(19)

*EP003191406B1*
(11) EP 3 191 406 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention

(51) Int Cl.:
of the grant of the patent:
C01F 7/56 (2006.01)
04.11.2020 Bulletin 2020/45

(86) International application number:

(21) Application number: 15781171.2
PCT/US2015/049839

(22) Date of filing: 11.09.2015

(87) International publication number:
WO 2016/040902 (17.03.2016 Gazette 2016/11)

(54) METHOD FOR PRODUCTION OF ALUMINUM CHLORIDE DERIVATIVES

VERFAHREN ZUR HERSTELLUNG VON ALUMINIUMCHLORIDDERIVATEN
PROCÉDÉ DE PRODUCTION DE DÉRIVÉS DE CHLORURE D’ALUMINIUM

(84) Designated Contracting States: (74) Representative: Høiberg P/S

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Adelgade 12
GR HR HU IE IS IT LI LT LU LV MC MK MT NL 1304 Copenhagen K (DK)
NO PL PT RO RS SE SI SK SM TR
(56) References cited:
(30) Priority: 12.09.2014 US 201462049457 P EP-A1- 0 530 598 WO-A1-90/08738
WO-A2-01/97768 DD-A1- 273 824
(43) Date of publication of application: US-A- 3 876 758 US-A- 5 985 234
19.07.2017 Bulletin 2017/29
• YANG LI ET AL: "Characteristics of High-purity
(73) Proprietor: Usalco LLC Polyaluminum Chloride Species Prepared by
Baltimore, Maryland 21226 (US) Homogeneous Alkalization", NATURAL
SCIENCE JOURNAL OF XIANGTAN
(72) Inventor: WONDER, Bruce UNIVERSITY, vol. 27, no. 4, 1 January 2005
Abingdon, MD 21009 (US) (2005-01-01), pages 68-72, XP055244430, DOI:
10.13715/i.cnki.nsjxu.2005.04.014
EP 3 191 406 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 3 191 406 B1

Description

Technical Field

5 [0001] The present disclosure relates to the production of a family of dry aluminum chloride products ranging from
zero percent basic, aluminum chloride hexahydrate (HEX), to 85.6 percent basic, aluminum chlorohydrate (ACH) using
non-elemental sources of raw materials through the use of an improved process of treating HEX to produce dry
aluminum chloride products of specific basicity.

10 Background

[0002] In the aluminum chloride market there is a demand for products ranging from solutions that contain free hydro-
chloric acid to products, both liquid and dry, of increasing levels of basicity. Aluminum chloride has the general
chemical

15
formula of Aln(OH)mCl3n-m. Basicity is defined as the ratio of where m is less than or equal to 5.2.
[0003] It is undesirable to use elemental aluminum as the source of aluminum to produce these products due to the
controlled availability and volatility of pricing of the metal on the commodity market. Sources of aluminum such as
aluminum ore (bauxite), refined aluminum ore (aluminum trihydrate (ATH)) or various pre-solubilized forms are more
desirable because of their availability and relatively stable pricing.
20
[0004] Production of high basicity products starting with aluminum from non-metallic sources requires rapidly
increasing
amounts of energy as basicity increases. In addition to the energy, the stability of the final product begins to decrease
once the basicity ratio is greater than 0.3. From this point (0.3 basicity ratio) up to a basicity ratio of 0.83 technology
similar to that disclosed in patent number 5,985,234 can be used, typically with aluminum metal as a starting material .
[0005] An alternate approach for increasing the basicity ratio is to remove chloride from the molecule rather than
25
adding aluminum. Under this approach, a simple solution of aluminum chloride is produced using a non-elemental
source of aluminum. It is known that solutions of aluminum chloride when concentrated beyond saturation form
crystals of
aluminum chloride hexahydrate and that these crystals, when exposed to heat, decompose, releasing hydrogen
chloride and water. This approach has been applied to produce high purity aluminum oxide and, to a lesser extent, to
produce basic aluminum chloride, but only in batching operations. A process that reduces the requirement of batching
operations
30
would result in increased efficiency of production, lower cost, and improved safety.
[0006] DD 273 824 relates to production of alumina (aluminum oxide) and discloses a method for production of
alumina comprising: milling aluminium chloride hexahydrate particles; thermal treating the aluminium chloride
hexahydrate par- ticles at 130-200°C until a ratio of nAl:nCl of 1:3 is obtained; letting the partially decomposed
particles react with water
to form a basic aluminum chloride sol; and calcinating the basic aluminum chloride sol at 400-700°C into aluminum
oxide.
35
[0007] Furthermore, WO 90/08738 relates to aluminum compounds and their preparation, and discloses a process of
reacting alumina with hydrochloric acid, possibly mixed with sulfuric acid to obtain a compound of formula
[Al2(OH)Cly(S04)z]n, which requires drying.
[0008] Several publications describe systems that utilize mills and rotational motion for dehydration and drying mate-
rials. See e.g., United States patents 6,145,765; 5,167,372; 4,390,131; 3,462,086; 2,470,315; and U.S. publication
40
number 2004/0040178. These systems do not address issues associated with the stringent requirements, such as
handling of evolved hydrochloric acid that must be addressed in the production of aluminum chloride products of
specific basicity. In another approach, flash dryer systems involve spraying slurry onto a dryer and applying high
temperature to evaporate gas and liquid components. See e.g., U.S. Patent 5,573,582.
[0009] Evaporation, crystallization, and recovery of formed crystals are well known in the art. See for example, McCabe
45
and Smith 1976, Unit Operations of Chemical Engineering, in particular, the following sections: Evaporation, pages 425-
463 to 11-118, Crystallization, pages 852 to 894, and Filtration, pages 922 to 953; and Perry’s Chemical Engineering
Handbook (7th Ed. Perry and Green, 1999), sections: Evaporation, pages 11-107 to 11-118, Crystallization, pages 18-
35 to 18-55, and Filtration, pages 18-74 to 18-125.

50
Summary

[0010] Embodiments of the present disclosure include aluminum chlorohydrate products comprising particles of alu-
minum chlorohydrate in fractured crystal form, the particles having a basicity in the range of 0% to about 85.6 %, and a
surface area to weight ratio of about 295 to about 705 m2/kg, inclusive of both endpoints and all numerical values
55
therebetween, where the ratio is measured by laser diffraction. In a related embodiment, the fractured crystal particles
have a mean particle size in the range of about 10 to about 15 microns. In a further embodiment, the particles have a

2
 EP 3 191 406 B1
basicity of about 83% and a surface area to weight ratio in the range of about 575 to about 700 square meters per

3
 EP 3 191 406 B1

kilogram, as measured by laser diffraction. In another related embodiment, the fractured crystal particles have a
basicity of about 50%, about 60%, about 72%, about 83%, or about 85%.
[0011] Embodiments of the present disclosure also include a method for producing aluminum chloride hexahydrate
particles of a desired basicity that includes applying a high temperature gas stream to a circular mill to establish and
5 maintain a circulating gas stream within the mill at a constant temperature. Aluminum chloride hexahydrate crystals are
introduced into the heated circular mill, where the crystals are formed into aluminum chlorohydrate particles and
separated based on particle density. The resulting particles having a basicity that is a function of the constant
temperature, and are dried and collected as they exit the circular mill. In a related embodiment of the present
disclosure, constant tem- perature is in the range of 200°F to 400°F and the dried particles collected from the mill have
a basicity range of about
10 50% to about 85.6%. In a further related embodiment of the present disclosure, the constant temperature is in the range
of 220°F to 240°F and dried particles comprise Al2Cl6 with a basicity of 0 to 5%.
[0012] In another related embodiment of the present disclosure, the constant temperature is in the range of 260 to
280°F, and the particles comprise Al2(OH)Cl5 with a basicity of about 14 to 18%. In a further related embodiment of
the present disclosure, the constant temperature is about 300 - 310° F and the dried particles comprise Al2(OH)2Cl4
and
15 have a basicity of about 31 to 35%.
[0013] In another related embodiment of the present disclosure, the constant temperature is about 340 - 350°F and the
dried particles comprise Al2(OH)3Cl3 and have a basicity of about 38 to 52%. In a further related embodiment of the
present disclosure, the constant temperature is about 350 to 360°F and the dried particles comprise Al 2(OH)4Cl2 and
have a basicity of about 64 to 68%. In yet another related embodiment of the present disclosure, the constant
temperature
20 is
about 380 to 400°F and the dried particles comprise Al2(OH)5Cl and have a basicity of about 81 to 85%.
[0014] In another related embodiment of the present disclosure, the gas stream comprises ambient air and steam.
[0015] In yet another related embodiment of the present disclosure, the dried particles have a bulk density of about
40 to about 65 pounds per cubic foot; and/or a surface area greater than about 300 square meters per kilogram and
less than about 700 meters per kilogram; and or a surface area of greater than 500 square meters per kilogram and
25 less than 600 meters per kilogram.
[0016] In an embodiment of the present disclosure, there is provided a method for producing aluminum chloride
hydrates of various basicity; the method includes applying a high temperature gas stream to a circular mill to maintain
a constant temperature creating a heated circular stream; feeding a HEX particle into the circular mill, wherein the
HEX particles begin to decompose forming particles of various basicities and densities; centrifugal forces inside the
circular
30 mill cause the particles to separate based on particle density; varying feed rate to maintain a constant exit temperature;
and collecting dried particles as the particles exit the circular mill.
[0017] Embodiments of the present disclosure also include aluminum chlorohydrate particles produced by the
methods described herein and/or with one or more particle properties described herein, including basicity in the range
of 0% to about 85.6 %; surface area to weight ratio of about 295 to about 705 m 2/kg; and a bulk density of about 40 to
about 65
35 pounds per cubic foot.
[0018] The aluminum chloride products described herein are produced efficiently using methods and systems that
greatly reduce the energy required to prepare aluminum chloride products having a desired basicity, and therefore a
corresponding reduction of production costs.
[0019] Embodiments of the present disclosure also include methods for utilizing the aluminum chlorohydrate particles
40 described herein in applications such as waste water treatment, manufacture of catalyst support systems, and other
applications of aluminum chloride products.

Brief Description of the Drawings

45 [0020] The foregoing features of embodiments of the present disclosure will be more readily understood by reference
to the following detailed description, taken with reference to the accompanying drawings, in which:

Figure 1 is a flow diagram of a method for the production of aluminum chloride of various basicities in accordance
with an embodiment of the present disclosure.
50
Figure 2 is a schematic representation of a one embodiment of the present disclosure of a system for the
production of aluminum chloride hydrates of various basicities in accordance with the method of Figure 1.

Figure 3 is a graph (A) showing results of particle size distribution analysis of aluminum chloride particles produced
55 by milling (first peak), spray drying (second peak), or using a fluid bed dryer (third peak). Also shown is a table (B)
showing numerical values of the particle size distributions. The aluminum chloride particles produced by milling
were produced in accordance with an embodiment of the present disclosure, and have a basicity of about 83%.

4
 EP 3 191 406 B1
The particles produced by spray drying were produced by prior art methods. Similarly the particles produced
using a

5
 EP 3 191 406 B1

fluid bed dryer were produced by prior art methods.

Figure 4 shows results of scanning electron microscopy (SEM) of the prior art aluminum chloride particles produced
by spray drying (which particles are also a subject of Figure 3), the SEM picture including particle size markings.
5
Figure 5 shows results of scanning electron microscopy of the prior art aluminum chloride particles produced in a
fluid bed dryer (FBD) (which particles are also a subject of Figure 3), the SEM picture including particle size
markings.

Figure 6 shows results of scanning electron microscopy of the aluminum chloride particles produced by milling
10 according to an embodiment of the present disclosure (which particles are also a subject of Figure 3), the SEM
picture including particle size markings.

Detailed Description

15 [0021] Definitions. As used in this description and the accompanying claims, the following terms shall have the meanings
indicated, unless the context otherwise requires:
[0022] Polyaluminum Chlorides: Polyaluminum chlorides are products of aluminum chloride hydroxide, AlCl(OH) 2,
AlCl2 (OH), and Al2 Cl(OH)5. A representative formula is: Al 2Cl6-n (OH)n, where n=2.7 to 5 for products formed via the
process disclosed herein. It is thought that, when these products are diluted, polymeric species such as: Al 13O4 OH)24
20 (H. O)12 + 7Cl are formed.
2
[0023] Basic Aluminum Chlorides: These are compounds having the formula: Al 2(OH)n (Cl)6-n where n is greater
than zero and less than or equal to 1.5. It is believed that solutions of these compounds contain: Al(H2O)6 +3Cl;
Al2(OH)2 (H2O)8 +4Cl; and Al(OH)(H2O)5 +2Cl.
[0024] Aluminum Salt Concentration of Reaction Products: The concentration of aluminum salt stated as present
25 in a reaction product refers to the amount of aluminum oxide that would have been necessary to make the product.
Thus, products are described as having a certain percentage of Al2O3 even though the aluminum oxide may not
actually be present in the product. This is common practice in the art and allows products to be compared based upon
their chemistry.
[0025] Laser diffraction: Laser diffraction is a method of determining, among other things, surface area per unit of
30 weight, using optical diffraction as described in ISO 13320:2009 "Particle Size Analysis - Laser Diffraction Methods".

[0026] Basicity: Aluminum chloride has the general chemical formula of Aln(OH)mCl3n-m. Basicity is the ratio of
where m is less than or equal to 5.2.
[0027] The invention is defined by the appended claims. Any embodiment not falling under the scope of the appended
35
claims does not form part of the invention.
[0028] The disclosure summarized above may be better understood by referring to the following description, the
accompanying drawings, and the claims listed below. The description embodiments, set out below to enable one to
practice an implementation of the disclosure, is not intended to limit the preferred embodiment, but to serve as a
particular
example thereof. Those skilled in the art should appreciate that they may readily use the conception and specific em-
40
bodiments disclosed as a basis for modifying or designing other methods and systems for carrying out the same
purposes of the present disclosure. Those skilled in the art should also realize that such equivalent assemblies do not
depart from the scope of the disclosure.
[0029] An optimized method for the production of aluminum chloride hexahydrate crystals is shown in the flow diagram
of Figure 1, and includes the following steps:
45
(1) Evaporation/Crystallization 200, (2) Crystal recovery 220, (3) Crystal drying and/or decomposition 230, and (4) Crystal
Collection and Processing 240.

(1) Evaporation/Crystallization 200:

50
[0030] Aluminum chloride hexahydrate crystals are created from an aluminum chloride solution , with evaporation of
unwanted water with heat in the general range of 230 - 250 degrees Fahrenheit. One method of performing the evapo-
ration/crystallization step 200 is in a batch system.
[0031] In an embodiment of the present disclosure, a standard commercially available aluminum chloride solution at
a concentration of 10.7% Al2O3 or 28.0% Al2Cl6 is charged to an agitated process tank. The solution is circulated
through
55
an external heat exchanger where process steam is used to raise the temperature of the solution to near boiling
(between
230°F and 235°F). The heated liquid is drawn through a venturi and back into the process tank where vacuum from an
induced draft fan causes localized boiling and evaporation of water from the system. The removal of water from the

6
 EP 3 191 406 B1

solution causes the concentration of aluminum chloride to increase to the saturation point of 12.4% Al 2O3 or 32.4%
Al2Cl6. When the solution concentration exceeds the saturation concentration, aluminum chloride hexahydrate (HEX)
crystals begin to form. This process is continued until the volume of crystals in the recirculating solution exceeds 30
percent by volume.
5 [0032] Once the 30 percent by volume crystal concentration is reached, the steam flow is stopped and the solution is
transferred into an agitated collection tank where it is cooled to between 160 °F and 180 °F to allow the crystals to
mature and grow in size to nominally between 30 and 40 Tyler mesh. This step facilitates removal of the mother liquor
from the crystals in the recovery step that feeds the crystal recovery step. The evaporator system is recharged with
aluminum chloride solution and the process is repeated.
10
(2) Crystal Recovery 220:

[0033] In the second step 220 of one preferred embodiment of the process of the present disclosure, the aluminum
chloride solution containing the HEX crystals is fed to a plate and frame filter where the crystals are separated from the
15 solution. The solution is returned to the aluminum chloride storage tank that feeds the evaporator system. Once the filter
chambers are full of crystal, the mother liquor contained in the cake is blown out of the crystal cake using compressed
dry air at between 10 to 20 PSIG. The crystals are then discharged from the filter are collected in a feed hopper
equipped with a variable rate feeder.

20 (3) Crystal drying and/or decomposition - 230:

[0034] In a third step of the process 230, the variable rate feeder discharges de-agglomerated aggregates into a flash
energy drying/grinding mill 540. The drying/grinding mill 540 is a circular tube. In some embodiments of the present
disclosure the tube is elongated as shown in Figure 2, however, it is contemplated that other circular shapes may be
25 utilized, but in all applications of this technology a system that applies centrifugal or gravitation forces to induce particle
separation based on density is required.
[0035] The drying/grinding mill 540 has an intake 585 through which the HEX from step 2 is introduced. The feed rate
is varied to maintain a constant exit temperature from the mill. This is important since basicity of the product is a time
and temperature dependent reaction and is based on the amount of energy that can be absorbed by the HEX. Since
30 the contact time inside the mill is short and consistent (5-10 seconds), maintaining the exit temperature of the mill 540
coupled with the gas supply temperature assists in producing the desired product.
[0036] Variations in free moisture of the feed to the mill affect the production rate of the product produced. As moisture
increases, more energy is consumed to evaporate the moisture. With less energy present, the feed to the mill needs to
be adjusted so that the ratio of dry HEX to energy absorbed is maintained to perform the decomposition reaction.
35 [0037] Because of the short residence time the feed is exposed to the thermal energy inside the mill, constant adjust-
ments to the feed rate must be made to adjust for any variability of the feed stock, in order to maintain a constant exit
temperature from the system. This is accomplished by use of a feedback control loop with the mill exit temperature
546 being the control variable, and the speed of the feeder 550 being the control element. Typical product basicity in
asso- ciation with the mill 540 exit temperature of each product is shown below in Table 1.
40
Table 1
Mill Operating Temperature Ranges for Various Products
Product Percent Basic Temperature Operating Range* Degrees Fahrenheit
45 Al2Cl6 0 to 5 220 to 240
Al2(OH)Cl5 14 to 18 260 to 280
Al2(OH)2Cl4 31 to 35 300 to 310
Al2(OH)3Cl3 48 to 52 340 to 350
50
Al2(OH)4Cl2 64 to 68 350 to 360
Al2(OH)5Cl 81 to 85 380 to 400
*Dependent on gas supply temperature to mill

55

[0038] The energy is applied convectively in the mill and comes from heated air and/or superheated steam through
tangential nozzle(s) 542, 543, 544. The addition of steam to the supply gas was found to increase the production rate.

7
 EP 3 191 406 B1

In an embodiment of the present disclosure, a portion of the air can be replaced with a condensable gas to ease the
volume of HCl-laden gas on the recovery system. In a preferred embodiment of the present disclosure, however,
steam is used. This mixture is supplied to the mill between 400 °F and 1,200°F and produces velocities inside the mill
of between 3000 and 6000 feet per minute.
5 [0039] .It is this porosity on the surface of the particle that causes the internal portion of the particle to be insulated from
the applied heat and thus resist decomposition. Collisions with other particles in the mill and impingement against the
walls of the mill prevent the crystals from agglomerating as the particles circulate around the inside of the mill. Such
collisions and movement also serve to scour finished product from the surface
10 of the particles exposing wetter and/or less decomposed material to the energy in the system. Such exposure presents a
distinct and unexpected advantage over prior known processes and makes the present process more beneficial over
other known methods of manufacturing the desired products. Without this scouring and/or grinding in the mill, the outer
surface of the particle will become over-decomposed, while the interior remains under-decomposed. Over-
decomposed products become insoluble and thus useless products and/or produce highly viscous solutions that are
difficult to use
15 or perform poorly in product applications.
[0040] Decomposition processes as described here and in prior art will produce dilute acid solutions during production
or when cleaning equipment. An important aspect of the products produced by the process of the present disclosure is
that these products can be made at higher than 83% basicity. The high basicity product can be diluted with the above
acidic solutions produced by decomposition, and still generate a liquid ACH with a basicity above 83%. To our
knowledge,
20 this is not possible with any prior known product, as material produced at an above average of 83% basicity will contain
over-decomposed product in the exterior of the particle and under-decomposed material in the center. This will
generate insoluble material that is extremely difficult to filter and result in loss of raw materials.
[0041] Currently commercial products of dry ACH are made by reacting aluminum chloride, basic aluminum chloride
or hydrochloric acid with metallic aluminum. This generates a 50% solution of ACH which is then spray dried. This is
an
25 energy intensive process for all the water must be evaporated and production of metallic aluminum is energy intensive as
well. The product of this spray drying process is spherical crystals of aluminum chlorohydrate dihydrate of which 90
percent are less than 71 microns. See Figure 3. Laser Light Diffraction has determined that these products have a
specific surface area of less than 100 square meters per kilogram. The small specific surface area may be limiting in
the usefulness of the product as a dry chemical reactant. The two waters of hydration also prohibit the use as a dry
30 reactant in that the ACH dihydrate dissolves rapidly in cold water.
[0042] Products of the earlier Fluid Bed Dryer Technology also have small specific surface areas of less than 100
square meters per kilogram. They are long crystalline cylinders which 90 percent of the material is less than 369
microns. See Figure 4. These products contain less than two waters of hydration but lack the specific surface area for
good reactivity as dry reactant. The small surface area may cause longer reaction times which may be problematic in
some
35 reactions.
[0043] The products of this disclosure are fractured crystals of which 90 percent are less than 17 microns. A
specifically unique feature of these products is the large surface area of the particles formed. See Figure 6. The
specific surface area of these products, at 83% basicity, based on laser diffraction analysis, is in the range of about
575 to about 700 square meters per kilogram. Since more water and hydrochloric acid are released from the
hexahydrate crystal as
40 basicity increases, it can be demonstrated that the lower basicity products would have a smaller surface area than the
higher basicity products. Table 2 below demonstrates what can be expected.

Table 2
% Basic Versus Surface Area
45
Percent Basic Operating Temperature °F Surface Area (m2/kg)
50% 345 295
72% 365 452
50 83% 395 607
85% 400 705

[0044] If appropriate conditions are not maintained, the average of the decompositions may be the desired value, but
55 the standard deviation will be wide producing a product that may not have the desired properties or stability. The
centrifugal forces inside the mill cause the material inside to separate based on particle density. The more dense
material (wetter/less decomposed) will migrate to the outer radius of the mill and away from the mill discharge 590 and
are retained longer,
8
 EP 3 191 406 B1

while the less dense (drier/more decomposed) travel towards the inner radius of the mill and exit the system through
the mill discharge 590 as the desired product. The decomposition releases water and hydrogen chloride in gas form
from the particles as they decompose.
[0045] The waters of hydration will vary with the basicity of the product produced. Material of about 70% basicity have
5 two waters of hydration, 83% basicity has about half a water of hydration and the product becomes totally anhydrous at
over 85% basicity. Commercially available ACH(83% basicity) has two waters of hydration.

(4) Crystal Collection and Processing.

10 [0046] In a final step 240 crystals of the appropriate basicity are collected and processed. The product exits from the mill
discharge 590 and also contains hydrogen chloride and water in a gaseous form. Primary separation is performed by a
cyclone separator 570. The discharged material from the cyclone will still contain hydrogen chloride gas and water
vapor. Before these components have an opportunity to condense and be absorbed by the product they are stripped
from the system by passing air through the product in a fluidized bed or by operating the cyclone under vacuum
conditions.
15 Once the product is separated from the gas stream it is conveyed to a storage bin. Once in the storage bin the product is
either packaged as is or sent to additional processing to produce a liquid product.
[0047] One advantage over this process over previous designs with Fluid Bed Dryer(FBD) technology is the heavier
bulk density of the product. The heavier bulk density allows for less storage bin space and will require less volume
when shipped. The bulk density of ACH made from this process can range from 55 to 60 pounds per cubic foot while
material
20 from a FBD system can range 18 to 25 pounds per cubic foot.

SYSTEM COMPONENTS

[0048] In one embodiment of the present disclosure, a system for the production of aluminum chlorides of various
25 basicities is shown in Figure 2. In the system, aluminum chloride hexahydrate crystals are put in a variable rate crystal
feeder 550. The variable rate crystal feeder is connected to the grinding mill 540 by a conduit 501 that attaches to the
mill’s intake 585. Air, steam, or gas is supplied to the grinding mill 540. Ambient air is provided through an air supply
blower 520 that is connected to an air heater 530. Steam is supplied through a steam supply source and a steam flow
meter 510 measures the initial flow of steam into the system. Steam supply flow is controlled by a steam flow control
30 valve 511. Steam or gas and ambient air are mixed and delivered to mixed gas supply header 541. Mixed air pressure
and temperature are measured at the blower and heater through a mixed supply pressure meter 531 and a mixed gas
supply temperature meter 532.
[0049] Mixed air is then divided into a number of mixed gas feed nozzles, 543, 543, 544. It is contemplated that the
number of nozzles may vary depending on the size of the grinding mill 540. The product exits the mill 540 at the mill
35 discharge 590 which connects to a product conveying line 560. Exit temperature and pressure are measured at the mill
discharge 590 or product conveying line 560 by a grinding mill exit pressure meter 545 and a grinding mill exit
temperature meter 546.
[0050] The product conveying line 560 delivers the product to the air/solid separating cyclone 570. The air/solid
separating cyclone 570 is connected to a system induced draft fan 580. The system induced draft fan 580 assists in
40 recovering excess air, water, and HCl. The air/solid separating cyclone 570 deposits dry aluminum chloride product to
the product air lock 572 and the product can then be collected.
[0051] Commercially available ACH is made by elemental digestion of aluminum in HCl or aluminum chloride
solutions. The dried product is then commonly made by spray drying ACH solutions, which is an expensive process.
When using such a system, it is advantageous to process particles of less than 100 microns in order to prevent
clogging of aerosol
45 sprayers. The aluminum chlorohydrate products produced as described herein are produced in a manner that eliminates
the expensive spray drying step, yet yields small particles with a high surface area and at desired basicity.
[0052] The embodiments of the disclosure described above are intended to be merely exemplary; numerous variations
and modifications will be apparent to those skilled in the art.

50
Claims

1. A method for producing aluminum chloride hydrate particles of a desired basicity, said method comprising:

55 applying a heated gas stream to a circular mill to establish and maintain a circulating gas stream within the
mill at a constant operating temperature in a range of between 93°C and 204°C (200°F and 400°F);
feeding aluminum chloride hexahydrate crystals into the circular mill, wherein aluminum chlorohydrate particles
are formed and the resulting particles are separated based on particle density, the particles having a basicity

9
 EP 3 191 406 B1

that is a function of the constant operating temperature; and

collecting dried aluminum chlorohydrate particles as the particles exit the circular mill.

2. The method of Claim 1, wherein the dried particles collected from the mill have a basicity range of 0 to 85.6%.
5
3. The method of Claim 1, wherein the constant operating temperature is in the range of between 104 and 116°C
(220 and 240°F), optionally wherein the dried particles collected from the mill comprise Al 2Cl6 and have a basicity
of 0 to 5%..

10 4. The method of Claim 1, wherein the constant operating temperature is in the range between 127 and 138°C (260 and
280°F), optionally wherein the dried particles collected from the mill comprise Al 2(OH)Cl5 and have a basicity of 14
to 18%.

5. The method of Claim 1, wherein the constant operating temperature is in the range between 149 and 154°C (300
15 and 310° F), optionally wherein the dried particles collected from the mill comprise Al2(OH)2Cl4 and have a
basicity of 31 to 35%.

6. The method of Claim 1, wherein the constant operating temperature is in the range of between 171 and 177°C
(340 and 350°F), optionally wherein the dried particles collected from the mill comprise Al 2(OH)3Cl3 and have a
basicity
20 of 38 to 52%.

7. The method of Claim 1, wherein the constant operating temperature is in the range of between 177 and 182°C
(350 and 360°F), optionally wherein the dried particles collected from the mill comprise Al 2(OH)4Cl2 and have a
basicity of 64 to 68%.
25
8. The method of claim 1, wherein the constant operating temperature is in the range of between 193 and 204°C
(380 and 400°F), optionally wherein the dried particles collected from the mill comprise Al 2(OH)5Cl and have a
basicity of 81 to 85%.

30 9. The method of claim 1, wherein the gas stream comprises ambient air and steam.

10. The method of claim 1, wherein said dried particles have a bulk density of 636 to 1042 kg/m 3 (40 to 65 pounds per
cubic foot).

35 11. The method of claim 1, wherein said dried particles have a mean particle size in the range of 10 to 15 microns.

Patentansprüche

40 1. Verfahren zum Herstellen von Aluminiumchloridhydrat-Partikeln einer gewünschten Basizität, wobei das Verfahren
Folgendes umfasst:

Anlegen eines erhitzten Gasstroms an eine Kreismühle, um einen zirkulierenden Gasstrom innerhalb der
Mühle bei einer konstanten Betriebstemperatur in einem Bereich zwischen 93 °C und 204 °C (200 °F und
400 °F)
45 herzustellen und aufrechtzuerhalten;
Zuführen von Aluminiumchloridhexahydrat-Kristallen in die Kreismühle, wobei Aluminiumchlorhydrat-Partikel
gebildet werden und die resultierenden Partikel auf Grundlage der Partikeldichte getrennt werden, wobei die
Partikel eine Basizität aufweisen, die eine Funktion der konstanten Betriebstemperatur ist; und
Gewinnen von getrockneten Aluminiumchlorhydrat-Partikeln, wenn die Partikel die Kreismühle verlassen.
50
2. Verfahren nach Anspruch 1, wobei die aus der Mühle gewonnenen getrockneten Partikel einen Basizitätsbereich
von 0 bis 85,6 % aufweisen.

3. Verfahren nach Anspruch 1, wobei die konstante Betriebstemperatur im Bereich zwischen 104 und 116 °C (220
55 und 240 °F) liegt, wobei wahlweise die aus der Mühle gewonnenen getrockneten Partikel Al2Cl6 umfassen und
eine Basizität von 0 bis 5 % aufweisen.

4. Verfahren nach Anspruch 1, wobei die konstante Betriebstemperatur im Bereich zwischen 127 und 138 °C (260 bis

10
 EP 3 191 406 B1

280 °F) liegt, wobei wahlweise die aus der Mühle gewonnenen getrockneten Partikel Al2(OH)Cl5 umfassen und
eine Basizität von 14 bis 18 % aufweisen.

5. Verfahren nach Anspruch 1, wobei die konstante Betriebstemperatur im Bereich zwischen 149 und 154 °C (300
5 und 310 °F) liegt, wobei wahlweise die aus der Mühle gewonnenen getrockneten Partikel Al 2(OH)2Cl4 umfassen
und eine Basizität von 31 bis 35 % aufweisen.

6. Verfahren nach Anspruch 1, wobei die konstante Betriebstemperatur im Bereich zwischen 171 und 177 °C (340
und 350 °F) liegt, wobei wahlweise die aus der Mühle gewonnenen getrockneten Partikel Al2(OH)3Cl3 umfassen
10 und eine Basizität von 38 bis 52 % aufweisen.

7. Verfahren nach Anspruch 1, wobei die konstante Betriebstemperatur im Bereich zwischen 177 und 182 °C (350
und 360 °F) liegt, wobei wahlweise die aus der Mühle gewonnenen getrockneten Partikel Al 2(OH)4Cl2 umfassen
und eine Basizität von 64 bis 68 % aufweisen.
15
8. Verfahren nach Anspruch 1, wobei die konstante Betriebstemperatur im Bereich zwischen 193 und 204 °C (380
und 400 °F) liegt, wobei wahlweise die aus der Mühle gewonnenen getrockneten Partikel Al2(OH)5Cl umfassen
und eine Basizität von 81 bis 85 % aufweisen.

20 9. Verfahren nach Anspruch 1, wobei der Gasstrom Umgebungsluft und Dampf umfasst.

10. Verfahren nach Anspruch 1, wobei die getrockneten Partikel eine Schüttdichte von 636 bis 1042 kg/m 3 (40 bis 65
Pfund pro Kubikfuß) aufweisen.

25 11. Verfahren nach Anspruch 1, wobei die getrockneten Partikel eine mittlere Partikelgröße im Bereich von 10 bis 15
Mikrometer aufweisen.

Revendications
30
1. Procédé de production de particules d’hydrate de chlorure d’aluminium d’une basicité souhaitée, ledit procédé
comprenant :

l’application d’un courant de gaz chauffé à un broyeur circulaire pour établir et maintenir un courant de gaz en
35 circulation à l’intérieur du broyeur à une température de fonctionnement constante dans une plage comprise
entre 93 °C et 204 °C (200 °F et 400 °F) ;
l’introduction de cristaux d’hexahydrate de chlorure d’aluminium dans le broyeur circulaire, dans lequel des
particules de chlorhydrate d’aluminium sont formées et les particules résultantes sont séparées sur la base de
la densité des particules, les particules ayant une basicité qui dépend de la température de fonctionnement
40 constante ; et
la collecte de particules de chlorhydrate d’aluminium séchées à mesure que les particules sortent du broyeur
circulaire.

2. Procédé selon la revendication 1, dans lequel les particules séchées collectées depuis le broyeur ont une plage de
45 basicité de 0 à 85,6 %.

3. Procédé selon la revendication 1, dans lequel la température de fonctionnement constante est dans la plage
comprise entre 104 et 116 °C (220 et 240 °F), éventuellement dans lequel les particules séchées collectées
depuis le broyeur
comprennent Al2Cl6 et ont une basicité de 0 à 5 %.
50
4. Procédé selon la revendication 1, dans lequel la température de fonctionnement constante est dans la plage
comprise entre 127 et 138 °C (260 et 280 °F), éventuellement dans lequel les particules séchées collectées
depuis le broyeur comprennent Al2(OH)Cl5 et ont une basicité de 14 à 18 %.

55 5. Procédé selon la revendication 1, dans lequel la température de fonctionnement constante est dans la plage comprise
entre 149 et 154 °C (300 et 310 °F), éventuellement dans lequel les particules séchées collectées depuis le
broyeur comprennent Al2(OH)2Cl4 et ont une basicité de 31 à 35 %.

11
 EP 3 191 406 B1

6. Procédé selon la revendication 1, dans lequel la température de fonctionnement constante est dans la plage
comprise entre 171 et 177 °C (340 et 350 °F), éventuellement dans lequel les particules séchées collectées
depuis le broyeur comprennent Al2(OH)3Cl3 et ont une basicité de 38 à 52 %.

5 7. Procédé selon la revendication 1, dans lequel la température de fonctionnement constante est dans la plage comprise
entre 177 et 182 °C (350 et 360 °F), éventuellement dans lequel les particules séchées collectées depuis le
broyeur comprennent Al2(OH)4Cl2 et ont une basicité de 64 à 68 %.

8. Procédé selon la revendication 1, dans lequel la température de fonctionnement constante est dans la plage
comprise
10 entre 193 et 204 °C (380 et 400 °F), éventuellement dans lequel les particules séchées collectées depuis le
broyeur comprennent Al2(OH)5Cl et ont une basicité de 81 à 85 %.

9. Procédé selon la revendication 1, dans lequel le courant de gaz comprend de l’air ambiant et de la vapeur.

15 10. Procédé selon la revendication 1, dans lequel lesdites particules séchées ont une densité apparente de 636 à 1 042
kg/m3 (40 à 65 livres par pied cube).

11. Procédé selon la revendication 1, dans lequel lesdites particules séchées ont une taille moyenne de particules dans
la plage de 10 à 15 microns.
20

25

30

35

40

45

50

55

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13
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14
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15
EP 3 191 406 B1

16
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17
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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

• WO 5985234 A [0004]
• US 4390131 A [0008]
• DD 273824 [0006]
• US 3462086 A [0008]
• WO 9008738 A [0007]
• US 2470315 A [0008]
• US 6145765 A [0008]
• US 20040040178 A [0008]
• US 5167372 A [0008]
• US 5573582 A [0008]

Non-patent literature cited in the description

• MCCABE ; SMITH. Evaporation. Unit Operations of

• PERRY ; GREEN. Perry’s Chemical Engineering
Chemical Engineering, 1976, 425-463, 11-118
Handbook. 1999 [0009]
[0009]
• Evaporation, 11-107, 11-118 [0009]
• Crystallization, 852-894 [0009]
• Crystallization, 18-35, 18-55 [0009]
• Filtration, 922-953 [0009]
• Filtration, 18-74, 18-125 [0009]

19