since nitric acid forms with cellulose

The advantages of wood fibre as a paper material have been fully
recognised in the United States and in many Continental countries,
but more especially in Norway, Sweden, and Germany, from whence
large quantities of wood pulp are imported into this country. There
is no doubt that our home manufacturers have recently paid much
attention to this material, and it is highly probable that wood, as
an inexhaustible source of useful fibre, will at no distant date
hold a foremost rank. Indeed, the very numerous processes which
have been patented since the Watt process was first made known,
indicate that from this unlimited source of fibre the requirements
of the paper-maker may be to a large extent satisfied, provided, of
course, that the processes for reducing the various suitable woods
to the condition of pulp can be economically and satisfactorily
effected. The great attention which this material has received at
the hands of the experimentalist and chemist–the terms not being
always synonymous–shows that the field is considered an important
one, as indeed it is, and if successfully explored will, it is to
be hoped, yield commensurate advantages both to inventors and the
trade.

The object of the numerous inventors who have devised processes
for the disintegration of wood fibre–that is, the separation of
cellulose from the intercellular matters in which the fibres are
enveloped–has necessarily been to dissolve out the latter without
injury to the cellulose itself, but it may be said that as yet the
object has not been fully attained by either of the processes which
have been introduced. To remove the cellular matter from the true
fibre or cellulose, without degrading or sacrificing a portion of
the latter, is by no means easy of accomplishment when practised
on an extensive scale, and many processes which present apparent
advantages in one direction are often found to exhibit contrary
results in another. The field, however, is still an open one, and
human ingenuity may yet discover methods of separating wood fibre
from its surrounding tissues in a still more perfect manner than
hitherto.

The various processes for treating wood for the extraction of its
fibre have been classified into: (1) chemical processes; and (2)
mechanical processes. We will give precedence to the former in
describing the various wood pulp processes, since the pulp produced
by the latter, although extensively used, is chiefly employed,
in combination with other pulps, for common kinds of paper. In
reference to this part of our subject Davis says:–“Experience
has dictated certain improvements in some of the details of
those earlier methods, by which so-called ‘chemical wood pulp’
is manufactured very largely on the Continent of Europe…. It
is possible to obtain a pulp of good quality, suitable for some
classes of paper, by boiling the chipped wood in caustic soda, but
when it is desired to use the pulp so prepared for papers having a
perfectly white colour it has been demonstrated in practice that
the action of the caustic soda solution at the high temperature
which is required develops results to a certain degree in weakening
and browning the fibres, and during the past five years much labour
has been expended in the endeavour to overcome the objections
named. The outcome of these efforts has been a number of patents,
having for their object to prevent oxidation and subsequent
weakening of the fibres.” In several of these patents, to which we
shall refer hereafter, bisulphite of lime is employed as the agent
to prevent oxidation and consequent degradation of the fibres, and
in other processes bisulphite of magnesia has been used for the
same purpose. Davis further remarks: “Although a common principle
runs through all these methods of preparing cellulose from wood,
they differ in detail, as in the construction of the digesters
employed, methods of treating the wood stock before boiling it in
the sulphurous acid solution, and also as regards pressure, blowing
off the sulphurous acid gas, etc., but all these processes present
a striking similarity to the method patented by Tilghmann in 1867.”
There can be no doubt that the action of caustic soda, under high
pressures, is highly injurious both to the colour and strength of
the fibres, and any process that will check this destructive action
in a thoroughly practical way will effect an important desideratum.

=I. Chemical Processes=: _Watt and Burgess’s Process_.–This
process, which, with some modifications, is extensively worked
in America, consists in boiling wood shavings, or other similar
vegetable matter, in caustic soda ley, and then washing to remove
the alkali; the wood is next treated with chlorine gas, or an
oxygeneous compound of chlorine, in a suitable vessel, and it is
afterwards washed to free it from the hydrochloric acid formed. It
is now treated with a small quantity of caustic soda in solution,
which instantly converts it into pulp, which only requires to
be washed and bleached, and beaten for an hour and a half in
the beating engine, when the pulp is ready for the machine. The
wood-paper process as carried out in America has been described by
Hofmann, from whose work[15] we have abridged the following:–

The wood, mostly poplar, is brought to the works in 5-feet lengths.
The bark having been stripped off by hand, it is cut into ½-inch
slices by a cutter which consists of four steel knives, from 8
to 10 inches wide by 12 to 15 inches long, which are fastened in
a slightly inclined position to a solid cast-iron disc of about
5 to 7 feet diameter, which revolves at a high speed, chopping
the wood–which is fed to the blades through a trough–into thin
slices across the grain. The trough must be large enough to receive
the logs, usually 10 or 12 inches thick, and it is set at such an
angle that the logs may slide down towards the revolving cutters;
this slanting position only assists the movement of the logs,
while a piston, which is propelled by a rack, pushes them steadily
forward until they are entirely cut up. The piston, or _pusher_,
then returns to its original position, fresh wood is put into the
trough, and the operation repeated. In this way many tons of wood
can be chopped up by one of these cutters in a day. The sliced wood
is conveyed by trucks to an elevator by which it is hoisted up two
storeys to a floor from which the boilers are filled. The boilers
are upright cylinders, about 5 feet in diameter and 16 feet high,
with semi-spherical ends, provided inside with straight perforated
diaphragms, between which the chips from one cord of wood are
confined. A solution of caustic soda, at 12° B., is introduced with
the chips, and fires are started in a furnace underneath. At other
works the boilers are heated by steam circulating through a jacket
which covers the bottom and sides of the boiler.

The boiling is continued for about six hours, when the digestion
is complete, and the contents of the boilers are emptied with
violence, under the pressure of at least 65 lbs. of steam, which
had been maintained inside. A large slide valve is attached to
the side of each boiler for this purpose close to the perforated
diaphragm, and connected by a capacious pipe with a sheet-iron
cylinder of about 12 feet diameter and 10 feet high, which receives
the contents–pulp, liquor, and steam. The object of these large
chambers–one of which serves for two boilers–is to break the
force of the discharging mass. The steam passes through a pipe on
the top of each, and from thence through a water reservoir, while
the liquid containing the pulp flows through a side opening and
short pipe into movable boxes, or drainers, mounted on wheels, and
each capable of holding the contents of one boiler; these boxes are
pushed along a tramway up to the collecting chambers, where the
pulp is received. In a building 132 feet long and 75 feet wide, ten
digesting boilers are arranged in one straight line, and parallel
with the boilers runs the main line of rails, side tracks extending
from it to each of the chambers, and a turn-table is supplied at
every junction. By this arrangement the drainer waggons can be
pushed from the side tracks on to the main line, which leads to
the washing-engines in an adjoining room. A system of drainage
is established below the tramways, by which all the liquid which
drains from the waggons is carried away and collected for treatment
by evaporation; these carriers remain on the side tracks until the
pulp is ready for the washing-engine.

When the greater portion of the liquor has drained off, warm
water is sprinkled over the pulp from a hose for the purpose of
extracting all the liquid which is sufficiently concentrated
to repay the cost of evaporation–the most advantageous method
of recovering the soda. The contents of the waggons–from the
same number of boilers–are then placed in two washing-engines,
each capable of holding 1,000 lbs. of pulp. After being
sufficiently worked in these engines the pulp is transferred
to two stuff-chests, and from thence conveyed by pumps to two
wet-machines. The screens (strainers) of the wet-machines retain
all impurities derived from knots, bark, and other sources, and the
pulp, or half-stuff, obtained is perfectly clean and of a light
grey colour. The pulp is bleached with solution of bleaching powder
like rags, then emptied into drainers and allowed to remain therein
with the liquid for twenty-four to forty-eight hours, or long
enough to render the use of vitriol in the bleaching unnecessary.
The portion of the white pulp which is to be worked up into paper
in the adjoining mill is taken from the drainers into boxes
running on tramways in the moist state, but all the pulp which has
to be shipped to a distance is made into rolls on a large cylinder
paper-machine with many dryers. The object being merely to dry the
pulp, a very heavy web can be obtained, since the water leaves this
pulp very freely. The wood pulp thus obtained is perfectly clean,
of a soft, white spongy fibre, and a greater portion of it is mixed
with a small proportion of rag pulp and worked into book and fine
printing papers. Sometimes the wood pulp is used alone or mixed
with white paper shavings for book paper. The fibres are rather
deficient in strength, but as a material for blotting paper they
are said to be unsurpassed, while the wood paper is much liked by
printers.

The wood from poplar, which is generally preferred, furnishes a
very white fibre, and is easily digested, but since the fibres are
short it is sometimes found advantageous to mix them with longer
fibres, as those of the spruce or pine, although the latter wood
requires a much more severe treatment in boiling with alkali than
the former. In reference to this process the following remarks
appeared in _The Chemist_,[16] 1855:–“The process occupies only
a few hours; in fact, a piece of wood may be converted into
paper and printed upon within twenty-four hours.” An interesting
verification of this was published a few years since in an American
paper, the _Southern Trade Gazette_, of Kentucky, which runs as
follows:–“At a wood-pulp mill at Augusta, Ga., a tree was cut
down in the forest at six o’clock A.M., was made into pulp, and
then into paper, at six o’clock in the evening, and distributed
amongst the people as a newspaper by six o’clock the next morning.
From a tree to a newspaper, being read by thousands, in the brief
round of twenty-four hours!” The wood-paper process referred to has
given rise to many subsequent modifications, some of which we will
briefly describe.

=Sinclair’s Process.=–The wood is first cut into pieces about
1 inch broad, ⅛th inch thick, and from 2 to 3 inches long. It is
then placed in a boiler and a solution of caustic soda, in the
proportions of 600 gallons to 10 cwts. of dry wood, is poured over
it. The boiler having been securely closed, the heat is raised
till a pressure of 180 to 200 lbs. on the square inch is obtained,
when the fire is withdrawn and the boiler allowed to cool, after
which the ley is blown off, the top door removed, and the contents
scalded. The discharge door is now opened and the pulp transferred
to a poaching-engine to be washed with pure water, when the resin,
&c., are easily removed and the clean fibres obtained, which, it is
said, are longer and firmer than those obtained by other methods.

=Keegan’s Process.=–By this method soft deal or pine is sawn up
into pieces from 6 to 12 inches long and ½ inch thick, it being
preferable that all the pieces should be of an equal size, but the
smaller they are the more rapid, of course, will be the operation.
The pieces of timber are placed in a cylindrical boiler, turning
upon a horizontal axis while the digestion is progressing. In a
second boiler is prepared a solution of caustic soda of about 20°
B. (specific gravity 1·161), which is introduced through a pipe
into the first boiler, this being afterwards hermetically closed,
and the soda is forced into the pores of the wood by means of a
pump. When the wood is not more than half an inch in thickness
a pressure of 50 lbs. on the square inch is sufficient, and the
injection of the caustic soda solution is completed in half an
hour. The superabundant liquor is pumped back into the second
boiler for the next operation. The excess of liquor having been
removed from the wood as stated, steam is introduced between the
double sides of the first boiler, and the temperature of the wood
raised from 150° to 190° C. (334° to 438° F.). The wood is next
washed in the usual way until the liquor runs off perfectly limpid,
and the half-stuff thus produced may be converted into pulp either
before or after bleaching, according to the quality and colour of
the paper to be produced.

=American Wood-Pulp System.=–Another method of carrying out the
wood-pulp process has recently been described by Mr. E. A. Congdon,
Ph.B.,[17] from which we extract the following:–“Poplar, pine,
spruce, and occasionally birch, are used in the manufacture of
chemical fibre. Pine and spruce give a longer and tougher fibre
than poplar and birch, but are somewhat harder to treat, requiring
more soda and bleach. Sticks of poplar, freed from bark, and
cleansed from incrusting matter and dirt, are reduced to chips by a
special machine having a heavy iron revolving disc set with knives,
and are then blown by means of a Sturtevant blower into large
stove chambers after passing over a set of sieves having 1¼-inch
for the coarse and 1⅛-inch mesh for the fine sieves, from whence
they pass to the digesters, which are upright boilers 7 by 27
feet, with a manhole at the top for charging the chips and liquor,
and a blow-valve at the bottom for the exit of the boiled wood. A
steam-pipe enters at the bottom, beneath a perforated diaphragm,
and keeps the liquor in perfect circulation during the boiling of
the wood by means of a steam-ejector of special construction.”

_Boiling._–The average charge of wood for each digester is 4·33
cords,[18] giving an average yield of 4,140 lbs. of finished fibre
per digester. A charge of 3,400 gallons of caustic soda solution
of 11° B. is given to each digester charged with chips, and the
manhead is then placed in position and steam turned on. Charging
the digester occupies from thirty to forty-five minutes, and steam
is introduced until the gauge indicates a pressure of 110 lbs.,
which occupies about three hours. This pressure is kept up for
seven hours, when it is reduced by allowing the steam to escape
into a large iron tank which acts as a separating chamber for the
spent liquor it carries, the steam entering in at one end and
passing out at the other through a large pipe, the liquor remaining
in the tank. The steam is allowed to escape until the pressure
is reduced to 45 lbs., when the digester is blown. The blow-cap
being removed, the blow-valve is raised and the contents of the
digester are discharged into a pan of iron covered with a suitable
hood. The contents strike against a dash-plate placed midway in
the pan, which thoroughly separates the fibres of the wood. The
time occupied in the foregoing operations is from eleven to eleven
and a half hours. It takes from nine to ten hours to free the pans
from alkali, when they are removed to washing-tanks with perforated
metal bottoms, where the material receives a final washing before
being bleached.

_Washing._–Each of the three digesters has a pan into which
its contents are discharged, and there are also four iron tanks
used for holding the liquors of various strengths obtained
from the cleansing of the pulp and a fifth tank is kept as the
separating-tank before mentioned. When the digester is blown,
the pulp is levelled down with a shovel, and the liquor from the
separating-tank is allowed to flow into it. The contents of the
next strongest pan are pumped upon it, while at the same time the
strongest store tank flows into this pan. This flowing from the
tank to the pan, pumping from here to the pan just blown, and from
there to the evaporators, is kept up until the liquor is not weaker
than 6° B. hot (130° F.). The second pan is now down to 4° B. hot,
and the process of “pumping back” is commenced. The two weakest
tanks are put upon this pan and pumped out of the bottom of it into
the two tanks in which are kept the strongest liquors. The two weak
tanks have been filled in the process of completing the cleansing
of the third pan (the weakest) on which water was pumped until the
last weak tank stood at only ½° B. This pan, now cleaned, is hosed
and pumped over to the washing tanks. A fresh blow is now made in
this pan, and the same treatment kept up as with the first pan.

The foregoing system is thus illustrated by Mr. Congdon:–

Pan A.–Just blown.
” B.–Partly cleaned.
” C.–Almost cleaned.

Tank 1.–3½° B. hot.
” 2.–2° ” ”
” 3.–1° ” ”
” 4.–½° ” ”

Separating tank, strong.

A is levelled down; contents of separating-tank allowed to flow
upon it; B is pumped on to A; at the same time liquor from the two
strong store tanks is put on it (B), and this continued to be sent
from A to the evaporator until it is now weaker than 4° B. hot; the
process of “pumping back” is then commenced. The two weakest are
allowed in succession to flow on to it, and the liquor purified
from the bottom of B into the two strong tanks, filling No. 1,
the stronger, before No. 2. The weakest are filled in the process
of completing the cleansing of C, on which water is pumped until
the last tank from it tests only ½° B. C is now hosed and pumped
over to the washing tanks. A fresh digester is blown in C, and the
process repeated as with A.

The above system has been modified by having an extra pan into
which the liquor from the last pan blown (after sending to the
evaporators until down to 6° hot, and bringing down to 4° hot, by
the stored liquor) is pumped. When the strength is reduced to 4°
the pumping is stopped. The liquor from this pan is put in the next
pan blown, after the liquor from the separating-tank has been put
upon it, whereby an economy in time is effected.

The pulp, after being partially cleaned in the pans, still
contains an appreciable quantity of soda. It is hosed over to the
washing-tanks and receives a final washing with hot water. When the
pulp is thoroughly free from alkali, and the water flowing from
under the tank is colourless, the contents are hosed down by hot
water into the bleaching-tanks. The superfluous water is removed
by revolving washers, and about 1,000 gallons of a solution of
chloride of lime at 4° B. are then introduced, and the contents
agitated as usual. The bleaching occupies about six or seven hours,
when the pulp is pumped into draining tanks, where it is left to
drain down hard, the spent bleach flowing away. The stock is then
hosed and pumped into a washing-tank, where it acquires the proper
consistency for the machine. From here it is pumped into the stuff
chest, whence it goes over a set of screens and on to the machine,
from which the finished fibre is run off on spindles. The rolls
are made of a convenient size to handle, averaging about 100 lbs.
each. The fibre is dried on the machine by passing over a series
of iron cylinders heated by steam. The finished product is a heavy
white sheet, somewhat resembling blotting paper. The whole of the
foregoing operations are stated to occupy forty-five hours.

=Aussedat’s Process.=–By this method the wood is disintegrated
by the action of jets of vapour. In one end of a cylindrical
high-pressure boiler, about 4½ feet in diameter and 10 feet high,
is fixed a false bottom, whereby the wood placed upon it may be
removed from the liquor resulting from steam condensed in the
chamber, the whole being mounted on lateral bearings which serve
for the introduction of the vapour, and the wood is fed through a
manhole at the upper end of the boiler. Taps are fixed at the upper
and lower ends for the liquid and uncondensed vapour. The wood
having been placed in the boiler, the jet is gradually turned on in
such a way that at the end of three or four hours the temperature
becomes about 150° C., the pressure being about five atmospheres,
which point is maintained for an hour. As the slightest contact
between the wood and the condensed water would at once discolour
the former, it is essential that the liquid be removed from time to
time by one of the outlets provided for the purpose.

The treatment above described is said to be suitable for all kinds
of wood, and although it is the usual practice to introduce it in
logs about a yard long, any waste wood, as chips, shavings, etc.,
may be used. It is preferable, though not necessary, to remove the
bark, but all rotten wood may be left, as it becomes removed in the
condensed water. The logs, after the above treatment, by which the
fibre is disintegrated and the sap and all matters of a gummy or
resinous nature are removed, are afterwards cut up by any suitable
means into discs of about an inch, according to the nature of the
fibre required. These are then introduced into a breaker, in which
they become converted into half-stuff, which, after being mixed
with a suitable quantity of water is passed through mills provided
with conical stones, in which it becomes reduced to whole-stuff.
The pulp thus prepared is principally used in the manufacture of
the best kinds of cardboard, but more particularly such as is used
by artists, since its light brownish shade is said to improve the
tone of the colours. Bourdillat says that in the above process
the vapour has a chemical as well as a mechanical action, for in
addition to the vapour traversing the cellular tissues of the wood
and dissolving a considerable portion of the cell-constituents,
acetic acid is liberated by the heat, which assists the vapour in
its action on the internal substance of the wood.

=Acid Treatment of Wood.=–A series of processes have been
introduced from time to time, the object of which is to effect
the disintegration of wood fibre by the action of acids. The
first of these “acid processes” was devised by Tilghmann in
1866, in which he employed a solution of sulphurous acid; the
process does not appear to have been successful, however, and
was subsequently abandoned, the same inventor having found that
certain acid sulphites could be used more advantageously. Other
processes have since been introduced, in which wood is treated in a
direct way by the action of strong oxidising acids, as nitric and
nitro-hydrochloric acids, by which the intercellular matters of the
wood become dissolved and the cellulose left in a fibrous condition.

=Pictet and Brélaz’s Process.=–By this process wood is subjected
to the action of a vacuum, and also to that of a supersaturated
solution of sulphurous acid at a temperature not exceeding 212° F.
In carrying out the process a solution of sulphurous acid is used,
consisting of, say from ⅕ to ⅓ lb. avoirdupois of sulphurous acid
to each quart of water, and employed under a pressure of from three
to six atmospheres at 212° F. Under these conditions the cementing
substances of the wood “retain their chemical character without a
trace of decomposition of a nature to show carbonisation, while
the liquor completely permeates the wood and dissolves out all the
cementing constituents that envelop the fibres.” In carrying out
the process practically, the wood is first cut into small pieces
as usual and charged into a digester of such strength as will
resist the necessary pressure, the interior of which must be lined
with lead. Water is then admitted into the vessel and afterwards
sulphurous acid, from a suitable receiver in which it is stored
in a liquid form until the proportion of acid has reached that
before named, that is, from 100 to 150 quarts of the acid to 1,000
quarts of water. The volume of the bath will be determined by the
absorbing capacity of the wood, and is preferably so regulated
as not to materially exceed that capacity. In practice it is
preferable to form a partial vacuum in the digester, by which
the pores of the wood are opened, when it will be in a condition
to more readily absorb the solution and thereby accelerate the
process of disintegration. When disintegration is effected, which
generally occurs in from twelve to twenty-four hours, according
to the nature of the wood under treatment, the liquor, which is
usually not quite spent in one operation, is transferred to another
digester, a sufficient quantity of water and acid being added to
complete the charge. In order to remove the liquor absorbed by the
wood, the latter is compressed, the digester being connected with
a gas-receiver, into which the free gas escapes and in which it
is collected for use again in subsequent operations. The bath is
heated and kept at a temperature of from 177° to 194° F. by means
of a coil in the digester supplied with steam from a suitable
generator. The wood, after disintegration, undergoes the usual
treatment to convert it into paper pulp, and may thus be readily
bleached by means of chloride of lime. The unaltered by-products
contained in the bath may be recovered and treated for use in the
arts by well-known methods.

=Barre and Blondel’s Process= consists in digesting the wood for
twenty-four hours in 50 per cent. nitric acid, used cold, by which
it is converted into a soft fibrous mass. This is next boiled for
some hours in water and afterwards in a solution of carbonate of
soda; it is then bleached in the usual way.

=Poncharac’s Process.=–In this process cold nitro-hydrochloric
acid (aqua regia) is employed for disintegrating wood in the
proportions of 94 parts of the latter to 6 parts of nitric acid,
the mixture being made in earthen vessels capable of holding 175
gallons. The wood is allowed to soak in the acid mixture for six to
twelve hours. 132 lbs. of aqua regia are required for 220 lbs. of
wood. When it is desired to operate with a hot liquid, 6 parts of
hydrochloric acid, 4 parts of nitric acid, and 240 parts of water
are used in granite tubs provided with a double bottom, and it is
heated by steam for twelve hours and then washed and crushed.

=Young and Pettigrew’s Process.=–These inventors use either nitric
or nitrous acids, and the acid fumes which are liberated are
condensed and reconverted into nitric acid.

=Fridet and Matussière’s Process.=–This process, which was
patented in France in 1865, consists in treating wood with
nitro-hydrochloric acid, for which purpose a mixture of 5 to 40 per
cent. of nitric acid and 60 to 95 per cent. of hydrochloric acid
is used, which destroys all the ligneous or intercellular matter
without attacking the cellulose. After the wood (or straw) has been
steeped in the acid mixture, the superfluity is drawn off, and
the remaining solid portion is ground under vertically revolving
millstones. The brownish-coloured pulp thus obtained is afterwards
washed and bleached in the usual way.

It is quite true that cellulose can be obtained from wood and
other vegetable substances by treatment with nitric acid alone,
or with a mixture of nitric and hydrochloric acids, but it will
be readily seen that the employment of such large quantities of
these acids as would be required to effect the object in view on a
practical scale, would be fraught with incalculable difficulties,
amongst which may be mentioned the insuperable difficulty of
obtaining vessels that would resist the powerful corrosive action
of the acids. Moreover, since nitric acid forms with cellulose an
explosive substance (_xyloidin_) of the gun cotton series, the risk
involved in the drying of the cellulose obtained would be quite
sufficient to forbid the use of processes of this nature.

=Sulphite Processes.=–An important and successful method of
treating wood has been found in employing sulphurous acid,
combined in certain proportions with soda, lime, or magnesia,
whereby a bisulphite of the alkaline or earthy base is obtained.
One of the principal attributes of these agents is that in
boiling wood at high pressures oxidation and consequent browning
of the fibres is prevented. Of these sulphite, or more properly
bisulphite, processes, several of those referred to below have
been very extensively adopted, and vast quantities of so-called
“sulphite pulp” are imported into this country from Norway,
Germany, Scandinavia, &c., the product from the latter source
being considered specially suited for the English market. Some of
these processes are also being worked in this country, but more
particularly those of Partington, McDougall, and Ekman.

=Francke’s Process.=–In this process, which is known as
the “bisulphite process,” the active agent employed for the
disintegration of wood is an acid sulphite of an alkaline or earthy
base, as soda or potassa, lime, &c., but it is scarcely necessary
to say that the process has since been modified by others. The
invention is applicable to the treatment of wood, esparto, straw,
etc., and may be thus briefly described:–A solvent is first
prepared, which is an acid sulphite of an alkali or earth, that
is, a solution of such sulphite with an excess of sulphurous acid.
As the cheapest and most accessible base the inventor prefers
lime. It has long been known that a solution of sulphite of lime,
combined with free sulphurous acid, would, at a high temperature,
dissolve the intercellular portions of vegetable fibres, leaving
the fibres in a suitable condition for paper manufacture; but Mr.
Francke claims to have determined the conditions under which this
can be effected with rapidity, and in such a way as to preserve the
strength of the fibres, and to have obtained a practical method
of preparing pulp by his process. For his purpose he employs a
moderately strong solution of the solvent at a high temperature,
with gentle but constant agitation. The acid sulphite is produced
by this process at small cost and at a temperature nearly high
enough for use in the following way:–A tower or column is charged
with fragments of limestone, which are kept wetted with a shower
of water; fumes of sulphurous acid, produced by burning sulphur,
or by roasting pyrites, etc., are then passed through the tower.
The liquid which collects at the bottom of the tower is the
desired solvent, which should have a strength of 4° to 5° B. It
is not essential that the limestone should be pure, as magnesian
limestone, etc., will answer equally well. The soluble alkalies,
as soda and potassa, may also be used when their greater cost is
not an objection. But for these alkalies the treatment is modified,
as follows:–The tower is charged with inert porous material, such
as coke, bricks, etc., and these are kept wetted by a shower of
caustic alkali at 1° to 2° B., while the sulphurous acid fumes
are passed through the tower. In like manner carbonate of soda or
potassa may be used, but in this case the solution showered on the
porous material should be stronger than that of the caustic alkali,
so that it may contain approximately the same amount of real
alkali. Whichever alkaline base be employed, the liquid collected
at the bottom of the tower should have a strength of 4° to 5° B.;
this being the acid sulphite of the base is used as the solvent
employed for the manufacture of pulp. When wood is to be treated,
it is freed as much as possible from resinous knots by boring and
cutting them out, and is then cut–by preference obliquely–into
chips of a ¼ to ¾ of an inch thick. Esparto, straw, and analogous
fibres are cut into fragments. The fibrous material and solvent
are charged into a digester heated by steam at a pressure of four
or five atmospheres, and consequently capable of raising the
temperature of the contents to about 300° F. As agitation greatly
promotes the pulping of the materials, Mr. Francke employs a
revolving cylindrical boiler, which is allowed to revolve while the
charge is under treatment.

=Ekman’s Process.=–In this process, which in some respects bears
a resemblance to the preceding, native carbonate of magnesia
(magnesite) is first calcined to convert it into magnesia; it is
then placed in towers lined with lead, and sulphurous acid gas,
obtained by the burning of sulphur in suitable furnaces, is passed
through the mass, a stream of water being allowed to trickle down
from the top of the towers. The supply of gas is so regulated that
a continual formation of a solution of bisulphite of magnesium, of
an uniform strength, is obtained; great care, however, is necessary
to avoid excess and consequent loss of sulphurous acid by its
conversion into sulphuric acid. In boiling, the fragments of wood,
previously crushed by heavy rollers, are placed in a jacketed,
lead-lined, cylindrical boiler, suspended on trunnions, so that it
can be inverted to remove the charge. The pressure in the outer
jacket is 70 lbs. per square inch, and that within the boiler is
90 lbs. per square inch. The boiling occupies twelve hours. This
process has been extensively worked by the Bergvik and Ala Company,
of Sweden, for many years with great success, and we understand
that the company has been turned over to an English company–the
Bergvik Company, Limited. The Ilford Mill and Northfleet Works have
been largely supplied with sulphite pulp from the Swedish works.

One great drawback to the bisulphite processes is that the boiling
cannot be effected in iron boilers unless these be lined with some
material which will protect the iron from the destructive action of
the bisulphite, which, being an acid salt, would exert more action
upon the iron than upon the fibre itself, and the solution of iron
thus formed would inevitably prove injurious to the colour of the
fibre. In several of the systems adopted iron boilers lined with
lead have been used, but the heavy cost of this material and its
liability to expand unequally with the iron, especially at the high
temperatures which the solvent necessarily attains under pressure,
causes the lead to separate from the iron, while it is apt to bulge
out in places, and thus becomes liable to crack and allow the acid
liquor to find its way to the interior of the iron boiler which it
was destined to protect. To overcome this objection to the simple
lead lining, Dr. Mitscherlich patented a process which has been
extensively adopted in Germany, and is now being carried out by
several companies in different parts of America. This process is
briefly described below.

=Dr. Mitscherlich’s Process.=–The digester employed in this
process is lined with thin sheet lead, which is cemented to the
inner surface of the boiler by a cement composed of common tar and
pitch, and the lead lining is then faced with glazed porcelain
bricks. In this process a weaker bisulphite of lime is used than
in Francke’s, and the time of boiling is consequently considerably
prolonged.

=Ritter and Kellner= have proposed to unite the inner surface of
the boiler to its lead lining by interposing a soft metal alloy,
fusible at a temperature lower than that of either metal, and it
is claimed that the iron and lead are thus securely united, while
the alloy being fusible under the normal working temperature of the
digester, the lead lining can slide freely on a boiler shell.

=Partington’s Process.=–This process, which has been for some
time at work at Barrow, and for the further development of which
a private company, entitled the Hull Chemical Wood Pulp Company,
Limited, has been formed, consists in the employment of sulphite
of lime as the disintegrating agent. The process consists in
passing gaseous sulphurous acid–formed by burning sulphur in a
retort, into which is forced a current of air at a pressure of
5 lbs. to the square inch–through a series of three vessels,
connected by pipes, the vessels being charged with milk of lime.
The first two of these vessels are closed air-tight, and the gas
is then introduced, while the third vessel remains open; from this
latter a continuous stream of nitrogen escapes, due to the removal
of the oxygen by the burning sulphur from the air passed into the
retort. This process is said to be a very economical one, so far as
relates to the cost of materials used.

=Blitz’s Process.=–This process consists of employing a mixture
composed of bisulphite of soda 2 parts, caustic soda 1 part; and
vanadate of ammonia 1 gramme, in hydrochloric acid 4 grammes to
every 6 kilogrammes of the bisulphite. The wood, after being cut
up in the ordinary way, is submitted to the action of the above
mixture, under a pressure of three or four atmospheres, for from
four to eight hours, and the pulp is then ground; it is said to
possess some of the qualities of rag pulp and to look much like it.

=McDougall’s Boiler for Acid Processes.=–This invention is
intended to obviate the difficulties which arise in using
lead-lined boilers, owing to the unequal expansion and contraction
of the lead and the iron on their being alternately heated by steam
and cooled, on the discharge of each successive batch of pulp. This
invention consists in constructing the boilers with an intermediate
packing of felt, or other compressible and elastic material,
so that when the interior leaden vessel is heated, and thereby
enlarged and pressed outwards by the steam, the compressible and
elastic packing yields to the pressure and expansion. Also in the
cooling of the vessels the packing responds to the contraction,
and approximates to its original bulk and pressure between the two
vessels, and so prevents the rupture or tearing of the lead and
consequent leakage and other inconveniences. Another part of this
invention consists in the construction of the outer iron or steel
vessel in flanged sections, which are fitted to incase the interior
leaden vessel with a space between the two vessels, into which the
compressible and elastic materials are packed. In the construction
of these vessels the iron or steel flanged sections are placed on
to the leaden vessel and packed with the compressible and elastic
lining in succession. As each section is packed it is screwed
close up to the adjoining section by the screw bolts, fitted into
corresponding holes in the flanges of the contiguous section until
completed. This method of construction secures economy by the
retention of the heat, which is effected by the packing between the
two vessels. The materials used for the packing are caoutchouc,
felt, flocks, asbestos, etc., and a space of about two inches
between the vessels is preferred, into which the packing is filled.

=Graham’s Process.=–This process consists in boiling fibrous
substances in a solution of sulphurous acid, or a sulphite or
bisulphite of soda, potash, magnesia, or lime, or other suitable
base and water. The boiling is preferable conducted in a closed
boiler, lined with lead, to protect it from the action of the
chemical substances used, and is fitted with a valve which can be
opened to allow the gases and volatile hydrocarbons contained in
and around the fibres to escape. The method of carrying out the
process has been thus described:–“In carrying out the process
there is a constant loss of sulphurous acid gas going on, and
consequently a continual weakening of the solution employed, to
avoid which it is preferable to employ monosulphite of potash,
soda, magnesia, lime, or other suitable base, and water. Either
of these substances, or a suitable combination of them, and
water are placed in the boiler with the fibrous substances to be
treated, and the temperature raised to the boiling point. After
the hydrocarbons, air, and gases natural to the fibrous substances
have been driven out by the heat and allowed to escape, sulphurous
acid, in its gaseous or liquid state, or in combination with
either of the bases referred to, is pumped or injected into the
boiler. There is thus forming in the closed boiler a solution
containing an excess of sulphurous acid above that required to
form, in combination with the base, a monosulphite. The operation
of injecting sulphurous acids, or the sulphites, may be repeated
from time to time during the boiling, so as to fully maintain,
and if necessary increase, the strength and efficiency of the
chemical solution. It is said that by this process a saving of the
chemicals employed is effected, as little or no sulphurous acid gas
is lost during the time the gaseous hydrocarbons, air, and other
gaseous matters are being expelled from the fibrous materials.
If an open vessel is used instead of a closed boiler, it will be
necessary to keep the solution at a fairly uniform strength, and
if necessary to increase the strength, but the result will be
substantially the same; but as it is evident that, when using an
open boiler, the excess of sulphurous acid supplied during the
boiling will be constantly driven off as gas, it must be replaced
by further injections, while the acid fumes may be conveyed away
and condensed, so as to be available for further use. When the
fibrous substances are boiled as above, with the addition of
potash, soda, etc., during the boiling, the result will be equally
beneficial. The inventor prefers to inject the sulphurous acid
or its combinations into the boiler at the bottom, and to cause
it to come in contact with the solution therein before reaching
the fibrous materials. For this purpose there is formed a kind of
chamber beneath the boiler, but separated from it by a perforated
disc or diaphragm of lead or other suitable material not acted upon
by the solution, so as to allow the latter to fill the chamber, to
which is connected a pipe, through which the sulphurous acid or
solutions of the sulphites is forced by any suitable apparatus.

=Objections to the Acid or Bisulphite Processes.=–While
the various methods of boiling wood in caustic soda at high
temperatures are well known to be open to serious objections, the
acid treatment of wood also presents many disadvantages, which
it is to be hoped may be yet overcome. In reference to this,
Davis makes the following observations:–“In the acid treatment
of wood for the purpose of converting the fibres into pulp for
use in paper manufacture, the general practice has been to use
alkaline solutions of soda, combined in various proportions with
certain acids, such, for instance, as sulphurous acid, hydrochloric
acid, etc. These solutions have been heated in digesting vessels,
and the high temperature resulting from this process of heating
developing a pressure of from six to seven atmospheres, the wood
being disintegrated by the action of the boiling solutions, the
gum, resinous constituents, and other incrustating or cementing
substances that bind the fibres together are decomposed, destroyed,
or dissolved, while pure cellulose, which constitutes the essential
element of the ligneous fibres, is separated therefrom. To this end
high temperatures had to be employed, otherwise the disintegration
was found to be only partial, the wood remaining in a condition
unfit for further treatment. The high temperature not unfrequently
converts a large proportion of the resinous and gummy constituents
of the wood into tar and pitch–that is to say, carbonaceous bodies
that penetrate into the fibre and render its bleaching difficult,
laborious, and costly, while the frequent washing and lixiviation
necessary to bleach such products seriously affect the strength
of the fibre and its whiteness, and also materially reduce the
percentage of the product, in some instances to the extent of 18
per cent. These difficulties and detrimental results materially
enhance the cost of production, while the fibre itself suffers
considerably in strength from the repeated action of the chloride
of lime…. The difficulties are chiefly due to the carbonisation
of certain constituent parts of the fibres under temperatures
exceeding 212° F., such carbonised matters being insoluble and
incapable of being bleached, and as they permeate the fibre, cannot
be entirely removed.

“To overcome these difficulties, the wood should be chemically
treated at a temperature sufficiently low to ensure that the
decomposition of the connecting substances of the fibres will
remain chemically combined with the other elements, such as
hydrogen, oxygen, and nitrogen, in order to obtain an increased
product of superior quality and render the process more economical.”

=Sulphite Fibre and Resin.=–A German manufacturer sent the
following communication to the _Papier Zeitung_, which may
be interesting to the users of sulphite pulp:–“In making
[disintegrating] cellulose by the soda or sulphite process, the
object in boiling is to loosen the incrusting particles in the
wood, resin included, and to liberate the fibres. The resin is
dissolved both in the soda and sulphite processes, but in the
former it is at the same time saponified, and is consequently
very easily washed out. In the case of sulphite fibre, however,
the resin attaches itself by its own adhesiveness to the fibres,
but can also be removed by as hot washing as possible, and adding
a little hydrochloric acid, which produces a very great effect.
At the same time, however, sulphite fibre loses in whiteness
by thorough washing, and assumes a reddish-grey shade. As the
paper manufacturer insists upon white fibre, the manufacturer of
sulphite fibre not only often omits washing, but adds some sulphite
solution (bisulphite of lime). This not only enables him to give
his customers white fibre, but he also sells a quantity of the
incrusting particles and sulphite residuum as cellulose.

“So long as the manufacturer looks more to white than to
well-washed cellulose, or does not wash it well before working up
the fibre, these annoyances cannot be avoided. Not only this, but
other disadvantages will be added in the course of time, as the
action of the sulphurous acid in the pulp will have very injurious
consequences on metals–[and on the fibre itself?] especially
iron–coming in contact with it. This should be the more avoided,
as the whiteness of the unwashed cellulose is of very short
duration. The paper made from it soon turns yellow and becomes
brittle. Well-washed sulphite fibre, on the other hand–provided
no mistakes have been made in the boiling process–makes a strong,
grippy paper, which can withstand both air and sunlight. I have
made no special studies as to resin, but believe that pine and fir
act differently, especially with solvents.”

=Adamson’s Process.=–Mr. W. Adamson, of Philadelphia, obtained
a patent in 1871 for the use of hydrocarbons in the treatment of
wood. His process consisted in treating the wood with benzine in
closed vessels, under a pressure of 5 to 10 lbs., according to the
nature of the wood. His digester consisted of an upright cylinder,
in which the wood-shavings were placed between two perforated
diaphragms. The mass was heated beneath the lower diaphragm by
a coil through which steam was passed. The vapours which were
given off were allowed to escape through a pipe on the top of the
digester, to which was connected a coil immersed in a vessel of
cold water, and the condensed liquid then returned to the lower
part of the digester. The remaining portion of the benzine in the
digester, which was still liquid but saturated with the extracted
matters, was drawn off through a faucet at the bottom. Benzine
being a very cheap article in America, a similar process was
recommended in another patent by the same author for extraction of
pitch and tar from rags [tarpaulin, ropes, &c.?], and for removing
oil from rags and cotton waste.

=Sulphide Processes.=–Many attempts were made about thirty years
ago, and in subsequent years, to employ the soluble sulphides as a
substitute for caustic soda in boiling wood and other fibres, but
these processes do not appear to have been very successful. Later
improvements in the construction of boilers or digesters, however,
seem to have induced further experiments in this direction, and we
understand that several sulphide processes are being worked on the
Continent, the processes of MM. Dahl and Blitz being amongst them.
One of the supposed advantages of these sulphides over caustic soda
is that by evaporation and calcination of the liquors, or leys, by
which the organic matters become destroyed, the original product
would be recovered, which merely requires to be dissolved out for
further use. There are, however, several important objections to
the use of sulphides in this way, amongst which may be mentioned
the deleterious vapours which they emit; and this alone would
doubtless prevent their employment–at all events in this country.

=II. Mechanical Processes.=–Besides the various chemical methods
of separating cellulose from woody fibres, before described,
certain processes have been devised for reducing wood to the
condition of pulp directly by mechanical means without the aid
of any chemical substance whatsoever. In this direction Heinrich
Voelter, of Wurtemburg, appears to have been the first to introduce
a really practical process for the conversion of wood into pulp
for paper-making, although, as far back as 1756, Dr. Schaeffer,
of Bavaria, proposed to make paper from sawdust and shavings
mechanically formed into pulp: the process was not successful,
however, with the machinery then at his command.

=Voelter’s Process for Preparing Mechanical Wood Pulp.=–In 1860-65
and 1873 Voelter obtained patents in this country for his methods
of treating wood mechanically, and the process may be thus briefly
described:–Blocks of wood, after the knots have been cut out by
suitable tools, are pressed against a revolving grindstone, which
reduces the material to a more or less fine condition, but not in
a powdery form, and the disintegrated fibre is caused to press
against a wire screen, which allows the finer particles to pass
through, retaining the coarser particles for further treatment.

[Illustration: Fig. 17A.–Voelter’s Wood-pulping Machine.

[_To face page 78._]

The apparatus employed, which is shown in Fig. 17A, consists of a
pulping apparatus A, with vat K, in which the revolving stone S is
placed; the blocks of wood are held against the stone at _p p_,
and water is introduced at G, and the revolving stone carries the
pulp against the screen E, which admits the passage of the finer
particles of the wood, while the coarser particles are led by the
trough F to the first refining cylinder B, after passing through an
oscillating basket, which retains the coarser particles. From
thence it is led through a distributing apparatus and hopper C, to
be uniformly supplied to the refining cylinder D, these cylinders
being of the ordinary construction, and, as usual, covered with
fine gauze wire sieves. The ground material which fails to pass
through the sieves is transferred by an elevator to the millstones
E, which are of ordinary construction, and after leaving these
unites with the finer fibres which pass through E, the whole now
entering a mixing reservoir F, whence it is thrown on to the
cylinder G, and the pulp which passes into this is distributed
on to a similar cylinder H, the contents of which then passes
through the last cylinder I, which is differently constructed
to the others, inasmuch as its lower part is surrounded by an
impervious leather jacket, so that the pulp ascends in order to
enter it. The disintegrated fibres that are retained by the wires
of the cylinders pass into the refiners, which consist of a pair
of horizontal cylinders of sandstone, one of which (the upper one)
only revolves, and by the action of these the coarser fibres become
further reduced, the finer particles, as before, passing through
the wire gauze of the cylinders, the operation being repeated in
the same order until the whole of the fibres have passed through
the sieves.


=Thune’s Process.=–Mr. A. L. Thune, of Christiana, U.S.A., has
recently patented an apparatus for disintegrating wood, which
consists of a grinding apparatus connected to a turbine. In this
arrangement the grindstone, fixed on a shaft, is worked by a
turbine, and the wood, which is used in small blocks, is pressed
against the stone by means of a series of hydraulic presses. The
fine pulp is afterwards made into thick sheets by means of a
board-machine, the pulp, mixed with water, passing down a shoot
into a vat beneath, in which is a revolving cylinder covered with
wire-cloth, which in its revolution carries with it a certain
quantity of pulp in a continuous sheet; this is taken on to an
endless travelling belt by means of a small couch-roll, and passes
on to a pair of rolls, round the upper one of which the sheet
becomes wound, and is removed when sufficiently thick.

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