the hot
air flue 21, of the apparatus. The pump sucks from under the hood 9, above the
coke discharging doors 8, so as to remove and dispose of any gases escaping during
the drawing of the coke. Pipe connections for gas, for heating the stoves are
shown at 34, and the chimney flue therefor at 35. Suitable valves 36, allow for
the alternate use of the stoves, one heating up with gas, while air for the hot
blast is being forced through the other.
The operation of the coking apparatus is as follows:-Coal elevated into the feed
hopper of the coking chamber is discharged thereinto, and as the charge works
downward, reaching a higher and higher temperature in its descent through heat
from the gas heated flues in the chamber walls and through the hot air blasts
until it finally reaches the maximum temperature at a point just above the doors
and within the zone of the converging air blast at which point all traces of volatile
matter are removed.
As the doors are at intervals partially opened, the incandescent coke drops into
the lower chamber where it meets the jets of steam and lower down is cooled by
sprays of water, the steam thus being superheated and decomposed in its passage
through the hot coke, setting free ammonia and also cooling the coke. The coke
is from time to time discharged through the doors at the bottom of the cooling
chamber, sliding down over the sloping floor thereof. Gas and all volatile pro-
ducts pass out through the pipe 23, and are conducted to the washers for removing
the tar and ammonia.
If ammonia is to be produced from the atmospheric nitrogen during the coking

page_text: which is again carried to the lower part of the apparatus and converted into
cyanide. It will thus be seen that only a small amount of alkali has to be added
to the coking material which will in no way deteriorate the quality of the coke.
Any cyanide in the coke is decomposed by the steam in the cooling chamber. The
steam from this chamber is conducted to a washing apparatus through a pipe 37,
to recover ammonia; or it is conducted into the coking chamber at a higher level,
shown by the dotted pipe 38, where the temperature is not sufficiently high to
destroy ammonia.
It has been observed before in gas works using ordinary gas retorts, that oxides
of alkaline earth metals act on the nitrogenous compounds of the coal, setting free
ammonia. As in the present case the temperature is much higher, such action
takes place to a greater extent.
If cyanide as such is to be manufactured, no steam is introduced into the upper
part of the coking apparatus. The cyanide is recovered from the gases leaving
the coking apparatus, by any of the methods which are in use for absorbtion and
recovery of cyanide in gas works.
Cyanide can also be recovered from the coke, after the coke has been dis-
charged, or the water-lute shown in another application of even date, can be used,
(7951/98, date under International Convention 7 Sept. 97.
When using the water-lute, as much cold solution as possible is passed through
it to prevent decomposition of the cyanide by steam. It will be noticed, that for
the decomposition of the cyanides to ammonia, I introduce steam in the upper
part of the coking column into the body of the coking material. This has the
important effect described, that alkali is recovered and again passes with with the
coking material to the lower part of the furnace and that thus a constant circula-
tion of alkali is obtained.
It is evident, that as in my process, air heated to the highest possible tempera-
ture is injected under pressure into a large body of highly incandescent fuel, the
highest temperatures can be reached and regularly maintained. These tempera-
tures are only limited by the dissociation of the products of combustion.

page_text: An important point is that only a small amount of alkali used in the process,
and that the same is finely distributed amongst a large amount of porous coke.
This prevents melting of the alkali, and destruction of the furnace.
I am aware, that many attempts have been made to produce cyanide and
ammonia from nitrogen by similar chemical reactions. I therefore do not claim
the chemical reactions as such individually but the method of carrying them out.
These processes have for its principal object always the production of cyanide
or ammonia from nitrogen, and have been unsuccessful, because nitrogen being a
very inert gas, its combination with carbon and alkali is necessarily a slow re-
action.
My process has for its principal object the manufacture of coke and gas, an·l
the heat which has to be produced for the coking is also utilized for the produc-
tion of cyanide from nitrogen. It is therefore evident that my process will be
remunirative if only a small amount of cyanide or ammonia from atmospheric
nitrogen is formed, because the same is obtained with little extra expense.
The apparatus without doors between the upper and lower part described in
another application of even date 7951./98, dated, under International Conven
tion, 7 Sept. 97, can be also used for carrying out the process, if no steam is
introduced into the lower part of the apparatus.
If steam is introduced into the lower part, the difficulty of destroying ammonia
by passing the same upwards, is avoided by drawing the gas off from the lower
part separately, without using doors which improvement forms part of a new
application.
Having now particularly described and ascertained the nature of my said
invention, and in what manner, the same is to be performed, I declare that what
I claim is :-
1. The process of producing coke, gas and by-products, which consists in pass-
ing fuel containing a small amount of an oxide or carbonate of an alkali or alka-
lino earth metal, downward through a shaft, injecting highly heated air into the
incandescent fuel in the lower part of said shaft, passing the gases upwards through
the fuel and injecting steam into the fuel some distance above the entrance of the
incandescent air.
2. The process of producing ammonia from nitrogen, which consists in combi-
ning nitrogen and carbon in the presence of an alkali in the lower part of a shaft,
passing the gases containing cyanide upwards through the fuel in the shaft, inject-
ing steam into the body of fuel in the upper part of the shaft, whereby ammonia is
produced, which passes with the gases, and whereby alkali is recovered, which 's
partly intercepted and carried downward by the fuel to the hotter part of the
furnace, where it is again converted into cyanide.
3. The hereindescribed process of combining the coking of fuel and the pro-
duction of cyanide or ammonia from nitrogen, which consists in utilizing the heat
and high temperature, obtainable in the production of coke from fuel, for the
simultaneous production of cyanide.
4. The process of producing coke, gas and by-products, which consists in pass-
ing fuel containing a small amount of an oxide or carbonate of an alkali or
alkaline earth metal through a shaft, injecting highly heated air into the incan-
descent fuel in the lower part of the shaft, passing the gases upwards through
the fuel in the shaft and treating the same for the recovery of ammonia and
cyanide, and treating the resultant coke in the part of the apparatus below the
entrance of the incandescent gas with steam, so as to decompose cyanide to
ammonia and to produce ammonia from the nitrogenous compounds in the coke
drawing off the gases from the lower part and treating them for the recovery of
ammonia.
5. The process of producing coke and ammonia from fuel, which consists in
intimately associating the fuel with a small amount of an oxide or carbonate of an

page_text: alkali or alkaline earth metal, and coking the same by injecting highly heated
air through the fuel.
6. The process of producing coke, gas and by-products from fuel and simulta-
neously ammonia from atmospheric nitrogen, which consists in injecting highly
5 heated air into a body of fuel containing an oxide or carbonate of an alkali or
alkaline earth metal, treating the resultant coke with steam and water, and then
conducting said steam containing some ammonia into the upper part of the coking
chamber, for decomposing the cyanide vapors.
7. The combination with the coking chamber having a tile wall provided with
a series of vertical heating flues, with openings to the outside wall of the chamber,
at the bottom and an annular flue surrounding the exit of the vertical flues at
the top and leading to a stack, of a gas supply pipe with branches extending with-
in the several mouths of the vertical flues.
8. The combination with the coking chamber and the cooling chamber, of a
hood surrounding the exit of the cooling chamber, and means connected with the
hood for drawing off escaping steam and gases when the said exit or coke dis-
charging doors are open.
9. In a coking apparatus for producing cyanides or ammonia from nitrogen, the
combination of a coking chamber above and a cooling chamber below forming a
O stack with a contracted neck separating the two and a ring of hot air ducts lead-
ing into the apparatus at the point of contraction.
10. An apparatus for producing coke simultaneously obtaining cyanides or
ammonia, comprising a coking apparatus, heating stoves for heating the air to be
forced through the coking material in the coking apparatus and washing arrange-
ments, to recover the products from the gases leaving the coking apparatus.
Dated this 27th day of May 1808