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An Interchangeable Liquid And Vapour Phase Reactor.

Abstract: An interchangeable liquid and vapour phase reactor comprises: at least a reaction vessel with a lid, said reaction being in liquid phase configuration or in vapour phase configuration depending upon the configuration of said reactor, said lid further comprising a plurality of securing means allowing a plurality of components which form a part of said reactor removed or attached within said reaction vessel; at least a modular stirring shaft with a detachable impeller, said impeller being chosen from a group of impellers consisting of liquid phase impellers and vapour phase impellers depending upon the configuration of said reactor; and at least an outlet valve on the underside of said reaction vessel.

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Notices, Deadlines & Correspondence

Patent Information

Application #
Filing Date
10 April 2013
Publication Number
16/2015
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application

Applicants

AMAR EQUIPMENTS PVT. LTD.
6, PARMAR INDUSTRIAL ESTATE, BAIL BAZAAR, KALE MARG, KURLA (W), MUMBAI 400 070, MAHARASHTRA, INDIA

Inventors

1. MALSHE VINOD CHINTAMANI
33-34, BUILDING NO 10, KAMDHENU, HARI OM NAGAR, MULUND (E), MUMBAI 400081, MAHARASHTRA, INDIA

Specification

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
As amended by the Patents (Amendment) Act, 2005
AND
The Patents Rules, 2003
As amended by the Patents (Amendment) Rules, 2006
COMPLETE SPECIFICATION
(See section 10 and rule 13)
TITLE OF THE INVENTION
An interchangeable liquid and vapour phase reactor
APPLICANTS
Amar Equipments Pvt. Ltd.; 6, Parmar Industrial Estate, Bail Bazaar, Kale Marg, Kurla (W), Mumbai 400 070, Maharashtra, India; an Indian Company.
INVENTOR
Malshe Vinod Chintamani residing at 33-34, Building No 10, Kamdhenu, Hari Om Nagar, Mulund (E), Mumbai 400081, Maharashtra, India; an Indian national.
PREAMBLE TO THE DESCRIPTION:
The following specification particularly describes the nature of this invention and the manner in which it is to be performed:

FIELD OF THE INVENTION:
This invention, relates to the field of mechanical engineering and chemical engineering.
Particularly, this invention relates to the field of reactors and autoclave equipment.
Specifically, this invention relates to an interchangeable liquid and vapour phase reactor.
BACKGROUND OF THE INVENTION:
Chemistry, a branch of physical science, is the study of the composition, properties and behavior of matter. In chemical engineering, chemical reactors are vessels designed to contain chemical reactions. One example is a pressure reactor.
Further, chemical reaction engineering is the branch of chemical engineering which deals with chemical reactors and their design, especially by application of chemical kinetics. The design of a chemical reactor deals with multiple aspects of chemical engineering as well as mechanical engineering suited to that effect.
Essentially, there are two types of reactors: 1) liquid phase reactors; and 2) vapour phase reactors.
A vapour phase reactor, typically, is a heavy vessel for carrying out chemical reactions on an industrial scale where efficient control over a vapor phase is needed, for example, in an oxidation process. Similarly, a liquid phase reactor,

typically, is a heavy vessel for carrying out chemical reactions on an industrial scale where efficient control over a liquid phase is needed.
According to prior art, there is a vapour phase reactor called a Berty Stationary Basket Catalyst Reactor. It consists of a high pressure reactor with bottom stirring, stationary catalyst basket, and vane blower up to 2500 rpm) used for laboratory, high temperature, and high pressure heterogeneous catalysis experiments with gas / solid phase reactants. It is used for internal reaction and it provides for varying reaction time for catalyst activation, catalyst regeneration, and catalyst endurance (catalyst life) for studying pressure up to 400 bar, temperature up to 650o C in MOC SS316, HC 276, and the like. In this prior art reactor, the vane blower is rotated from bottom by a magnetic drive assembly. Here, the stationary basket is a woven wire mesh basket which retains solid catalyst and allows gas / vapour circulation with low pressure drops.
A vapour phase reactor, typically, consists of reactor vessels of different volumes with suitable lids, clamps, and bolts in order to withstand high pressure. There may be magnetic drive coupling (used for shaft sealing) which is rotated by motor. The drive coupling rotates the shaft and impeller (of different designs), connected to it, inside the vessel. It also has a catalyst basket in the vessel which holds the catalyst(s); a thermowell for temperature sensor; a blower; and a dip pipe for gas charging and liquid sampling. External to the vessel, at its operative bottom, an outlet valve, a condenser, and a receiver cum separator pot are provided.
According to prior art, there are also packed-bed tubular reactors. Multi-phase reactions like hydrogenation are of tremendous importance to the fine chemical and pharmaceutical industries. These reactions are usually carried out in slurry semi-batch reactors, where the catalyst is usually suspended in the liquid which is

continuously agitated with a stirrer. Other types of reactor designs for carrying out catalytic reactions include trickle-bed, fluidized-bed, conventional packed-bed configurations. In these reactors, the reaction kinetics for fast Gas-Liquid-Solid reactions is often limited by external mass-transfer of gas to the catalyst surface. This is because of poor Gas/Liquid/Solid contact provided by these reactors. As a result, the reaction volume is over-sized in terms of the active volume leading to low yield of the product.
According to prior art, there are also liquid phase reactors. A lliquid phase reactor is used to carry out different types of high pressure and / or high temperature chemical reactors like alkylation, amination, bromination, carboxylation, catalytic reduction, chlorination, dehydrogenation, esterification, ethoxylation, halogenation, hydrogenation, methylation, nitration, oxidation, ozonization, polymerization, sulphonation, etc. at high pressure / vacuum & temperature. This is mainly to invent new chemicals, study reaction parameters; to produce chemicals in small quantity in batch or continuous mode; for synthesis; for quality control and process improvements; for heterogeneous mixing to carry out catalytic reactions; for high throughput catalyst screening; and the like applications.
A liquid phase reactor, typically, consists of reactor vessels of different volumes with suitable lids, clamps, and bolts in order to withstand high pressure. There may be magnetic drive coupling (used for shaft sealing) which is rotated by motor. The drive coupling rotates the shaft and impeller (of different designs), connected to it, inside the vessel. It also has internal cooing coil for cooling and for temperature control; a thermowell for temperature sensor ; and a dip pipe for gas charging and liquid sampling.

Initially, the vessel lid is opened and filled with suitable reactants (substrate) and powder/catalyst as required. The vessel is then sealed with the lid and clamp is tightened. As required, gas is charged under pressure, stirring and heating is started to reach desired temperature of reaction(s). After the reaction is over, the reactor is cooled.
A typical chemical laboratory requires equipment to carry out reactions in liquid phase or vapour phase. It requires distinctly different equipment which are expensive, need more space for operation, need specialized personnel to operate them. Both are high cost thus restricting the laboratory facilities.
Hence, there is a need for a universal design or an interchangeable design which would interchange between its functions of a liquid phase reactor and a vapour phase reactor, due to its modular design, in order to mitigate the costs associated with having two different assemblies (reactors).
OBJECTS OF THE INVENTION:
An object of the invention is to provide a single-unit liquid phase reactor and a vapour phase reactor.
Another object of the invention is to provide an interchangeable liquid phase reactor and a vapour phase reactor.
Yet another object of the invention is to provide a single-unit liquid phase reactor and a vapour phase reactor such that they are interchangeable between its functions of a enabling liquid phase reactions and enabling vapour phase reactions.

Still another object of the invention is to provide a modular reactor which functions as a liquid phase reactor as well as a vapour phase reactor, the modularity being imparted by mechanical configuration of the reactor. SUMMARY OF THE INVENTION:
According to this invention, there is provided an interchangeable liquid and vapour phase reactor comprising:
• at least a reaction vessel with a lid, said reaction being in liquid phase configuration or in vapour phase configuration depending upon the configuration of said reactor, said lid further comprising a plurality of securing means allowing a plurality of components which form a part of said reactor removed or attached within said reaction vessel;
• at least a modular stirring shaft with a detachable impeller, said impeller being chosen from a group of impellers consisting of liquid phase impellers and vapour phase impellers depending upon the configuration of said reactor; and
• at least an outlet valve on the underside of said reaction vessel.
Typically, said reactor comprises at least a relatively long thermowell inside said reaction vessel in its liquid phase configuration.
Typically, said reactor comprises at least a relatively short thermowell in a T-junction connection to said at least an outlet valve in its vapour phase configuration.
Typically, said reactor comprises at least a dip tube inside said reaction vessel in its liquid phase configuration.

Typically, said reactor comprises at least a cooling coil inside said reaction vessel in its liquid phase configuration.
Typically, said at least a modular stirring shaft comprises at least a top rod extending with at least a bottom rod, said at least a bottom rod being remove-ably secured to said at least a top rod, in that said at least a bottom rod adapted to be detached from said at least a top rod.
Typically, said at least a modular stirring shaft comprises at least a top rod extending with at least a bottom rod, said at least a bottom rod being remove-ably secured to said at least a top rod, in that said at least a bottom rod adapted to be detached from said at least a top rod, characterised, in that, said operative distal end of said at least a top rod comprising a first impeller and further, characterised, in that, said at least a bottom rod comprising a second impeller at its operative distal free end.
Typically, said reactor comprises at least a removable catalyst basket adapted to be used in said reaction vessel in order to render said reactor as a vapour phase reactor and adapted to be removed from said reaction vessel in order to render said reactor as a liquid phase reactor.
Typically, said reactor comprises at least an agitator connected to said lid in its liquid phase configuration.
Typically, said reactor comprises at least a blower connected to said lid in its liquid phase configuration.
Typically, said reactor comprises at least a dead plug adapted to be located under the operative bottom of said reaction vessel in its liquid phase configuration.

Typically, said reactor comprises means located under the operative bottom of said reaction vessel in order to receive additional components from a group of components consisting of an outlet valve, a condenser, and a receiver cum separator pot in its vapour phase configuration.
Typically, said reactor comprises at least a condenser tube for enabling liquid or gas to be fed through in to said reactor.
Typically, said reactor, in its liquid phase configuration, comprises at least a condenser in order to condense liquid products to be collected at a receiver cum separator pot below said reaction vessel and further to allow for collection of non condensable vapours from said at least a condenser.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS:
The invention will now be described in relation to the accompanying drawings, in
which:
Figure 1 illustrates a schematic drawing of a vapour phase reactor; Figure 2 illustrates a schematic drawing of a liquid phase reactor; Figure 3 illustrates an isometric view of the lid;
Figure 4a illustrates an isometric view of the impeller of the vapour phase; Figure 4b illustrates a front view of the impeller of the vapour phase;

Figure 4c illustrates a top view of the impeller of the vapour phase;
Figure 5a illustrates an isometric view of the impeller of the vapour phase;
Figure 5b illustrates a top view of the impeller of the vapour phase;
Figure 5c illustrates a side view of the impeller of the vapour phase;
Figure 6a illustrates a sectional view of the modular stirring shaft; and
Figure 6b illustrates an isometric view of the modular stirring shaft.
DETAILED DESCRIPTION OF THE ACCOMPANYING DRAWINGS:
According to this invention, there is provided an interchangeable liquid and vapour phase reactor.
Figure 1 illustrates a schematic drawing of a vapour phase reactor.
Figure 2 illustrates a schematic drawing of a liquid phase reactor.
In accordance with an embodiment of this invention, there is provided a reaction vessel (12) with a lid (10). This reaction vessel (12) is the area where reactions take place. Reactions may take place in the liquid phase or in the vapour phase. This is determined before the modular changes to be carried out in order to enable the reactor to function in various modes. The reactor of this invention is operable in two distinct interchangeable embodiments: 1) liquid phase reactor embodiment;

and 2) vapour phase reactor embodiment. The lid (10) comprises a plurality of securing means such that a plurality of components which form a part of the reactor and are to be inserted within the vessel (12) can be removed or attached with ease. The removal or attachment and selection of the plurality of components are based on the function(s) that the reactor aims to achieve.
Figure 3 illustrates an isometric view of the lid (10).
In its liquid phase operation, the lid (10) securely attaches to itself liquid phase related components such as a stirring shaft (14) (suitable to liquid phase stirring and with a liquid phase impeller (17) advantageously made out to that effect), thermowell (relatively long) (16), dip tube (22), cooling coil (24), and dead plug (26). Typically, the shaft is threaded to a magnetic drive; hence modular and removable.
Figure 5a illustrates an isometric view of the impeller (17) of the liquid phase.
Figure 5b illustrates a top view of the impeller (17) of the liquid phase.
Figure 5c illustrates a side view of the impeller (17) of the liquid phase.
In its vapour phase operation, the lid (10) securely attaches to itself vapour phase related components such as a stirring shaft (14) (suitable to vapour phase stirring and with a vapour phase impeller (15) advantageously made out to that effect), and thermowell (relatively short) (18). In its vapour phase, the relatively shorter thermowell is removed from the vessel and is placed in a T-junction connection to an outlet valve (32). This provides better results in the vapour phase module. Typically, the shaft is threaded to a magnetic drive; hence modular and removable.

Figure 4a illustrates an isometric view of the impeller (15) of the vapour phase.
Figure 4b illustrates a front view of the impeller (15) of the vapour phase.
Figure 4c illustrates a top view of the impeller (15) of the vapour phase.
Typically, the stirring shaft (14) is a modular stirring shaft. It comprises an elongate rod made up a top rod extending with a bottom rod. The bottom rod is remove-ably secured to the top rod, in that the bottom rod can be detached from the top rod. The end of the top rod comprises a first impeller enveloping the elongate rod. The bottom rod comprises a second impeller at its free end. The impellers are screwed on to the rod, making it easy to remove and secure.
Figure 6a illustrates a sectional view of the modular stirring shaft (14).
Figure 6b illustrates an isometric view of the modular stirring shaft (14).
In accordance with an embodiment of this invention, there is a stationary catalyst basket (42) adapted to be used in the vessel in order to render the reactor as a vapour phase reactor. There is an arrangement for recycling vapour through a stationary catalyst bed which is contained in the space which is used for liquid phase reactions. The catalyst basket (42) is placed in the vessel (12) cavity, typically, with about 5 mm gap from the heating walls. The agitator which is connected to the top lid is removed and replaced with a blower for use as vapour phase reactor.
In accordance with an embodiment of this invention, there is provided a dead plug (26) adapted to be located under the operative bottom of the vessel (12); exterior to the vessel (12). The dead plug (26) is in place while the reactor is used as a liquid phase reactor. The dead plug (26) is adapted to receive additional components from

a group of components consisting of an outlet valve (32), a condenser (34), and a receiver cum separator pot (36) while the reactor is used as a vapour phase reactor.
Typically, the liquid or gas to be fed in the reactor is through a condenser tube. The liquid is fed through a metering pump. As the liquid travels downwards, it evaporates and is sucked by a blower and the vapours are pushed through the catalyst basket (42). The addition of liquid leads to slight increase in pressure of the gas phase. The product is withdrawn from the bottom discharge valve (32) and is passed through a condenser (34) to condense the liquid products to be collected at the receiver cum separator pot (36). Non condensable vapors are collected from the condenser (34).
In order to change from vapour phase reactor embodiment to liquid phase reactor embodiment, the following parts are interchanged. The lid (10) is opened and separated from the vessel (12). Vapour phase reactor embodiment has short stirring shaft (14) with blower / impeller (15) which is removed and a long stirring shaft (14) with impeller (17) is secured on the underside of the lid (10). Catalyst basket (42) from vapour phase reactor embodiment is removed. Relatively shorter thermowell (18) from vapour phase reactor embodiment is removed from the underside of the lid (10) and a relatively longer thermowell (16) is secured to the underside of the lid for liquid phase reactor embodiment. Cooling coil (24) is attached to the underside of the lid (10) for liquid phase reactor embodiment. Further, a dip tube (22) is attached to the under underside of the lid (10) for liquid phase reactor embodiment. Outlet valve (32), condenser (34), and receiver cum separator part (36) are removed from the underside of vessel (12) and a dead plug (26) is attached to the underside of the vessel in order to change from vapour phase reactor embodiment to liquid phase reactor embodiment. The bottom discharge which is blocked is opened.

The INVENTIVE STEP of the current invention lies in provisioning a single or unitary apparatus which provides a cover lid or a cover plate to a vessel, which cover lid or cover plate is modified to provide fixation of various sub-parts in order to render the reactor vessel suitable for liquid phase reactions or for gas phase reactions.
While this detailed description has disclosed certain specific embodiments of the present invention for illustrative purposes, various modifications will be apparent to those skilled in the art which do not constitute departures from the spirit and scope of the invention as defined in the following claims, and it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation.

We claim,
1. An interchangeable liquid and vapour phase reactor comprising;
• at least a reaction vessel with a lid, said reaction being in liquid phase configuration or in vapour phase configuration depending upon the configuration of said reactor, said lid further comprising a plurality of securing means allowing a plurality of components which form a part of said reactor removed or attached within said reaction vessel;
• at least a modular stirring shaft with a detachable impeller, said impeller being chosen from a group of impellers consisting of liquid phase impellers and vapour phase impellers depending upon the configuration of said reactor; and
• at least an outlet valve on the underside of said reaction vessel.

2. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a relatively long thermowell inside said reaction vessel in its liquid phase configuration.
3. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a relatively short thermowell in a T-j unction connection to said at least an outlet valve in its vapour phase configuration.
4. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a dip tube inside said reaction vessel in its liquid phase configuration.

5. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a cooling coil inside said reaction vessel in its liquid phase configuration.
6. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said at least a modular stirring shaft comprising at least a top rod extending with at least a bottom rod, said at least a bottom rod being remove-ably secured to said at least a top rod, in that said at least a bottom rod adapted to be detached from said at least a top rod.
7. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said at least a modular stirring shaft comprising at least a top rod extending with at least a bottom rod, said at least a bottom rod being remove-ably secured to said at least a top rod, in that said at least a bottom rod adapted to be detached from said at least a top rod, characterised, in that, said operative distal end of said at least a top rod comprising a first impeller and further, characterised, in that, said at least a bottom rod comprising a second impeller at its operative distal free end.
8. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a removable catalyst basket adapted to be used in said reaction vessel in order to render said reactor as a vapour phase reactor and adapted to be removed from said reaction vessel in order to render said reactor as a liquid phase reactor.
9. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least an agitator connected to said lid in its liquid phase configuration.

10. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a blower connected to said lid in its liquid phase configuration.
11. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a dead plug adapted to be located under the operative bottom of said reaction vessel in its liquid phase configuration.
12. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising means located under the operative bottom of said reaction vessel in order to receive additional components from a group of components consisting of an outlet valve, a condenser, and a receiver cum separator pot in its vapour phase configuration.
13. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor comprising at least a condenser tube for enabling liquid or gas to be fed through in to said reactor.
14. The interchangeable liquid and vapour phase reactor as claimed in claim 1, wherein said reactor, in its liquid phase configuration, comprising at least a condenser in order to condense liquid products to be collected at a receiver cum separator pot below said reaction vessel and further to allow for collection of non condensable vapours from said at least a condenser.

Documents

Application Documents

# Name Date
1 1348-MUM-2013-FER.pdf 2019-11-06
1 FORM28 [04-04-2017(online)].pdf 2017-04-04
2 1348-MUM-2013-ABSTRACT(9-4-2014).pdf 2018-08-11
2 Form 18 [04-04-2017(online)].pdf 2017-04-04
3 EVIDENCE FOR SSI [04-04-2017(online)].pdf 2017-04-04
3 1348-MUM-2013-CLAIMS(9-4-2014).pdf 2018-08-11
4 ABSTRACT1.jpg 2018-08-11
4 1348-MUM-2013-CORRESPONDENCE(2-9-2013).pdf 2018-08-11
5 1348-MUM-2013-Power of Attorney-151015.pdf 2018-08-11
5 1348-MUM-2013-CORRESPONDENCE(9-4-2014).pdf 2018-08-11
6 1348-MUM-2013-OTHER DOCUMENT(9-4-2014).pdf 2018-08-11
6 1348-MUM-2013-Correspondence-151015.pdf 2018-08-11
7 1348-MUM-2013-FORM 5(9-4-2014).pdf 2018-08-11
7 1348-MUM-2013-CORRESPONDENCE.pdf 2018-08-11
8 1348-MUM-2013-FORM 3.pdf 2018-08-11
8 1348-MUM-2013-DESCRIPTION(COMPLETE)-(9-4-2014).pdf 2018-08-11
9 1348-MUM-2013-DESCRIPTION(PROVISIONAL).pdf 2018-08-11
9 1348-MUM-2013-FORM 28(9-4-2014).pdf 2018-08-11
10 1348-MUM-2013-DRAWING(9-4-2014).pdf 2018-08-11
10 1348-MUM-2013-FORM 2.pdf 2018-08-11
11 1348-MUM-2013-DRAWING.pdf 2018-08-11
11 1348-MUM-2013-FORM 2(TITLE PAGE).pdf 2018-08-11
12 1348-MUM-2013-FORM 1(2-9-2013).pdf 2018-08-11
12 1348-MUM-2013-FORM 2(TITLE PAGE)-(9-4-2014).pdf 2018-08-11
13 1348-MUM-2013-FORM 1.pdf 2018-08-11
13 1348-MUM-2013-FORM 2(9-4-2014).pdf 2018-08-11
14 1348-MUM-2013-FORM 1.pdf 2018-08-11
14 1348-MUM-2013-FORM 2(9-4-2014).pdf 2018-08-11
15 1348-MUM-2013-FORM 1(2-9-2013).pdf 2018-08-11
15 1348-MUM-2013-FORM 2(TITLE PAGE)-(9-4-2014).pdf 2018-08-11
16 1348-MUM-2013-DRAWING.pdf 2018-08-11
16 1348-MUM-2013-FORM 2(TITLE PAGE).pdf 2018-08-11
17 1348-MUM-2013-FORM 2.pdf 2018-08-11
17 1348-MUM-2013-DRAWING(9-4-2014).pdf 2018-08-11
18 1348-MUM-2013-DESCRIPTION(PROVISIONAL).pdf 2018-08-11
18 1348-MUM-2013-FORM 28(9-4-2014).pdf 2018-08-11
19 1348-MUM-2013-DESCRIPTION(COMPLETE)-(9-4-2014).pdf 2018-08-11
19 1348-MUM-2013-FORM 3.pdf 2018-08-11
20 1348-MUM-2013-CORRESPONDENCE.pdf 2018-08-11
20 1348-MUM-2013-FORM 5(9-4-2014).pdf 2018-08-11
21 1348-MUM-2013-Correspondence-151015.pdf 2018-08-11
21 1348-MUM-2013-OTHER DOCUMENT(9-4-2014).pdf 2018-08-11
22 1348-MUM-2013-CORRESPONDENCE(9-4-2014).pdf 2018-08-11
22 1348-MUM-2013-Power of Attorney-151015.pdf 2018-08-11
23 1348-MUM-2013-CORRESPONDENCE(2-9-2013).pdf 2018-08-11
23 ABSTRACT1.jpg 2018-08-11
24 1348-MUM-2013-CLAIMS(9-4-2014).pdf 2018-08-11
24 EVIDENCE FOR SSI [04-04-2017(online)].pdf 2017-04-04
25 Form 18 [04-04-2017(online)].pdf 2017-04-04
25 1348-MUM-2013-ABSTRACT(9-4-2014).pdf 2018-08-11
26 FORM28 [04-04-2017(online)].pdf 2017-04-04
26 1348-MUM-2013-FER.pdf 2019-11-06

Search Strategy

1 searchstrategy_06-11-2019.pdf