IMPROVEMENTS IN THE TREATMENT OF ORGANIC SUBSTANCES FOR THE PRODUCTION OF AMMONIA, AND APPARATUS TIIEREFOR
Year: 1881

page_text: LETTERS PATENT to William Lloyd Wise, of 7, Whitehall Place, in the City
of Westminster, for an Invention of "IMPROVEMENTS IN THE TREATMENT OF
ORGANIC SUBSTANCES FOR THE PRODUCTION OF AMMONIA, AND APPARATUS
TIIEREFOR." A communication from abroad by Dr. Hubert Grouven, of
Leipzig, Saxony, in the Gorman Empire.
PROVISIONAL SPECIFICATION left by the said William Lloyd Wise at the
Office of the Commissioners of Patents on the 1st June 1881.
WILLIAM LLOYD WISE, of 7, Whitehall Place, in the City of Westminster.
"IMPROVEMENTS IN THE TREATMENT OF ORGANIC SUBSTANCES FOR THE
PRODUCTION OF AMMONIA, AND APPARATUS THEREFOR." A communication from
abroad by Dr. Hubert Grouven, of Leipzig, Saxony, in the German Empire.
This Invention has reference to the conversion of the nitrogen in organic
substances into carbonate of ammonia by the reduction to ash of the said organic ⚫
substances in an atmosphere of steam at a high temperature (as for instance from
400 to 700 degrees), and to the conduction of the products so obtained with an
excess of steam through a glowing substance or substances, by preference that
substance described in the Specification of Letters Patent, No. 1136 of 1878, and in
the Provisional Specification, No. 5504 of 1880, and which is called by my foreign
correspondent" Grouven contact substance."
This process may be carried out either in apparatus of small dimensions for the
quantitatives analysis of nitrogen, or on a larger scale for the commercial production
of carbonate of ammonia.
In one form of apparatus employed for carrying out this Invention a graduated
water vessel, provided with an Erdmann's float, is connected to a trickling
apparatus. This trickling apparatus is formed of a thick india-rubber or other
tube, through which is drawn a skein of fine cotton threads, filling it tightly. These
latter have for object to furnish at a certain part of the tube where a regulating

page_text: screw pressure cock is placed a through passage of such cross-sectional dimensions
that the water oozes through in a minute continuous stream without intermission.
This regular trickling supply of water is conducted into a steam generator, where
it is transformed into a perfectly regular flow of steam.
By noting the speed of the flow of the water, by means of the graduations on the
water vessel, an exact control may be maintained over the generation of steam.
The steam generator may be an ordinary iron gas pipe closed at the front end by a
suitable asbestos plug, and at its opposite end fitted tightly and brazed with copper
into the pipe in which the ammonia is produced. It is filled with pieces of
ordinary porous stone, which suck up water in the manner of a sponge, and cause
the water dropping into the said pipe from the trickling apparatus to at once
spread itself over a large surface, and to become rapidly transformed into steam by
reason of the red heat at which the pipe is kept by means hereinafter described.
The flow of steam generated in the pipe is consequently regular and constant.
It passes slowly through the glowing bed of porous stone, and is thereby super-
heated to that degree of temperature at which it is capable of quickly reducing any
organic substance to ash.
The reduction into ash of the organic substance and the formation of the
ammonia take place in a second pipe provided at both ends with conical or other
shaped asbestos plugs.
These plugs may be conveniently formed of plates of asbestos cut in the form of
discs or columns out of pure American or other asbestos board, and connected
firmly together by rivets passing through an exterior copper plate. This arrange-
ment of plug or stopper gives a tight closure, and possesses the important property
of not wasting away at any temperature of the pipe, and of always being easy of
removal.
There are three of these plugs or stoppers in the apparatus, viz., one in the steam
generator, and which is bored to receive a connecting pipe from the trickling
apparatus, a second which closes the entrance by which the organic substance is
introduced to the pipe in which the ammonia is produced, and a third at the
opposite end of the ammonia pipe, and through which a tube goes to the condensing
arrangement.
Before the apparatus is used it is necessary that the steam generator and the
ammonia pipe should be heated to the temperature of melting copper or thereabouts,
and whilst so heated for a couple of hours a stream of steam should be kept con-
stantly passing through them. This steam becomes decomposed in contact with
the iron interior walls, and covers them with a compact layer of blue hydrocyanate
of protoxide of iron, which has the property in the case of the temperatures ruling
in the apparatus of being neutral with respect to the ammonia.
The substance or substances to be operated upon are placed for combustion in
porcelain boats of different dimensions, according to the nature of the substance to
be analysed. As the cold boat easily breaks on being slid into the glowing pipe,
there is previously placed round each of its ends an asbestos band, so that no direct
contact may take place between the porcelain and the metal.
The combustion boat is slid in the ammonia tube just under the junction of the
steam generator and the ammonia tube, so that its contents may be impinged upon
vertically by the glowing steam, and no part of the carbon may escape oxidisation.
The opposite end of the ammonia tube is filled by preference with what my foreign
correspondent calls "Grouven contact substance" in the form of small lumps
shaken with the pipe close together and retained in position by two iron caps.
This contact substance is the same that has been already described in the Specifi-
cation of Letters Patent, No. 1136 of the year Eighteen hundred and seventy-eight,
and in the Provisional Specification No. 5504 of the year Eighteen hundred and
eighty, and is of the kind with which the large retorts of the ammonium furnaces
described in the said Specification are filled.
This contact substance operates in the present ammonia pipe precisely as in the
hereinabove mentioned ammonium retorts.

page_text: After the vapours resulting from the combustion of the contact substance,
together with an excess of steam, have passed through the glowing bed of this
contact substance, or through a glowing bed of pieces of pumice stone, or
meerschaum, or asbestos, or porous sandstone, or clay lumps, or burnt tufa-stone,
or burnt groy-lime, or sifted coal cinders, or generally of neutral materials, which
present to the passing gases an extremely large glowing surface, they contain no
longer anything that is organic. All the elements of the organic substance to be
analysed leave the apparatus in the forms of hydrogen gas, carbonic oxide, carbonic
acid, and ammoniacal gns only.
The products of condensation collecting in the cooling apparatus are not at all
colored and tarry, as is usual for the products of condensation to be in nitrogen
analysing apparatus after Varrentrapp and Will, but, on the contrary in striking
contrast thereto, are colorless and bright as water. There are pure solutions of
carbonate of ammonia that may always be easily titrated, but for the immediate
condensation of the ammonia normal muriatic acid or normal sulphuric acid are
supplied to the condensing apparatus, according to the quantity and quality of
the sample used for the analysis.
The condensing apparatus is kept cool by a small but constant jet of cold water.
Its connection with the ammonia pipe is effected by a small india rubber or other
tube provided with hemp packing; therefore after each analysis or combustion
process it is only necessary to withdraw the front packing out of the tube, and
place a new packing in the same place for the next succeeding combustion
process.
Occasionally the contact substance must be regenerated by means of a current
of air which is drawn through it while in a glowing condition for the space of a
quarter of an hour. This air has a cleansing effect on the microscopically fine
pores of the substance, and maintains them in a stato of efficiency for a long
time.
At the commencement of each combustion process the boat is first of all placed
in the combustion pipe; after a short interval the pipe is connected to tho
condenser. By this means the air present in the pipe is driven by the steam.
The decomposition of the organic substance relatively to the evolution of gas is
greatest during the first five minutes. It may be made inuch slower by somewhat
cooling part of the combustion pipe before sliding in the boat, partly by screwing
down the burners which are situated under the ammonia pipe, and which serve to
heat both that pipe and the steain generator, and partly by removing certain heat
screens which there surround the pipe, and further by the temporary application of
a flap of wetted asbestos.
The water of the substance to be analysed also operates in favour of a slow
commencement of tho liberation of the gas, especially if the substance be highly
hydrated, as is generally the case. For the purpose of analysis the sample should
not be dried beforehand, but should be placed in the boat in its natural state,
although it may contain 20, 60, 75, or even as much as 90 per cent. of water.
The perfection of the analysis, that is to say, the perfection of the nction of the
steam and contact substance, requires the combustion pipe to be in a condition of
glowing heat, which must be maintained within certain limits. This temperature
may be determined by experience, or by the use of the No. 1 pyrometer grain,
which I have described in the Specification of Letters Patent, No. 1136, 1878.
The heating of the combustion or ammonia pipe, with which is at the same
connected the heating of the steam generator, which may conveniently be situated
above it, may be effected by a row of exceptionally large Bunsen gas burners placed
underneath, or by large Benzelius spirit burners.
It will be evident that the analytic procedure hereinabove described can be easily
applied for commercially obtaining ammonia from animal refuse, such as horn,
leather, glue, wool, etcetera, by means of apparatus constructed on a suitable scale.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said William Lloyd Wise in the Great Seal Patent Office on the
30th November 1881.
THE
WILLIAM LLOYD WISE, of 7, Whitehall Place, in the City of Westminster.
"IMPROVEMENTS IN THE TREATMENT OF ORGANIC SUBSTANCES FOR
PRODUCTION OF AMMONIA, AND APPARATUS THEREFOR." (A communication from
abroad by Dr. Hubert Grouven, of Leipzig, Saxony, in the German Empire.)
This Invention has reference to the conversion of the nitrogen in organic
substances into carbonate of ammonia by the reduction to ash of the said organic
substances in an atmosphere of steam at a high temperature (as, for instance, from
400 to 700 degrees), and to the conduction of the products so obtained with an
excess of steam through a glowing substance or substances, by preference that
substance described in the Specification of Letters Patent, No. 1136, of 1878, and
in the Specification of Letters Patent, No. 5504, of 1880, and which is called by
my foreign correspondent "Grouven contact substance."
This process may be carried out either in apparatus of small dimensions for the
quantitative analysis of nitrogen, or on a larger scale for the commercial production
of carbonate of ammonia.
It is
Referring to the accompanying Sheet of Drawings, which show an apparatus of
small dimensions for the quantitative analysis of nitrogen, Fig. I is a sectional
elevation, and Figs. 2, 3, 4, 5, and 6 arc detail views. A is an ordinary water
gauge 25 millimetres in diameter and 200 millimetres in height, graduated in half
cubic-centimetres and provided with Erdmann's float; B is a trickling apparatus
hanging about one metre below the gauge, from which it receives its water.
formed of a thick india rubber or other tube, 200 millimetres long and 10 milli-
metres bore, through which is drawn a skein of fine cotton threads filling it tightly.
These latter have for object to furnish at the part of the tube where the regulating
screw pressure cock is placed a through passage of such cross-sectional
dimensions that the water oozes through in a minute continuous stream without
intermission.
This regular trickling supply of water is conducted into a steam generator C,
where it is transformed into a perfectly regular flow of steam varying from 3/,
gramme to at most 1 grammes per minute.
By noting the speed of the flow of the water by means of the graduations on
the water vessel an exact control may be maintained over the generation of steam.
The steam generator C is an ordinary iron gas pipe about 25 millimetres in
diameter, which, as shown in Fig. 1, is closed at the front end by a suitable
asbestos plug, and is at its opposite end fitted tightly and brazed with copper at
D into the pipe E, in which the ammonia is produced. This pipe (C) is filled with
pieces of ordinary porous stone, which suck up water after the manner of a sponge,
and cause the water dropping into it from the trickling apparatus to at once
spread itself over a large surface, and to become rapidly transformed into steam
by reason of the red heat at which the pipe is kept by means hereinafter
described.
The flow of steam generated in the pipe is consequently regular and constant.
It passes slowly through the glowing bed of porous stone (about 700 millimetres in
length), and is thereby superheated to that degree of temporature at which it is
capable of quickly reducing any organic substance to ash.
The reduction into ash of the organic substance and the formation of the
ammonia take place in the ammonia pipe E, the length of which is about 1 metre,
and its bore about 32 millimetres. It is provided at both ends with conical or
other shaped asbestos plugs.

page_text: These plugs are formed of plates of asbestos cut in the form of discs or columns
out of pure American or other asbestos board, 5 millimetres thick, and connected
together firmly by rivets passing through an exterior copper plate (see Figs. 4, 5,
and 6). This arrangement of plug or stopper gives a tight closure, and possesses
the important property of not wasting away at any temperature of the pipe, and
of always being easy of removal. The plug F is solid; the plug G is bored, and
through it passes a strong small brass tube about 5 millimetres bore. Plug H, the
the diameter of which is smaller than either of the above, receives a similar brass
pipe for carrying the water from the trickling apparatus B amongst the porous
stone pieces. Both plugs H and G remain usually closed, that is, they are not
removed either at the commencement or at the end of a combustion process. The
plug F however must be removed to admit the boat D, which contains the weighed
substance to be analysed at the commencement of each operation, and must then
be again placed in the pipe.
It is necessary that the apertures of the pipes at F, G, and H should be bored
out conical and smooth for a length of about 20 millimetres, so that they may
present to the asbestos plugs a good surface for forming a tight joint.
Brass tubes should be laid through the stoppers H and G, because when glass
tubes are used in their stead they frequently break. Before the apparatus is used
it is necessary that the steam generator and the ammonia pipe, which may be
either wrought or cast iron, should be heated to the temperature of melting copper
or thereabouts, and whilst so heated for a couple of hours a stream of steam should
bo kept constantly passing through them. This steam becomes decomposed in
contact with the iron interior walls, and covers them with a compact layer of blue
hydrocyanate of protoxide of iron, which has the property, in the case of the
temperatures ruling in the apparatus, of being neutral with respect to the
-aminonia.
Pipes of brass, bronze, copper, silver, nickel, German silver, and platinum are
found to decompose nearly all the ammonia, whilst pipes of glass and porcelain are
apt to melt or break.
The substance or substances to be operated upon are placed for combustion in
porcelain boats of different dimensions, according to the nature of the substance to
be analyzed. As the cold boat easily breaks on being slid into the glowing pipe
thero is previously placed round each of its ends (see Fig. 1) an asbestos band, so
that no direct contact may take place between the porcelain and the metal. The
combustion boat is slid into the ammonia tube just under the junction of the
steam generator and the ammonia tube, so that its contents may be impinged upon
vertically by the glowing steam, and no part of the carbon may escape oxidisation.
The opposite end of the ammonia tube E is filled by preference with what my
foreign correspondent calls "Grouven contact substance" in the form of small
Jumps, 6 to 12 millimetres in length, shaken into the pipe close together, and
retained in position by two wire caps, Figs. 2 and 3. This contact substance is
the same that has been already described in the Specification of Letters Patent,
No. 1136, of the year Eighteen hundred and seventy eight, and in the Specification
of Letters Patent, No. 5504, of the year Eighteen hundred and eighty, and is of the
kind with which the large retorts of the ammonium furnaces described in the said
Specifications are filled.
This contact substance operates in the present ammonia pipe precisely as in the
hereinabove mentioned ammonium retorts.;
The action of the contact substance is as follows -
1. Every organic substance burnt in glowing steam of a certain temperature,
400°-700° C., liberates approximately 45-55 per cent. of its contents of nitrogen
in the form of carbonate of ammonia, the remainder about 50 per cent. in the form
of organic and alkaloidal vapours which form tar upon condensation.
2. No trace of nitrogen escapes in the form of free nitrogen as is otherwise to
a great extent the case at each combustion process conducted by means of air.
3. If those vapours, representing 50 per cent. of nitrogen, are passed through

page_text: glowing pipes filled with pieces of pumice stone, or meerschaum, or asbestos, or
porous sandstone, or clay lumps, or burnt tufa-stone, or burnt grey lime, or sifted
coal cinders, or generally of neutral materials which present to the passing gases
an extremely large glowing surface, then in the case of there being an excess of
steam and the air being excluded, an additional portion, about of the said
vapours becomes transformed into carbonate of ammonia.
"
4. But a total conversion of that 50 per cent. into carbonate of ammonia is
attained by no other substance than by means of the Grouven contact substance."
5. This substance physically considered is one of the lightest and most porous
solid mineral substances that are generally obtainable. Chemically considered it
may be described as an argillaceous earth, containing 50 per cent. of lime in the
forin of silicate of lime. Time also is an important factor in its action, as each
volume of gas must remain at least 10 seconds in contact with it, and therefore in
accordance with this consideration its volume is calculated for a given passage
of gas.
6. After the vapours resulting from the combustion of the contact substance,
together with an excess of steam have passed through the glowing bed of this
contact substance, presenting a length of about 400 millimetres and a diameter of
about 32 millimetres, they contain no longer anything that is organic; all the
elements of the organic substance to be analysed leave the apparatus in the forms
of hydrogen gas, carbonic oxide, carbonic acid, and aminoniacal gas only.
7. Hydrogen gas always predominates therein. For example, the resultant gas
in the manufacture of ammonia from turf or peat, according to the previous
Inventions already recited, contains a fairly constant volume of 64 per cent. of
hydrogen gas, 12 per cent. carbonic oxide, and 24 per cent. carbonic acid gas.
8. For the complete combustion of organic matters in steam, it is characteristic
that about 70 per cent, of the organic carbon becomes thereby transformed into
carbonic acid, and 30 per cent. into carbonic oxide. The oxygen of both is derived
from the decomposed water. The quantity of this latter varies according to the
carbon present, and amounts to 1-2-2 grammes per gramme of organic dried
substance.
To give, in conclusion, a short statement of the approximate parallel with the so
called dry distillation, it may be mentioned that generally an organic substanco
heated to glowing heat in a closed retort without admission of air and steam only
allows of its nitrogen to pass over in the form of ammonia, about 1/, remaining
behind in tar and carbon; the remainder of the nitrogen, at least 2/, escapes as free
nitrogen gas.
ני
The products of condensation collecting according to this Invention in the cooling
apparatus L are not at all coloured and tarry, as is usual for the products of
condensation to be in nitrogen analysing apparatus after Varrentrapp and Will,
but on the contrary, in striking contrast thereto, are colorless and bright as water.
There are pure solutions of carbonate of ammonia that may always be easily
titrated, but for the immediate condensation of the ammonia normal muriatic acid
or normal sulphuric acid are supplied to the condensing apparatus, according to the
quantity and quality of the sample used for the analysis.
As
The condensing apparatus L has spheres of about 70 millimetres diameter.
the Drawing shews it is kept cool by a small but constant jet of cold water. Its
connection with the ammonia pipe is effected by a small india rubber or other tube
N provided with hemp packing. Therefore after each analysis or combustion
process it is only necessary to withdraw the front packing out of this tube and
place a new packing in the same place for the next succeeding combustion process.
Occasionally (say after ten burnings) the contact substance inust be regenerated
by means of a current of air which is drawn through it while in a glowing condition
for the space of a quarter of an hour. This air has a cleansing effect on the
microscopically fine pores of the substance, and maintains them in a state of
fficiency for a long time.
At the commencement of each combustion process the boat is first of all placed

page_text: in the combustion pipe, after a short interval the pipe is connected to the condenser
By this means the air present in the pipe is driven out by the steam at N, and is
thus prevented from forcing out the acid through the fore part in the violence of
its passage outwards.
The decomposition of the organic substance relatively to the evolution of gas is
greatest during the first five minutes. It may be made much slower by somewhat
cooling part of the combustion pipe at D before sliding in the boat, partly by
screwing down the burners which are situated under the ammonia pipe, and which
serve to heat both that pipe and the steam generator, and partly by removing
certain heat screens which there surround the pipe, and further partly by tho
insertion of a cold bar of iron one inch thick into the pipe by the stop hole F.
If heating is obtained by a coal furnace the cooling is simply and efficaciously
obtained by pouring half a litre of water into the glowing coals.
The water of the substance to be analysed also operates in favour of a slow
commencement of the liberation of the gas, especially if the substance be highly
hydrated, as is generally the case. For the purpose of the analysis the sample
should not be dried beforehand, but should be placed in the boat in its natural
state, although it may contain 20, 60, 75, or even as much as 90 per cent. of water.
All green vegatables (grasses, kitchen vegetables, roots, etcetera), fresh all
animal matters (flesh, blood, eggs, etcetera), as also all wet industrial refuse,
are placed in the boat and burned direct without special preparation or the usual
pulverisation. Dry foods (corn, seeds, bread, meal, etcetera), as also air dried manure
(guano, bone-dust, leather scraps, etcetera), are also filled in in suitable pieces
unpulverised, but previously softened with a little water. Fluids of the consistency
of milk, root juice, beer, etcetera, are placed in the boat in quantities of from 10
to 20 cubic centimetres, and are mixed therein with sufficient argillaceous powder
in a glowing hot state to form a paste. But for the latter object care should bo
exercised not to take oxides of iron or sulphates (gypsum, etcetera), as all matters
which at the glowing heat give off oxygen to organic substances act destructively
on the ammonia; the addition of chlorides also, such as kitchen salt, etcetera, are
equally injurious.
The apparatus may conveniently burn up to 5 grammes of the dried organic
substance, for which reason the quantity is measured proportionately, so that
between 3-5 grammes of the dried substanco result for analysis. The duration of
the combustion process is governed somewhat by the nature of tho substance.
Most matters require only 30 minutes for analysis, many only 20 minutes.
only require 40 minutes. In all cases the end of the process may be known by
the ceasing of the gas bubbles, which at the commencement flow copiously through
the fore part, and always grow less towards the end.
A few
The perfection of the analysis, that is to say, the perfection of the action of the
steam and contact substance requires the combustion pipe to be in a condition of
glowing heat, which must be maintained within certain limits. This temperature
may be determined by experience, or by the use of the No. 1 pyrometer grain*
which I have described in the Specification of Letters Patent, No. 1136, of 1878.
The heating of the combustion or ammonia pipo E with which is at the same time
connected the heating of the steam generator, which may conveniently be situated
above it, may be effected by a row of exceptionally large Bunsen gas burners placed
underneath. The simplest and cheapest apparatus for heating will however be a
small coal furnace of the length of the pipe and of about 150 millimetres in width
and depth. If such oven is fed with a mixture of 3 volumina of coke and of one
volumen of charcoal, the heat will be perfect while the consumption will be about
half a kilo. of coal per analysis.
It will be evident that the analytic procedure 'hereinabove described can be
easily applied for commercially obtaining ammonia from animal refuse, such as
horn, leather, glue, wool, etcetera, and from concentrated or semi-fluid residuary
liquors of molasses by means of apparatus constructed on a suitable scale. This,
notwithstanding the relative cheapness of these refuse matters, has hitherto

page_text: returned little profit, and at most places has been given up, the cause lies in the
fact that by means of the dry distillation hitherto employed only a small part of
the nitrogen was got as ammonia, and that in the form of tar, difficult to clean.
Having thus described the nature of the said Invention and the manner in which
it is to be or may be performed, as communicated to me as aforesaid, I would have it
understood, that what is considered to be novel and original, and is therefore claimed
as secured to me under the Letters Patent hereinbefore first in part recited is,―
1. Converting nitrogen of organic substances into carbonate of ammonia by
reducing such organic substances to ash with steam at a temperature of from 400
to 700 degrees centigrade in an atmosphere from which air is excluded, and con-
ducting the products of the resulting combustion in admixture with an excess of
steam through glowing "Grouven contact substance," substantially as described.
2. The use for effecting the quantitative analysis of nitrogen of apparatus
constructed, arranged, and operating substantially as described and shewn in the
Drawings.
3. In apparatus for effecting quantitative analysis of nitrogen, and also in
similar apparatus constructed on a larger scale for the commercial production of
carbonate of ammonia, substantially as described, arranging the pipe for the
generation of the superheated steam over the combustion pipe in the same furnace,
so that both are heated by that furnace, as above set forth.
4. In apparatus of the kind referred to in Claims 2 and 3, the use as and for the
purposes specified of asbestos plugs, substantially such as described above.
5: In apparatus of the kind referred to in Claims 2 and 3, the application and use
of trickling apparatus, substantially as and for the purpose described above.
In witness whereof, I, the said William Lloyd Wise, have hereunto set my
hand and seal, this Thirtieth day of November, in the year of our Lord
One thousand eight hundred and eighty one.