TEPZZ¥Z97Z5ZB_T

(19)

(11) EP 3 097 050 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C01B 11/18 (2006.01) C06B 21/00 (2006.01)
16.05.2018 Bulletin 2018/20
(86) International application number:
(21) Application number: 14830935.4 PCT/CZ2014/000164

(22) Date of filing: 29.12.2014 (87) International publication number:

WO 2015/110095 (30.07.2015 Gazette 2015/30)

(54) A METHOD FOR PROCESSING OF EXPIRED SOLID ROCKET PROPELLANT

VERFAHREN ZUR VERARBEITUNG VON AUSGESTOSSENEM
FESTSTOFFRAKETENTREIBSTOFF
PROCÉDÉ DE TRAITEMENT DE CHARGE PROPULSIVE SOLIDE PÉRIMÉE POUR FUSÉE

(84) Designated Contracting States: • CERNOCH, Michal

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 74235 Mankovice (CZ)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • KUPKA, Jan
PL PT RO RS SE SI SK SM TR 70800 Ostrava-Poruba (CZ)
• MYSIK, Jan
(30) Priority: 21.01.2014 CZ 20140048 70800 Ostrava-Poruba (CZ)

(43) Date of publication of application: (74) Representative: Krmencik, Vaclav et al

30.11.2016 Bulletin 2016/48 Rott, Ruzicka, Guttmann
Patent Trademark and Law Office
(73) Proprietor: ERUCA TECHNOLOGIES S.R.O. Vinohradska 37
735 95 Bohumin (CZ) 120 00 Praha 2 (CZ)

(72) Inventors: (56) References cited:

• SOUCEK, Martin US-A- 4 198 209 US-A- 4 662 893
747 06 Opava (CZ) US-A- 4 854 982 US-A- 5 331 106
US-A- 5 346 512
EP 3 097 050 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 3 097 050 B1

Description

Technical Field

5 [0001] The invention relates to processing of expired solid rocket propellant, which contains ammonium perchlorate,
powdered aluminium and a rubber-based binder as the three main components, for the purpose of ammonium perchlorate
recycling.

Background Art
10
[0002] Several documents deal with processing of rocket propellant for the purpose of ammonium perchlorate recycling.
[0003] The patent US 4,854,982 uses liquid ammonia for the processing. It is just the presence of liquid ammonia
(necessity to maintain a high pressure, toxicity of ammonia) that represents a disadvantage of this method, along with
a low capacity of the technology related to a unit of investment costs.
15 [0004] However, most patents use leaching of ammonium perchlorate into an aqueous solution as the principally basic
part of the processing.
[0005] The patent US 3,451,789 gradually processes propellant by disintegration, leaching of ammonium perchlorate
into a hot aqueous solution followed by multiple-stage separation of the solid residue after leaching from the obtained
solution.
20 [0006] The patent US 4,662,893 deals with the construction of the leaching unit. A disadvantage of the two above
mentioned patents is the problem of formation of agglomerates of solid residues of the propellant during disintegration,
leaching and their separation from the solution, which results in high energy and construction demands and a reduction
of efficiency of the recycling process.
[0007] The patent US 4,198,209 solves this problem by adding surfactants (surface active agents). A disadvantage
25 of this treatment is contamination of the obtained ammonium perchlorate solution by a foreign substance and formation
of foam causing technological problems during further processing.
[0008] The US patent No. 5, 346, 512 A- (Miks Kathryn F. et al) discloses a method for treating of recovered ammonium
perchlorate. Activated carbon is contacting only an ammonium perchlorate solution. The solution is obtained by two-
step filtration process comprising coarse screen and 25-micron filter which is more demanding that one-step filtration.
30 According to this US patent activated carbon is used only to remove contaminants from the solution.
[0009] The published US patent does not solve the problem of agglomeration during the leaching step. There is no
effect of activated carbon or another inert material on solid substances in the suspension.
[0010] The above problem is further dealt with in the U.S. patents US 4,198,209 - Frosch et al.: "Process for the
leaching of AP from propellant." (1980); US 3,451,789 - McIntosh: "Oxidizer recovery process" (1969); US 4,662,893 -
35 McIntosh: "Hydraulic waste propellant macerator and method of use" (1997); US 4 854 982 - Melvin et al.: "Method to
dimilitarize extract, and recover ammonium perchlorate from composite propellants using liquid ammonia" (1989); and
US 4,098,627 (1998).

Disclosure of Invention
40
[0011] The subject of the invention is an improved method for processing of expired solid rocket propellant that contains
ammonium perchlorate, powdered aluminium and a rubber-based binder as its three main components while the purpose
is to obtain and recycle ammonium perchlorate contained in it in a sufficient purity and to at least overcome some
disadvantages resulting from the prior art disclosed above.
45 [0012] This means that the invention deals with a method for processing of expired rocket propellant containing
ammonium perchlorate, powdered aluminium, a rubber-based binder and remaining minority admixtures to recycle
ammonium perchlorate that it comprises the following steps:

• wet mechanical-physical-chemical disintegration of the said solid propellant while a suspension of solid substances
50 in a solution is produced;
• b) leaching of the stirred said suspension at an increased temperature in water and/or unsaturated ammonium
perchlorate solution containing added inert material based on porous carbon, diatomaceous earth and/or polymer;
• c) de-agglomeration and prevention of re-agglomeration of solid substances in the suspension with the use of the
said inert material during the leaching process;
55 • d) separation of the ammonium perchlorate solution from the solid substances;
• e) refining of the separated ammonium perchlorate solution from step d) with the said inert material, except the
polymer-based material, at an increased temperature;
• f) separation of the inert material from the ammonium perchlorate solution optionally followed by concentrating the

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solution;
• g) crystallization and optional re-crystallization of the recycled ammonium perchlorate.

[0013] Besides the three main components, i.e. ammonium perchlorate, powdered aluminium and a rubber-based
5 binder the expired rocket propellant also contains minority admixtures including e.g. ferric oxide, cupric dichromate, di(2-
ethylhexyl)adipate, di(2-ethylhexyl)azelate, triphenylbismuth, pyrogallol, magnesium oxide, or 2,4-pentanedione.
[0014] In accordance with the above mentioned method for processing according to the invention the solid rocket
propellant removed from the rocket engine in a considerate mechanical-physical-chemical way (preferably e.g. by being
cut out with a water jet) is disintegrated under wet conditions (while the medium is water or a diluted ammonium perchlorate
10 solution), preferably in a mill, providing a suspension of solid substances and a solution.
[0015] Solid rocket propellant can also be preferably disintegrated by cutting in a cutter, crushing in a crusher or in
another suitable device.
[0016] While being stirred, the resulting suspension is fed into a leaching tank where the leaching solution (water or
an unsaturated ammonium perchlorate solution) and inert material was placed in advance.
15 [0017] As the inert material any inorganic or organic material can be used that is chemically inert to water and/or the
ammonium perchlorate solution, is composed of particles with a size of 1 mm to 20 mm, whose density in the wet state
is 800-2000 kg m-3, and that does not exhibit adhesive or self-adhesive properties in the wet state.
[0018] The inert material is a material based on porous carbon, more preferably powdered active carbon while the
most preferably material is used powdered active carbon from the previous refining of the ammonium perchlorate, or a
20 material based on diatomaceous earth, more preferably kieselguhr, or a polymer-based material, which is preferably a
thermoplastic, in particular polyethylene or polypropylene.
[0019] A crushed thermoplastic material that includes e.g. polyethylene, polypropylene, etc. is more preferable.
[0020] In the method in accordance with the invention the quantity of the added inert material is preferably at least 0.5
% by weight, more preferably 1.5 % by weight based on the dry basis weight of the solid propellant residues (i.e. dry
25 basis of the binder with admixed aluminium powder).
[0021] In accordance with the invention the particle size of the inert material is preferably in the range from about 1.0
mm to about 20 mm for roughly spherical particles. Particles of an elongated shape, in particular flat, may be larger than
20 mm in one direction.
[0022] Leaching of the stirred suspension is preferably carried out at elevated temperature, which is from about 50
30 °C to about 90 °C for at least 15 minutes while ammonium perchlorate is leached into the solution.
[0023] During the leaching step the present inert material in the suspension causes de-agglomeration of the solid
substances and prevents their re-agglomeration, which makes the entire leaching process of ammonium perchlorate
considerably more efficient. This process uncovers the surface of the solid substances, which supports easier and more
intensive leaching of ammonium perchlorate into the solution.
35 [0024] The suspension is then subjected to separation of the resulting solution from the solid substances, i.e. solid
propellant residues (wet binder with admixed aluminium powder) e.g. by means of filtration while a filtration device can
be preferably used that enables pressure action during the filtration and washing of the filtration cake (with a diluted
solution of ammonium perchlorate and/or water), which results in a high degree of separation.
[0025] After that, the separated solution of ammonium perchlorate proceeds to the next processing step (refining the
40 solution and obtaining pure crystals of recycled ammonium perchlorate by means of crystallization).
[0026] The solution can be further preferably refined with powdered active carbon with subsequent filtration, more
preferably pressure filtration while the used active carbon can be re-used for introduction into the leaching solution in
step b) leaching as the inert material.
[0027] The main advantage of the said method in accordance with the invention is elimination of agglomerates during
45 the processing in the leaching step. These agglomerates, consisting of sticky disintegrated pieces of solid rocket pro-
pellant, have the character of dense elastic matter. The inert material prevents formation of agglomerates during the
leaching process, considerably improving the leaching process (easier and less energy-demanding stirring and more
efficient leaching as well as a relatively simpler design of the equipment).
[0028] In the method according to the invention the inert material further prevents agglomeration of solid propellant
50 residues during the separation, which enables improvement of the separation process and use of solid residues of the
propellant as even after pressure filtration they can be easily reshaped into a bulk material with a low content of remaining
ammonium perchlorate, which makes its further processing and use possible.
[0029] Without addition of an inert material pressure filtration turns solid propellant residues into a homogeneous
elastic mass.
55 [0030] Another advantage of the above mentioned process is that recycled ammonium perchlorate obtained using the
method in accordance with the invention is not contaminated by addition of any other chemical as the inert material
remains part of the solid propellant residues after the separation.

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Examples

1.1. Laboratory demonstration

5 [0031] In the first trial wet propellant residues were compressed in the bulk state in a press whose body was a metallic
tube. The compression temperature was 80 °C, compression pressure 0.7 MPa, compression time 30 minutes. The
result was solid matter of propellant residues in a cylinder shape.
[0032] The second trial was carried out similarly with the difference that wet solid propellant residues were mixed with
powdered active carbon before the trial (3.5 % by weight of carbon based on the dry basis weight of the solid propellant
10 residues). The result of the compression was cylinders that had a larger diameter than cylinders from the first trial due
to lower cohesion (effort for elastic return to the original uncompressed state). The cylinders from the second trial could
be easily crumbled up to the bulk state.
[0033] The third trial was carried out similarly to the second trial, but the wet solid propellant residues were mixed with
1 mm polypropylene particles before the trial (1.5 % by weight of polypropylene based on the dry basis weight of the
15 solid propellant residues). The results were similar to the second trial.
[0034] The fourth trial was carried out similarly to the second trial, but the wet solid propellant residues were mixed
with 10 mm particles of crushed PET before the trial (1.5 % by weight of crushed PET based on the dry basis weight of
the solid propellant residues). The results were similar to the second trial.
[0035] The fifth trial was carried out similarly to the second trial, but the wet solid propellant residues were mixed with
20 filtration kieselguhr before the trial (2.0 % by weight of filtration kieselguhr based on the dry basis weight of the solid
propellant residues). The results were similar to the second trial.

1.2. Operation test

25 [0036] A leaching tank was charged with 2500 kg of a 15% solution of ammonium perchlorate and 50 kg of an inert
material, powdered active carbon with the moisture content of 50 %. This active carbon had been previously used for
refining of an ammonium perchlorate solution. The mixture was stirred and maintained at the temperature of 85 °C.
[0037] The processed material was solid rocket propellant in the form of 50340330 cm prisms obtained by cutting
from a rocket engine with a water jet, having the following weight composition: ammonium perchlorate 40 %, water 18
30 %, solid residue 42 %.
[0038] 3500 kg of solid rocket propellant, being sprayed with a 15% solution of ammonium perchlorate (the total amount
of 1000 kg of the sprinkling solution with the temperature of 25 °C was used), were disintegrated in an industrial cutter
and the resulting mixture was continuously transported to the leaching tank the content of which was continuously stirred
while its temperature was maintained at 85 °C. After completion of the disintegration the suspension mixture was stirred
35 for 15 min in the leaching tank.
[0039] Then, the mixture was separated with the use of a chamber filter press. The filter press being full, the filling
pressure achieved about 1 MPa. After that the filtration cake was blown with air, washed with demineralised water (3000
kg in total) and compressed using the pressure of 0.5 MPa).
[0040] The separated solution and washing water concentrated by evaporation were refined with active carbon while
40 after removal of active carbon by filtration a recycled ammonium perchlorate of high purity was obtained by crystallization
and re-crystallization, see Table 1.
[0041] After opening of the chamber filter press the filtration cake of solid residues of the propellant was retained in a
collection tank and crumbled up into the form of bulk and easy to process matter with a low remaining content of
ammonium perchlorate. The properties of the separated solid propellant residues are shown in Table 2. The calculated
45 yield from the point of view of ammonium perchlorate recycling was 99.0 %.
[0042] The same trial conducted without any addition of active carbon, however in addition of PET chips (80 kg) with
particle size of 10 mm resulted in free-flowing and easily workable mass having a low residual content of ammonium
perchlorate, see Table 3.
[0043] The same trial conducted without any addition of active carbon, however in addition of 10 kg of surface active
50 agent (SDS-sodium dodecyl sulphate) resulted in more difficult workable mass having a medium residual content of
ammonium perchlorate, see Table 4. In addition the surface active agent contained in solutions caused technological
difficulties in subsequent procession (e.g. solution foaming, changes in the crystallization process etc.).
[0044] The same trial conducted without any addition of active carbon or any different additive resulted in the filtration
cake being caught in the collection tank in the form of solid coherent plates that could not be processed any longer. The
55 content of ammonium perchlorate in the material obtained this way was 4.3 % by weight, see Table 5, because both
blowing-through and filter-washing effect were considerably decreased due to compactness of plates in the filtrate cake.

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 EP 3 097 050 B1

Table 1:
Purity of recycled ammonium perchlorate

5 Property in accordance with STANAG 4299, type 1 Requirement Result

Purity [% by weight] ≥ 99.0 99.8
Cl- as NH4Cl [% by weight] ≤ 0.1 0.001
ClO 3- as NH4ClO3 [% by weight] ≤ 0.02 < 0.003
10
BrO3- as NH4BrO3 [% by weight] ≤ 0.004 < 0.002
Sulphate ashes [% by weight] ≤ 0.15 < 0.02
Substances insoluble in water [% by weight] ≤ 0.03 0.007

15 pH [-] <4.3-5.8> 4.5

SO42- as (NH4)2SO4 [% by weight] ≤ 0.20 0.004
Fe as Fe2O3 [% by weight] ≤0.0035 0.00086
Sum of Na, K, Ca [% by weight] ≤ 0.08 0.0075
20
Substances soluble in ether [% by weight] ≤ 0.01 <0.001

Table 2:
25
Properties of the solid propellant residues after separation (addition of active carbon)
Property Value
Moisture [% by weight] 18

30 Content of ammonium perchlorate [% by weight] 0.7

Content of ammonium perchlorate in the dry basis [% by weight] 0.9

35 Table 3:
Properties of the solid propellant residues after separation (addition of PET chips)
Property Value
Moisture [% by weight] 19
40
Content of ammonium perchlorate [% by weight] 0.6
Content of ammonium perchlorate in the dry basis [% by weight] 0.7

45
Table 4:
Properties of the solid propellant residues after separation (addition of SDS)
Property Value

50 Moisture [% by weight] 17
Content of ammonium perchlorate [% by weight] 1.5
Content of ammonium perchlorate in the dry basis [% by weight] 1.8

55

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Table 5:
Properties of the solid propellant residues after separation (without any addition)
Property Value
5
Moisture [% by weight] 19
Content of ammonium perchlorate [% by weight] 4.3
Content of ammonium perchlorate in the dry basis [% by weight] 5.3

10
Industrial utilization

[0045] The method in accordance with the invention can be used in the industrial scale to process solid rocket propellant
that contains ammonium perchlorate, powdered aluminium and a rubber-based binder as its three main components
15 for the purpose of recycling the ammonium perchlorate contained in it.
[0046] Recycled ammonium perchlorate prepared with the use of the method in accordance with the invention exhibits
a purity of up to 99.8 %.

20 Claims

1. A method for processing of expired solid rocket propellant containing ammonium perchlorate, powdered aluminium,
a rubber-based binder and remaining minority admixtures for the purpose of recycling ammonium perchlorate,
characterized in that it comprises the following steps:
25
• a) wet mechanical-physical-chemical disintegration of the said solid propellant while a suspension of solid
substances in a solution is produced;
• b) leaching of the stirred suspension at an elevated temperature in water and/or unsaturated ammonium
perchlorate solution containing added inert material based on porous carbon, diatomaceous earth and/or a
30 polymer;
• c) de-agglomeration and prevention of re-agglomeration of solid substances in the suspension with the use
of the inert material during the leaching process;
• d) separation of the ammonium perchlorate solution from the solid substances;
• e) refining of the separated ammonium perchlorate solution from step 1d) with the said inert material, except
35 the polymer-based material, at an elevated temperature;
• f) separation of the inert material from the ammonium perchlorate solution optionally followed by concentrating
the solution;
• g) crystallization and optional re-crystallization of the recycled ammonium perchlorate.

40 2. The method in accordance with claim 1, characterized in that step 1a) - the mechanical-physical-chemical disin-
tegration is carried out in a wet state by grinding in a mill, crushing in a crusher or cutting in a cutter.

3. The method in accordance with claim 1 or 2, characterized in that when the inert material is based on porous
carbon, then the porous carbon is powdered active carbon.
45
4. The method in accordance with claim 1 or 2, characterized in that when the inert material is based on diatomaceous
earth, then the diatomaceous earth is kieselguhr.

5. The method in accordance with claim 1 or 2, characterized in that when the inert material is based on a polymer,
50 then the polymer is a thermoplastic, in particular polyethylene or polypropylene.

6. The method in accordance with claim 3, characterized in that the powdered active carbon is used powdered active
carbon from steps 1e) and 1f).

55 7. The method in accordance with claims 1 to 6, characterized in that the size of the inert material particles is from
1.0 mm to 20 mm.

8. The method in accordance with claims 1 to 7, characterized in that the amount of the added inert material is at

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least 0.5 % by weight based on the total dry basis weight of the solid substances in the suspension.

9. The method in accordance with claim 8, characterized in that the amount of the added inert material is from 1.5
% by weight, based on the total dry basis weight of the solid substances in the suspension.
5
10. The method in accordance with claims 1 to 9, characterized in that the leaching steps 1b) and 1c) are carried out
at a temperature from 50 °C to 90 °C for at least 15 minutes.

11. The method in accordance with claims 1 to 10, characterized in that in the separation step 1d the suspension is
10 subjected to filtration or pressure filtration with subsequent washing of the filtration cake of solid substances with
water and/or diluted solution of ammonium perchlorate.

Patentansprüche
15
1. Verfahren zur Verarbeitung von überaltertem festem Raketentreibstoff, der Ammoniumperchlorat, pulverisiertes
Aluminium, ein auf Kautschuk basierendes Bindemittel und restliche begleitende Beimischungen enthält, zum Zwe-
cke des Recyclings von Ammoniumperchlorat, dadurch gekennzeichnet, dass es die folgenden Schritte umfasst:

20 • a) nasse mechanisch-physikalisch-chemische Zerkleinerung des Festtreibstoffs, wobei eine Suspension von

Feststoffen in einer Lösung hergestellt wird,
• b) Auslaugen der gerührten Suspension bei erhöhter Temperatur in Wasser und/oder ungesättigter Ammo-
niumperchloratlösung, das/die zugesetztes inertes Material auf Basis von poröser Kohle, Diatomeenerde
und/oder eines Polymers enthält,
25 • c) Desagglomeration und Verhinderung der Reagglomeration von Feststoffen in der Suspension, unter Ver-
wendung des inerten Materials, während des Auslaugungsprozesses,
• d) Trennung der Ammoniumperchloratlösung von den Feststoffen,
• e) Raffination der abgetrennten Ammoniumperchloratlösung aus Schritt 1d) mit dem inerten Material, mit
Ausnahme des polymerbasierten Materials, bei erhöhter Temperatur,
30 • f) Trennung des inerten Materials von der Ammoniumperchloratlösung, worauf gegebenenfalls eine Konzen-
tration der Lösung folgt,
• g) Kristallisierung und optionale Rekristallisierung des recycelten Ammoniumperchlorats.

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Schritt 1a) - die mechanisch-physikalisch-che-
35 mische Zerkleinerung - in nassem Zustand durch Mahlen in einer Mühle, Grobzerkleinern in einem Brecher oder
Schneiden in einer Schneidmaschine erfolgt.

3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass, wenn das inerte Material auf poröser Kohle
basiert, diese poröse Kohle pulverisierte Aktivkohle ist.
40
4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass, wenn das inerte Material auf Diatomeenerde
basiert, diese Diatomeenerde Kieselgur ist.

5. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass, wenn das inerte Material auf einem Polymer
45 basiert, dieses Polymer ein Thermoplast ist, insbesondere Polyethylen oder Polypropylen.

6. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass es sich bei der pulverisierten Aktivkohle um gebrauchte
pulverisierte Aktivkohle aus den Schritten 1e und 1f handelt.

50 7. Verfahren nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, dass die Größe der Partikel des inerten Materials
1 mm bis 20 mm beträgt.

8. Verfahren nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, dass die Menge des zugesetzten inerten
Materials mindestens 0,5 Gewichts-% beträgt, bezogen auf dem Gesamt-Trockenbasisgewicht der Feststoffe in
55 der Suspension.

9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die Menge des zugegebenen inerten Materials 1,5
Gewichts-%, bezogen auf das Gesamt-Trockenbasisgewicht der Feststoffe in der Suspension, beträgt.

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10. Verfahren nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, dass die Auslaugungsschritte 1b) und 1c) bei
einer Temperatur von 50 °C bis 90 °C über einen Zeitraum von mindestens 15 Minuten durchgeführt wird.

11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass in dem Trennschritt 1d die Sus-
5 pension einer Filtration oder Druckfiltration mit anschließendem Waschen des Filterkuchens aus Feststoffen mit
Wasser und/oder verdünnter Lösung von Ammoniumperchlorat unterzogen wird.

Revendications
10
1. Un procédé de traitement d’un propergol de fusée périmé sous forme solide contenant du perchlorate d’ammonium,
de l’aluminium pulvérulent, un liant à base de caoutchouc et des produits en faibles proportions, aux fins de recycler
le perchlorate d’ammonium, caractérisé en ce qu’il comprend les étapes suivantes:

15 • a) désintégration par voie physico-chimique mécanique en milieu humide dudit propergol solide pour produire
une suspension de substances solides dans une solution;
• b) lixivation de ladite suspension sous agitation à température élevée dans de l’eau et/ou une solution de
perchlorate d’ammonium insaturée contenant un ajout formé d’une matière inerte à base de carbone poreux,
de terre de diatomées et/ou d’un polymère;
20 • c) désagglomération et prévention de la ré-agglomération des substances solides dans la suspension avec
utilisation de la matière inerte pendant l’étape de lixiviation;
• d) séparation de la solution de perchlorate d’ammonium des substances solides;
• e) affinage de la solution de perchlorate d’ammonium recueillie dans l’étape 1d) par action de ladite matière
inerte à l’exception de la matière à base de polymère, à température élevée;
25 • f) séparation de la matière inerte contenue dans la solution de perchlorate d’ammonium suivie éventuellement
de la concentration de la solution;
• g) cristallisation et éventuellement recristallisation du perchlorate d’ammonium recyclé.

2. Le procédé selon la revendication 1, caractérisé en ce que dans l’étape 1a), la désintégration par voie physico-
30 chimique mécanique est réalisée à l’état humide par broyage dans un broyeur, écrasement dans un concasseur
ou découpage dans un broyeur.

3. Le procédé selon la revendication 1 ou 2, caractérisé en ce que lorsque de la matière inerte est à base de carbone
poreux, ce carbone poreux est du charbon actif pulvérulent.
35
4. Le procédé selon la revendication 1 ou 2, caractérisé en ce que lorsque de la matière inerte est à base de terre
de diatomées, cette terre de diatomées est du kieselguhr.

5. Le procédé selon la revendication 1 ou 2, caractérisé en ce que lorsque de la matière inerte est à base de polymère,
40 ce polymère est un thermoplastique, en particulier du polyéthylène ou du polypropylène.

6. Le procédé selon la revendication 3, caractérisé en ce que le charbon actif pulvérulent est du charbon actif pul-
vérulent provenant des étapes 1e) et 1f).

45 7. Le procédé selon les revendications 1 à 6, caractérisé en ce que la taille des particules de matière inerte est
comprise entre 1,0 mm et 20 mm.

8. Le procédé selon les revendications 1 à 7, caractérisé en ce que la quantité de matière inerte ajoutée est d’au
moins 0,5% en poids par rapport au poids sec total des substances solides présentes dans la suspension.
50
9. Le procédé selon la revendication 8, caractérisé en ce que la quantité de la matière inerte ajoutée est de 1,5% en
poids, sur la base du poids sec total des substances solides dans la suspension.

10. Le procédé selon les revendications 1 à 9, caractérisé en ce que les étapes de lixiviation 1b) et 1c) sont réalisées
55 à une température comprise entre 50°C et 90°C pendant au moins 15 minutes.

11. Le procédé selon les revendications 1 à 10, caractérisé en ce que dans l’étape de séparation 1d, la suspension
est soumise à une filtration ou à une filtration sous pression suivie d’un lavage du gâteau de filtration formé par les

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 EP 3 097 050 B1

substances solides avec de l’eau et/ou une solution diluée de perchlorate d’ammonium.

10

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30

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 EP 3 097 050 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 4854982 A [0003] [0010] • US 4198209 A [0007] [0010]

• US 3451789 A [0005] [0010] • US 5346512 A, Miks Kathryn F. [0008]
• US 4662893 A [0006] [0010] • US 4098627 A [0010]

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