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CONTINUOUSPROCESS FOR MANUFACTURE OF values are essentially completely and economically
NITROCELLULOSE recovered for reuse and a virtually pollution-free
The invention described herein may be manufac system is obtained.
tured, used and licensed by or for the Government for A further object is to provide a novel method for
governmental purposes without the payment to us of 5 recovering nitric acid and magnesium nitrate values
any royalties thereon. from aqueous liquors containing same.
This invention relates to an improved continuous, Other objects and advantages of this invention will
pollution-free process for the manufacture and purifi appear or be obvious from the description of the inven
cation of nitrocellulose, wherein cellulose is nitrated tion set forth below.
with a nitrating medium containing nitric acid and mag O In general, these objects are accomplished according
nesium nitrate. It also relates to a novel method for to this invention by a continuous process, which com
recovering nitric acid and magnesium nitrate from prises
aqueous liquors containing same. 1. feeding dry cellulose, e.g. cotton or wood pulp,
The conventional commercial process for manufac 15 and a nitrating medium of nitric acid and magnesium
turing nitrocellulose comprises nitrating cellulose with nitrate into an attrition type mill, wherein the cellulose
"mixed acid', i.e. a mixture of nitric and sulfuric acids. is reduced to more or less controlled size particles,
This produces large amounts of sulfates, nitrates and freshly exposed surfaces of cellulose are brought into
fines as waste products and pollutants. Further, the immediate and intimate contact with the nitrating
nitrocellulose product must be subjected to lengthy and 20 medium and nitration of the cellulose is initiated;
costly purification treatments to remove sulfuric acid 2. completing the reaction to the desired degree of
and sulfate ester contaminants retained in the nitrocel nitration in the attrition mill or other suitable continu
lulose. ous flow nitrator;
It has been proposed to effect the nitration of cellu 3. separating the spent nitration medium from the
lose with a nitrating agent comprising essentially nitric 25 nitrocellulose in a centrifuge, vacuum filter or other
acid, magnesium nitrate and water. Thus, as stated in suitable means and concentrating it for reuse in the
U.S. Pat. No. 2,776,966, this nitrating agent provides a system;
number of advantages over the mixed acid process, e.g. 4. purifying the nitrocellulose by washing it with
it penetrates and wets even dense aggregates of cellu water on a belt or other suitable filter to remove
lose particles more rapidly and uniformly, provides a 30 retained nitric acid and magnesium nitrate impurities;
more rapid nitration reaction and a more uniform 5. contacting the wash liquors containing nitric acid
nitrocellulose product, and eliminates the need for long and magnesium nitrate with an ion exchange medium
and tedious treatments to purify and stabilize the which removes the nitrate and magnesium ions from
nitrocellulose produced. The patent discloses a con said liquors;
tinuous process for preparing nitrocellulose, wherein a 35 6. recovering the magnesium and nitrate ions as mag
sheet of cellulose is continuously passed through a nesium nitrate and recycling the magnesium nitrate
nitrating bath of said type and thereafter subjected to thus obtained to the system.
countercurrent washing with water in a series of zones A preferred method of processing the wash liquors
to remove nitric acid and magnesium nitrate retained in containing nitric acid and magnesium nitrate (step 5
the nitrocellulose. The spent nitrating agent and wash 40
above) comprises
liquors are concentrated in a distillation apparatus and a. contacting the liquors with a basic, nitrate ion
recycled to the nitrating bath along with fresh nitric selective ion exchange resin capable of being
acid and magnesium nitrate to replace that lost from regenerated with ammonium hydroxide, whereby the
the system so as to keep the system in balance. The nitrate ions are absorbed and magnesium hydroxide is
washed nitrocellulose sheet is then passed into a disin 45
tegration bath vessel where it must be reduced to a par formed,
ticulate form for further purification, dehydration, etc. b. contacting the ion exchange resin with aqueous
About 85 percent of the nitric acid and magnesium ammonia to form ammonium nitrate and regenerate
nitrate values retained in the spent acid remaining in the resin,
the nitrocellulose is removed by countercurrent wash 50 c. heating a mixture of the aqueous ammonium
ing, and about 15 percent of such nitric acid and mag nitrate and magnesium hydroxide thus obtained to
nesium nitrate values are left in the nitrocellulose sheet form magnesium nitrate and gaseous ammonia,
after washing. Due to the physical state of the nitrocel d. recovering the ammonia and magnesium nitrate
lulose thus obtained this latter amount is difficult to and recycling same to the system.
eliminate, and its removal requires relatively tedious 55 The following description together with the accom
and costly treatments, e.g. comminution of the panying schematic drawing illustrate a preferred em
nitrocellulose sheet followed by extensive extractions bodiment of the process of the invention.
with aqueous alkalis and water. Thus it is lost from the As shown in the drawing, a continuous sheet of
system and must be replaced. 60
fibrous cellulose from roll 1 or loose linters is passed
An object of this invention is to provide an improved into a dryer 2 and thence to a shredder 3 which reduces
continuous process for nitrating cellulose with nitric the cellulose sheet to a suitable size for use in the nitra
acid-magnesium nitrate nitrating agent, which tion, e.g. pieces not exceeding about three-fourths inch
produces a more rapid and uniform reaction and a in largest dimension. The cellulose pieces from the
nitrocellulose product which can be more readily and 65
shredder and nitrating agent, preheated or precooled as
more completely purified by washing. desired, consisting of nitric acid, magnesium nitrate
Another object is to provide a continuous process of and water, are fed into an attrition mill 4. The attrition
said type wherein the nitric acid and magnesium nitrate mill contains one or more rotating circular plates
3,714, 143
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(discs) in close proximity to one or more stationary the wash liquor increases in each succeeding zone in
companion plates. The milling surfaces of the plates are opposite direction to the movement of the belt and is
grooved, serrated or otherwise formed to provide vari greatest in the first zone. Wash liquor from the
ous degrees of milling action. The rotating discs are aforesaid first zone flows through liquid cyclone
mounted on a drive shaft and can be adjusted to pro separator 10 to ion exchange bed 11. Nitrocellulose
vide various clearances with the companion stator fines recovered in separators 8 and 10 are returned to
plates. A clearance of 0.002 to 0.02 inch is satisfactory. the continuous belt filter prior to its entry into said first
Instead of a mill with rotor and stator disc plates, other zone. The purified nitrocellulose leaving the last wash
attrition mills can be employed, which by means of a O
zone is forwarded to a conventional thermal dehydra
solid surface moving at high speed and in close prox tor (not shown).
imity relative to another solid surface of any suitable An important advantage provided by nitration in an
shape, (e.g. a cone, cylinder, dished plate, etc.) pro attrition mill employed in this invention is that the
vides a rubbing and abrasive action on cellulose parti nitrocellulose product is produced in a soft, fluffy
cles in the liquid nitration mass passing between such 5 physical form, which can be readily purified by washing
surfaces. with a medium of water. Thus, adhering nitric acid and
In the attrition mill the reaction mixture in the form magnesium nitrate can be essentially completely
of a thin slurry flows between the stator and high speed removed by washing with less than 1 pound of water
rotor plates, whereby the cellulose pieces are reduced per pound of nitrocellulose produced. This makes com
to fine particles of a more or less controlled size, freshly mercially feasible the recovery of the magnesium and
exposed surfaces of the cellulose are brought into im nitrate values from the wash liquors by means of cer
mediate and intimate contact with the nitrating agent, tain ion exchange systems described below.
nitration of the cellulose is initiated and water of reac When the nitrocellulose product possesses a nitrogen
tion is immediately removed to the main body of nitrat content substantially greater than 12 percent by
ing agent. Ratios of nitric acid to magnesium nitrate 25 weight, it is advantageous to apply a neutralization
and water in the nitrating agent, as well as ratios of wash with aqueous ammonia after most of the nitric
nitrating agent to cellulose, reaction temperatures, etc. acid and magnesium nitrate have been washed out with
which are suitable, are well known in the art, as dis water and then follow with a final water wash. The use
closed in U.S. Pat. No. 2,776,966. The reaction mix of aqueous ammonia (or ammonium carbonate) to
ture leaving the mill may be recycled, passed through 30 wash the nitrocellulose product is uniquely compatible
another attrition mill or conducted to one or more con with the ion exchange system for recovering nitric acid
ventional continuous flow nitrators 5 and 6, as and magnesium nitrate from wash liquors, as described
required, to complete the reaction to the desired below. w
degree of nitration of the cellulose. The wash liquors from the liquid cyclone separator
The nitration mass then flows to a continuous cen 35 10 are conducted to an anionic ion exchange resin bed
trifuge 7, wherein the nitrocellulose is separated from 11 packed with coarse particles of a nitrate ion selec
the spent nitrating agent. The spent nitrating agent tive ion exchange resin capable of being regenerated
discharged from the centrifuge flows through a liquid with ammonia. During continuous operation the wash
cyclone separator 8 for removal of fines, and thence to 40 liquors usually contain about 10 to 20 parts HNO and
a system (not shown) for concentrating nitric acid and about 100 to 200 parts Mg(NO), per million, although
magnesium nitrate by distillation. If desired, the much higher concentrations are present for a short
nitrocellulose in the peripheral or discharge zones of time at start of operations. Suitable ion exchange resins
the centrifuge can be washed e.g. sprayed with a are strongly basic synthetic resins in free hydroxide
limited amount of water to remove a portion of the ad 45 base form, such as a quaternary ammonium hydroxide
hering spent nitrating agent. The resulting wash liquors type resin based on a styrene-divinylbenzene
can be conducted through separator 8 to the concen copolymer. Commercially available anionic ion
tration system, or through separator 10 to ion exchange exchange media of this type include those marketed as
bed 11. Since washing increases the dilution and cost of Amberlite" Ion Exchange Resins IRA 47 and IRA 68 by
concentrating the spent acid by distillation, the concen 50 Rohm and Haas Co. Nitrate ions are thus completely
tration and method of processing such wash liquors will removed from the liquors and the magnesium hydrox
be determined by an economic balance between (a) ide formed thereby as a suspension of fine particles in
concentration by distillation and (b) recovery by ion the liquor readily passes through the bed of relatively
exchange. The nitrocellulose cake continuously coarse resin particles and is separated in a fine sand or
discharged from the centrifuge can be slurried in water 55 other suitable filter 12. The effluent from filter 12 is es
and pumped or dumped directly onto a continuous sentially deionized, pollution-free water, which can be
moving belt filter 9 for purification by countercurrent sewered or recycled to continuous belt filter 9 for
washing with water. The belt passes through a number washing nitrocellulose pulp. When aqueous ammonium
of successive separate wash zones. Fresh water is 60 hydroxide or carbonate is also used for washing
sprayed through nozzles onto the nitrocellulose cake in nitrocellulose, the effluent from filter 12 contains am
the last zone and drawn through the cake by means of a monium hydroxide and is advantageously recycled to
slight vacuum. The wash liquor from the last zone is the system, e.g. for washing nitrocellulose. .
then pumped through another set of nozzles onto the When the capacity of ion-exchange bed 11 is
cake in the penultimate zone and the filtrate from that 65 reached (when effluent contains nitrate ions) the flow
zone is pumped onto the cake in the next preceding of wash liquor from separator 10 is directed to a
Zone, and so on until the first zone. In this manner the duplicate resin bed 13 and filter 14. Filter 12 is then
concentration of magnesium nitrate and nitric acid in backwashed with a minimum of water to recover the
3,714,143
S 6
magnesium hydroxide as a fine aqueous suspension, create essentially no pollution problems. The spent
which flows via a by-pass of bed 11 (not shown) to nitric acid-magnesium nitrate mixture thus concen
storage tank 15. The ion exchange resin bed 11 is trated and recovered can be mixed with (1) fresh con
backwashed with aqueous ammonia to regenerate the centrated nitric acid to replace that consumed in the
resin and remove the displaced nitrate ions as a solu nitration and (2) fresh magnesium nitrate, if necessary,
tion of ammonium nitrate, which flows to storage tank to replace small amounts lost in the system, and
16. Aqueous ammonium hydroxide solutions of about 4 returned to the system for nitrating cellulose.
to 12 percent, concentration, such as are recovered in Other ion-exchange systems can be employed for
the system described below, can be employed for 10
recovering the nitrate and magnesium values from
backwashing the resin. The ammonium hydroxide aqueous liquors obtained in the present process. For
stripping solution can be recycled through the bed if example, the liquors can be passed through a three
desired to increase the concentration of ammonium column system as follows:
nitrate in the effluent forwarded to the storage tank. The first column contains a bed of anionic ion
When regeneration is complete, the flow of wash liquor 15
exchange resin composed of quaternary ammonium
from separator 10 can be returned to ion exchange bed resin in hydroxide form, which has been converted
11. Duplicate bed 13 is deionized and regenerated in from the free hydroxide base form to the bicarbonate
similar manner. form by washing with aqueous carbonic acid solution.
Ammonium nitrate solution from storage tank 16 This bed removes the nitrate ions and converts the
and magnesium hydroxide suspension from storage liberated magnesium ions to soluble magnesium bicar
tank 15 are continuously fed into a heat exchanger 17, bonate. The effluent from the first column containing
which may comprise one or more vertical agitated ves magnesium bicarbonate flows through a second
sels provided with heating coils, bottom inlet ports for column packed with a cationic ion exchange resin in
introducing liquid reactants, overflow outlet near the free acid form, which removes the magnesium ions by
top for liquid effluent, nd an outlet at the top for con 25 ion-exchange. An illustrative, commercially available
ducting ammonia and water vapors to a water absorber cationic ion exchange resin suitable for this purpose is
or condenser for producing ammonium hydroxide (not marketed as Amberlite. IRC 84 by Rohm and Haas Co.
shown). The concentration of the ammonium nitrate The effluent from the second column, consisting essen
solution is generally about 4 to 12 percent by weight, tially of aqueous carbonic acid solution free from
since the ammonium hydroxide solution used for 30 nitrate and magnesium ions, is passed through a third
regenerating the resin bed is usually of similar concen column packed with the aforesaid quaternary ammoni
tration. The magnesium hydroxide slurry is also of um ion exchange resin in hydroxide form. The resin is
similar concentration. The aqueous ammonium nitrate thereby converted to the bicarbonate form. The ef
and magnesium hydroxide are introduced in essentially 35 fluent from this column is completely deionized water,
a 2:1 molar ratio into the heat exchanger, wherein they which can be recycled to the system for washing the
are mixed and maintained at or near the boiling point nitrocellulose product, or sewered.
under ordinary pressure, e.g. about 100°C., and react When the resin in the first column is exhausted, as
to form ammonia and magnesium nitrate according to shown by the presence of nitrate ions in the effluent
the following equation: 40 therefrom, the liquid flow is shifted to the third column,
which functions in the same manner as the first column.
2NHNO+ Mg(OH) - Mg (NO) + NH+2 HO Thereafter, the bed in the first column is washed with a
Since some free nitric acid is extracted from the stream of aqueous ammonium hydroxide solution,
nitrocellulose, a slight excess of ammonium nitrate is which removes the nitrate ions therefrom by formation
usually present. Also, the reaction mixture is usually at 45 of ammonium nitrate and converts the resin to the
most only slightly acid, since the ammonium nitrate hydroxide form. When the bed in the first column has
liquor contains some free ammonia resulting from the been completely divested of nitrate ions in this manner,
regeneration of the ion-exchanged bed with ammonium it is converted to the bicarbonate form by introducing
hydroxide. Since the system generates a somewhat the effluent from the second column consisting essen
larger ratio of ammonium nitrate than is required for 50 tially of aqueous carbonic acid solution free from
the aforesaid reaction, additional amounts of magnesi nitrate and magnesium ions.
um hydroxide from an outside source may be fed to the When the resin in the second column is exhausted, as
storage tank to maintain the required ratio thereof. indicated by the presence of magnesium ions in the ef
The ammonium hydroxide solution thus recovered fluent therefrom, the liquid flow is transferred to a
together with additional fresh ammonium hydroxide, as 55 standby column containing a bed of identical cationic
required in the system, is recycled for use in regenerat resin. The resin in the second column is then washed
ing the ion exchange bed and/or in washing the with a stream of dilute nitric acid, e.g. 5-10% strength,
nitrocellulose pulp. The magnesium nitrate solution ex which removes the magnesium ions as magnesium
iting from heat exchanger 17 may be concentrated 60
nitrate and converts the resin to the original free acid
separately or sent along with spent nitrating agent form. When the magnesium ions have been completely
separated from nitrocellulose pulp, to a system for con removed in this manner, the column can be placed on
centrating nitric acid-magnesium nitrate nitrating stream again. The standby column is processed in
medium (not shown). Suitable systems for concentrat identical manner.
ing nitric acid by distillation with magnesium nitrate 65 The magnesium nitrate solution thus obtained which
are well-known, as illustrated in aforesaid U.S. Pat. No. may also contain free nitric acid is recycled to the
2,776,966. Such systems, as ordinarily operated, system for concentrating and fortifying the nitration
produce practically no waste effluents and hence medium. The amount of ammonium nitrate formed and
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7 8
recovered the aforesaid system is relatively small. Thus, 1. It eliminates the conventional use of mixed acid as
in nitration of cellulose according to the process of this the nitrating agent together with the lengthy purifica
invention, not more than about 1 pound of ammonium tion treatments and pollution problems attending its
nitrate per 1,000 pounds of nitrocellulose product are use, and produces a nitrocellulose product of at least
generally formed. Such small amounts can be disposed equal quality.
of as fertilizer. 2. It provides a continuous process for the manufac
It is advantageous to integrate and operate all steps ture and purification of nitrocellulose, which is safe and
of the novel process in an overall continuous process, economical; it also provides an essentially completely
as described above. However, it is possible to operate 10
closed system, which generates no waste products to
some steps discontinuously, if desired, e.g. the concen pollute the environment. The spent nitrating agent con
tration and fortification of the spent nitrating medium, sisting of nitric acid and magnesium nitrate is concen
the recovery of the magnesium and nitrate values in the trated, fortified and returned to the system. Nitrocellu
ion exchange system, etc. lose fines are collected and returned to the system.
The following example illustrates the process of the 15 Nitric acid and magnesium nitrate washed from the
invention: nitrocellulose product are recovered as magnesium
Dry cellulose sheet in 4 inch squares (from southern nitrate and returned to the system.
pine base pulp) and nitrating medium, consisting of 3. It provides an improved continuous method for
64.6 percent nitric acid, 19.47 percent magnesium nitrating cellulose with nitric acid-magnesium nitrate
nitrate and 15.93 percent water, were continuously fed 20 nitrating agent, which comprises passing the cellulose
into a laboratory attrition mill (Bauer Bros. Co. No. material and nitrating agent through an attrition type
148-1-BE) consisting essentially of a stainless steel, ver mill, wherein the cellulose is reduced to fine particles in
tically rotating circular plate in close proximity to a the presence of the nitrating medium. In this manner
companion stationary circular plate. The plates were 8 the nitrocellulose product is obtained in a fluffy physi
in. in diameter, possessed radial grooves and were con- 25 cal form, which possesses a normally soft surface and is
tained in a stainless steel housing. The feed entered the more readily purified by washing than the relatively
mill through the center hole of the stationary plate and hard-surfaced nitrocellulose product obtained by batch
centrifugal force carried the feed into the milling sec nitration with said nitrating agent.
tion of the plates and the nitrocellulose pulp to the mill 30
4. It provides a novel, economical method, involving
cavity surrounding the plates for discharge at the bot use of a nitrate ion selective ion-exchange medium, for
tom of the cavity. The effluent from the mill was recir recovering nitric acid and magnesium nitrate values
culated a second time. The reaction conditions were as from aqueous wash liquors such as are obtained in the
follows: . nitration of cellulose and other organic compounds e.g.
35
glycerine, pentaerythritol, etc. with nitric acid-mag
Ratio nitrating medium/cellulose 50/1 nesium nitrate nitrating agent. These values are
Reaction temperature 40°C. recovered as magnesium nitrate which can be recycled
Time through mill, each pass 100 sec.
Mill plate clearance 0.003-0,005 in. to the nitrating agent.
Mill plate speed 3510 rpm 5. It provides a nitrocellulose product, which can be
40 completely purified by washing with small amounts of
The reaction mixture flowed from the mill to an water, rendering recovery of nitric acid and magnesium
agitated tank, wherein its average sojurn period was nitrate from wash liquors economically attractive.
sufficient to complete the reaction to the desired We wish it to be understood that we do not desire to
degree of nitration (overall nitration cycle about 6 be limited to the exact detail of construction shown and
minutes), and thence to a continuous centrifuge, which 45 described for obvious modification will occur to a per
separated the nitrocellulose from the spent nitrating son skilled in the art.
medium. The nitrocellulose was transferred to a con What is claimed is:
tinuous belt filter and washed counter-currently with 1. A continuous process for the manufacture of
hot (85C) water until acid-free and dried. The wash nitrocellulose which comprises
liquors were processed in the ion-exchange system and 50 a. passing cellulose and liquid nitrating agent consist
manner described above in relation to the drawing 1 to ing essentially of nitric acid, magnesium nitrate
recover their contents of nitric acid and magnesium and water, and containing a ratio of from about 1.2
nitrate as magnesium nitrate. The recovered magnesi to 2.2 parts by weight of magnesium nitrate per
um nitrate and recovered spent nitrating agent were part of water and sufficient nitric acid to yield
concentrated and fortified in conventional manner and 55 nitrocellulose of at least about 11 percent by
recycled to the process. weight of nitrogen, through an attrition mill under
The nitrocellulose thus obtained contained 11.9 per conditions wherein the cellulose is abraded and
cent nitrogen. The chemical and physical charac nitrated,
teristics of the nitro-cellulose thus obtained were
60
. separating the nitrocellulose from the spent nitrat
equivalent to those of nitrocellulose produced by con ing agent,
ventional nitration with mixed acid (nitric-sulfuric acid . concentrating the spent nitrating agent by distilla
mixtures) and were superior to those of nitrocellulose tion and recycling it to the system,
obtained by batch nitration of shredded cellulose sheet . purifying the nitrocellulose by washing it with
with nitric acid-magnesium nitrate mixture. water to remove nitric acid and magnesium nitrate
From the foregoing description it can be seen that 65 impurities,
the invention provides a number of advantages over the . contacting the wash liquors containing nitric acid
prior art. Thus: and magnesium nitrate with an ion exchange
3,714, 143
9 10
system which removes the nitrate and magnesium c. The aqueous ammonium nitrate and magnesium
ions from said liquors, hydroxide thus obtained are mixed and heated to
f. recovering the nitrate and magnesium ions, form magnesium nitrate and gaseous ammonia,
g. converting said magnesium ions to magnesium d. The magnesium nitrate and ammonia thus ob
nitrate, and i recycling the magnesium nitrate thus 5 tained are recovered and recycled to the system.
obtained to the system. 6. The process according to claim 5, wherein the
2. The process according to claim 1, wherein the wash liquor contacted with the ion exchange medium
reaction mixture from the attrition mill is conducted to contains from about 10 to 20 ppm HNO and from
an agitated vessel to complete the nitration. about 100 to 200 ppm of Mg(NO).
3. The process according to claim 1, wherein the O 7. The process according to claim 1, wherein
nitrocellulose separated from spent nitrating agent is a. The wash liquors containing nitric acid and mag
washed with aqueous ammonia subsequent to washing nesium nitrate are contacted with an anionic ion
with water and thereafter washed with water. exchange resin in bicarbonate form, which
4. The process according to claim 1, wherein removes the nitrate ions and converts the magnesi
nitrocellulose fines are separated from the spent nitrat 15 um ions into soluble magnesium bicarbonate,
ing medium and aqueous wash liquors and recycled to b. the anionic resin containing the nitrate ions is con
the nitrocellulose product subjected to washing. tacted with ammonium hydroxide which removes
5. The process according to claim 1, wherein the nitrate ions and forms ammonium nitrate,
a. The wash liquors containing nitric acid and mag 20 c. the magnesium bicarbonate is contacted with a ca
nesium nitrate are contacted with a basic nitrate tionic ion exchange resin, which removes the mag
ion selective ion exchange medium capable of nesium ions and forms carbonic acid solution,
regeneration with aqueous ammonia, thereby d. the cationic ion exchange resin containing the
removing the nitrate ions and forming magnesium magnesium ions is contacted with dilute nitric
hydroxide, acid, which removes the magnesium ions and
b. The ion-exchange medium is thereafter contacted 25 e. forms
the
soluble magnesium nitrate, and
magnesium nitrate thus obtained is recycled to
with aqueous ammonia to remove the nitrate ions the system.
as ammonium nitrate and regenerate the ion
exchange medium,
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