Description

The present invention relates to a dosage system and to a method for dosing liquids into vessels. Preferably, the dosage system and method are used in connection with dosing reaction liquids into reaction a plurality of reaction vessels.

The dosage system comprises the handling of a hydraulic liquid whereby the handling of hydraulic liquid can be performed in a highly reproducible way. The present invention provides a method for dosing which is more robust over the method which is established in the state of the art. The dosing and the transfer of the feed is decoupled and divided into a first step of measurement and control of liquid which is performed with a hydraulic liquid and a second step of controlled release of a liquid which can be any liquid from low boiling to high boiling range, preferably within the range from 28 - 800 °C. The boiling temperature is given as a.e.t. which means atmospheric equivalent temperature. The viscosity of the feeds may be in the range from 0,2 mPa ^* s at 20°C to 500 mPa ^* s at 150 °C. According to SI units the unit mPa-s means millipascal-second. The use of the invention in connection with the field of high throughput units which are equipped with a series of parallel reaction vessels brings an advantage that the flexibility of the testing unit can be improved in such a way that the operation can be performed without the need to adjust the testing unit in a time-consuming way.

The PCT-application WO 2012/160076 A1 discloses a device for feeding reactant liquids and illustrates that the dosing of heavy feeds is of high technical relevance. Therefore, the WO 2012/160076 A1 provides a technical solution in which the temperature of the feed capillaries are wrapped around a body which exhibits a high heat capacity in order to provide the conditions for an improved tempering of the capillaries.

One of the objects of the present invention is to provide a device and associated methods for dosing liquids which is improved in comparison with the prior art. Furthermore, it was an object that the dosing system should be flexible.

These and other objects are achieved according to the invention by providing a dosage system for dosing liquids into vessels (101) which comprises a hydraulic liquid supply vessel (15), means for pressurizing and transferring hydraulic liquid, a multi-chamber storage device (301) and at least one transfer line (201) which is in connection with the multi-chamber storage device (301), whereby the dosage system is characterized in that, that the hydraulic liquid supply vessel (15) and the multi-chamber storage device (301) are in the a operative connection which exhibits either a throttle (501 ) or a flow controller (50) in case that the operative connection is equipped with a throttle (501) then the means for pressurizing hydraulic liquid comprising a high pressure pump (12) and in case that the means are equipped with a flow controller (50) then the means pressurizing hydraulic liquid comprising a pressure gas supply line (16) which is attached to the hydraulic liquid supply vessel (15).The operating pressure of the high pressure pump (12) depends on the given set-up of the dosage system and may be in the range from 0 - 500 barg which represents the pressure in bars above atmospheric pressure.

The dosage system provides a decoupling of the device region which has the technical function of measuring and control and device region which has the function of handling the fluids to be dosed or injected. By the invention it is possible to improve the accuracy of the dosing over the direct dosing which are known in the prior art. The hydraulic liquid comprises a well-known calibration solution with known physical properties. The handling of the hydraulic solution is easy and comfortable. In a preferred embodiment the hydraulic solution is tempered at a desired temperature in the range from 20 °C - 150 °C.

Concerning the hydraulic liquids which are suitable in connection with the dosing system the following has to be said: hydraulic liquids are known to the person who is skilled in the art.

The dosage system preferably also comprises a high precision balance (14) which is in a functional connection with the hydraulic liquid supply vessel (15), whereby it is preferred that the system which is equipped with a high precision balance (14) comprises a high pressure pump (12) as means for transferring hydraulic liquid from the supply vessel (15) to the multi chamber storage device (301, 302, 203, ...), preferably the multi chamber storage device (301 , 302, 203, ...) is selected from the group of membrane vessel, vessel with a blister reservoir, container with piston accumulator, preferably the storage volume for liquid is in the range from 0.1 - 10 L, more preferably in the range from 0.2 - 5 L, most preferably in the range from 0.4 - 2.5 L. The resolution of the high precision balance (14) may be 0,1 g or higher. In a preferred embodiment the multi chamber storage device (301, 302, 203, ...) encompasses two chambers whereby one chamber forms the up-take chamber for the hydraulic liquid and the other chamber forms the storeroom for dosing liquid. The hydraulic liquid which is transferred into the first chamber of the storage device leads to a displacement of the dosing liquid which is transferred into the exit line and the vessel.

Preferably the system comprises a vessel (101) which is connected to the multi-chamber storage device by the transfer line (201); preferably the vessel is a tubular vessel (101), more preferably a reactor tube which has an inner volume in the range from 0.5 ml. - 250 ml_, more preferably the inner volume is in the range from 1 ml. to 100 ml_.

In a preferred embodiment the dosage system comprises a plurality of multi-chamber storage device (301 , 302, 303, ... ), a plurality of transfer lines (201 , 202, 203), and a plurality of vessels (101, 102, 103,...) whereby each vessel (101, 102, 103,...) is connected with a separate multi chamber storage device (301, 302, 303, ...) by an individual transfer line (201, 202, 203, ...); the operative connection comprises a hydraulic main line (11), a splitter (60) and plurality of hydraulic side lines (401, 402, 403, ...) which are connected to the multi-chamber storage device (301 , 302, 303, ... ), preferably the number of vessels is in the range from 2 - 100, more preferably in the range from 2 - 40, even more prefer-ably from 4 to 20;

(a) in case of the set-up with the high pressure pump (12): the high pressure pump (12) is arranged in the hydraulic main line (11), each hydraulic side line (401, 402, 403, ...) is equipped with a throttle (501 , 502, 503);

(b) in case that the set-up is based on pressurization set-up by gas via pressure line (16): the system comprises either one flow controller (50) which is arranged in the hydraulic main line (11) and a plurality of throttles (501, 502, 503, ...) which are arranged in the hydraulic side lines (401, 402, 403, ...) or a plurality of flow controllers (50i, 50N, 50iii, ...) whereby each of the hydraulic side lines (401, 402, 403, ...) is equipped with a flow controller (50i, 50N, 50iii, ...). Preferably the system is part of a high throughput apparatus for testing catalyst whereby the catalysts are arranged within the vessel (101, 102, 103,...) which are preferably given by tubular reactors.

In another embodiment which is also preferred the dosage system comprises plurality of pressure sensors (701, 702, 703, ...) and the pressure sensors (701, 702, 703, ...) are arranged in the hydraulic side lines (401, 402, 403, ...) downstream of the throttles (501, 502, 503, ...) or downstream of the flow controllers (50i, 50N, 50iii, ...).

The pressure sensors (701, 702, 703, ...) have the additional advantage that the clogging of the vessels may be easily detected. The clogging may disrupt the whole operation due to the uncontrolled changes in the flow. The detection of reactor clogging gives an indication to remove or disconnect an individual vessel, preferably tubular reactor, from the fluid stream. Other possibilities would be to store the selected vessel under inert gas conditions or regenerate the catalysts by a treatment under combustion conditions in order to remove the depositions. The indication for blockage of reactor vessels is given by an unforeseen high pressure increase in the supply line. The pressure detection provides the advantage that the reactors which show the pressure changes can be removed from the feed supply. Thus it is possible to reduce or avoid interruptions or malfunctions of the experiments which are associated with overloading of a blocked reactor vessel.

Furthermore it is preferred that the dosage system is provided in an embodiment whereby the operative connection comprises one or more switch valves (62), preferably a multi-port valve (62), more preferably the multi-port valve (62) is arranged in the position of the splitter (60) which connects the hydraulic main line (11) with the hydraulic side lines (401, 402, 403, ...). The switch valves (62) provides the means that liquids can be transferred to a selected number of reaction vessels.

A multi-port valve (62) may provide a set-up with more flexibility in case that the operator has the option to select certain groups of vessels which can be accessed with feed whereas other vessels in the same arrangement are not accessed with feed.

The dosage system for dosing liquids into vessels preferably comprises a plurality of gas supply lines (801, 802, 803,...) and either the transfer line (201, 202, 203, ...) or the vessels (101, 102, 103, ...) are connected with a gas supply lines (801, 802, 803, ...) whereby each arrangement of transfer line and vessel is in contact with one gas supply line.

Preferably the dosage system for dosing liquids is provided in an embodiment in which the hydraulic liquid supply vessel (15) has a storage volume in the range from 0.5 L to 50 L, preferably in the range from 1 L to 25 L, more preferably in the range from 2 L to 20 L; and/or whereby the throttles (501, 502, 503, ...) which are arranged in each hydraulic side lines (401, 402, 403, ...) are restrictors (501, 502, 503, ...), preferably capillary restrictors (501 , 502, 503, ...), more preferably capillaries which have an inner diameter in the range from 50 - 1000 pm, preferably in the range from 75 - 750 pm and a length in the range from 10 - 500 cm , even more preferably steel capillaries, more preferably equipped with heating systems; the diameter of the hydraulic main line is in the range from 1 - 20 mm, the diameter of the hydraulic side lines is in the range from 1 - 20 mm. Throttles (501, 502, 503, ...) may be given as flow restriction elements in the form of micro regulation valves.

An advantage is that throttle (501), preferably capillaries, can be highly sensitive with respect to corrosion. Therefore, the invention also has the advantage that the measurement and control parts according to the present invention are not exposed to the dosing liquids which may comprise acid solutions, alkaline components and/or water. Furthermore, the different liquids may exhibit pronounced differences in viscosity. Fluids with a very high viscosity are more difficult to handle over liquids which have a low viscosity. An advantage which is given in connection with the present invention is that the calibration work is significantly reduced or may be completely omitted when the operation comprises a change of the type of fluid which shall be dosed with the apparatus according to the invention. In case that the throttles have the embodiment of capillaries then these capillaries may be given in the form of metal capillaries, preferably steel capillaries, or non-metal capillaries, preferably silica comprising capillaries, more preferably fused silica comprising capillaries. Without the use of the dosing system according to the invention the switch of feed type may cause a complex and tedious process to modify and adjust the restrictors to the viscous property of the new type of liquid. The adjustment of the steel capillaries to reach an equal flow distribution is a difficult task which is time consuming. The system according to the invention makes such complications superfluous.

A preferred embodiment of the invention is given in case that the dosing system is part of a high throughput testing apparatus whereby the dosing system is used to transfer the liquid into the plurality of vessels. In such an embodiment it is also preferred that the dosing system is provided in a configuration in which the hydraulic liquid is transferred by a high pressure pump via throttles, more preferably restrictors which are arranged in the lines downstream of the splitter. The high pressure pump is preferably given as FIPLC pump. The use of restrictors in combination with a FIPLC pump have the advantage that the single fluid flow which is pumped with the FIPLC pump is divided into several flows in each line which provides the possibility of high precision dosing of very low rates. An example would be given by a FIPLC pump which could provide a flow rate in the range from 0,01 - 1000 mL/min. The combination with 10 vessels would mean that 10 restrictor elements would be arranged in the lines prior to the multi chamber storage device. In such an embodiment the flow rate which is provided by the FIPLC pump is reduced to a tenth of the flow rate to each vessel in the range from 0,001 to 100 mL. A synergistic effect is provided by an assembly of the dosing system in connection with a high throughput testing apparatus which is equipped with a parallel arrangement of reactor vessels, preferably 2 to 50 vessels, further preferred a set-up with 4 to 40 vessels.

The dosing of fluids according to the state of the art may require an adjustment of feed capillaries in case the operator switches the system from one type of feed to another type of feed which has different physical properties.

The invention relates to a method for dosing liquids into vessels by using a dosage system for dosing liquids is provided in the disclosure herein whereby the method comprises the following steps:

(i) hydraulic liquid is pumped or transferred from the supply vessel (15) to one or more multi chamber storage devices (301 , 302, 303, ...), (ii) the introduction of the hydraulic liquid in the one or more multi-chamber storage devices (301, 302, 303, ...) displaces the reaction liquid;

(iii) reaction liquid is transferred into transfer line(s) (201, 202, 203, ...) and the vessel(s) (101, 102, 103, ...)

Preferably the method for dosing liquids into vessels by using a dosage system for dosing liquids which is characterized is characterized by such that the hydraulic liquid supply vessel (15), whereby the one or more multi-chamber storage devices (301, 302, 303, ...) are heated and/or tempered at a temperature in the range from 0 °C to 250 °C, prefer-ably at a temperature in the range from 25 °C to 200 °C.

It is preferred that the method for dosing liquids into vessels is used to dose liquids which are selected from the group of naphtha feeds, diesel, heavy diesel, oil, gas oil, vacuum gas oil, heavy oil such as residues of atmospheric or vacuum distillation, bio oil selected from the group of pyrolysis oil, resins, fatty acids and/or the process which is carried out in the vessels is selected from the group of hydrodesulfurization, hydro-denitrogenation, hydro-deoxygenation, hydro-dearomatization (in general hydrotreating) and hydrocracking. The use of the system and method is associated with different advantages whereby the high flexibility with respect to the use of different types of feeds is a very beneficial advantage. Furthermore, it is possible to handle those liquid fluids which cause technical problems in connection with pumping. For example, very heavy oils and resids which are solid at room temperature. The very heavy feeds exhibit a viscosity in the range from 30 mPa ^* s at 100 °C to 500 mPa ^* s at 150 °C. The invention provides an unexpected high flexibility with respect to the dosing of liquids which are difficult to handle and the change from one type of liquid to another type of liquid which are associated with very different properties in terms of melting point and viscosity. The viscosity of a diesel feed may be in the range from 1 to 5 mPa ^* s at 25 °C. The viscosity of a VGO feed may be in the range from 1 to 50 mPa ^* s at 100 °C. Another advantage is also given by the fact that liquid materials can be transferred which contain solid particles.

In a preferred embodiment the method for dosing liquids into vessels is used in connection with high pressure processes. Preferably the processes which are carried out in the vessels (101 , 102, 103, ...) are operated at a pressure in the range from 1 barg to 500 barg, preferably in the range from 10 barg to 300 barg, more preferably in the range from 15 barg - 250 barg; and/or the processes which are carried out in the vessels are carried temperatures in the range from 50 °C to 1000 °C, preferably from 100 °C to 800 °C, more preferably from 100 to 500 °C.

The term flow controller (50) according to the present inventions means a flow controller with a loop back control.

It is also noted that the invention relates to a computer program on a data carrier to control a system according for dosing liquids according to the present invention and/or use a computer program to perform the method according to the present invention.

Detailed description of the invention Further embodiments of the dosing system according to the present invention are shown in the Figures. It is noted that these embodiments show different illustrations without any intension to narrow or limit the subject of the present invention.

The different Figures illustrate the dosing system can be used in a very flexible way in different technical set-ups. It is pointed out that the dosing system may be used in a continues operation without the need to exchange the multi chamber storage vessel (301) during the operation of the system whereby the continues operation is provided by a transfer of hydraulic liquid to the hydraulic liquid supply vessel (15) and refilling the multi chamber storage vessels during the process. Furthermore, the multi chamber storage vessel may be arranged in a parallel set-up in connection with a system which allows to refill of the multi chamber storage vessels (301) while these storage vessels are installed in the unit as shown in Figure 9.

In an embodiment in which the focus is to test many different feeds then the operator may have the different feeds stored in different multi chamber storage vessel by having the corresponding number of storage containers for each type of feed and each individual reactor vessel. For example, a 16-fold testing apparatus shall be operated with 5 different types of feeds on a regular base. In a preferred embodiment the operator would hold 5 sets of 16 multi chamber storage vessel whereby each set of storage vessel would be filled with a different type of feed. The switch or change of the feed type would be easily performed by replacement of the whole set multi chamber storage vessel. This would be a simple manual operation without the need of any adjustment of the restrictors.

In another embodiment the 16-fold testing apparatus could be operated with 5 different feeds in parallel whereby the operator can adjust the corresponding storage vessels in a flexible way according to the desired testing plan. This would provide the possibility to perform various types of feed studies within the same operating time of the testing apparatus.

A switch of the type of feed is provided by changing of one multi chamber storage vessel (301 ) to another multi chamber storage vessel (301 ^* ) which had been filled with a different feed. An advantage is given that the handling, filling and/or cleaning of multi chamber storage vessel (301, 301’,...) is conducted in an external space which is independently of the testing apparatus.

In another embodiment one individual reactor of a testing apparatus may be connected with two multi-chamber storage vessels (30T) and (301”). The multi-chamber storage vessels (30T) and (301”) may contain different feeds and the type of feed which is dosed into the reactor can be selected by switching of valves which are arranged in the lines up-stream and down-stream of each of the multi-chamber storage vessels (30T) and (301”). In another embodiment the feeds may be the same in both multi-chamber storage vessel (30T) and (301”) whereby the operator may switch from the first to the second vessel (i.e. from the multi-chamber storage vessel (30T) to the vessel (301”) in case that the first would have been emptied during the system is in operation.

In a preferred embodiment the multi chamber storage vessel can be precisely tempered at a target temperature in order to keep the feed in the liquid stage. It is remarkable that the dosing process is not impaired by the presence of solid material within the feed which means that it is possible by the invention to precisely dose heavy resid feeds which contains solid particles which would normally block the technical set-up in a standard systems for testing heavy feeds which is given in the state of the art. Consequently, one aspect of the present invention is given by a simplification of the testing process which is given omitting more complex system which may include a feed filtration unit. Feed filtration would cause an additional investment and higher technical complexity. The feed filters may be blocked and could create additional technical problems. The testing significance is beneficial in case that heavy feeds are tested in the as is stage without being subjected to filtration pre processing which may modify the feed composition in such a way that the resulting testing data may have a lower degree of significance over an unprocessed feed which is in its original state. Flence, the system is suitable for handling complex systems. The term solid material refers to particles which have a size in the range from 1 - 1000 pm, preferably the size of the particles is £ 100 pm (smaller or equal to 100 pm). Preferably, in particular for fixed-bed applications the size of the particles is £ 7 pm, more preferably is £ 1 pm, more preferably. The processing of feeds which comprise solid particles which are larger than 7 pm requires the use of a fluidized bed reactor. It is clear for the person who is skilled in the art, that the solid particles above 2 mm may cause coking and blockage or reactor vessels and deterioration of the process.

A preferred embodiment of the invention is given when the dosing system according to the invention is combined with a testing apparatus which is used for testing catalyst under ebulated bed conditions. More preferred the testing apparatus is equipped with 2 to 20 parallel reactor vessels, even more preferred is a testing apparatus with 4 to 16 parallel reactors vessels.

Brief description of the figures:

Figure 1 shows a schematic diagram of an embodiment of the dosage system which is equipped with a single line of hydraulic liquid supply vessel (15), hydraulic main line (11) with flow controller (50) and multi chamber storage vessel (301) which is equipped with a transfer line (201). The hydraulic liquid supply vessel (15) is connected to pressure line (16).

Figure 2 shows a schematic diagram of an embodiment of the dosage system which is equipped with three multi chamber storage vessels (301, 302, 303, ...) which are arranged in parallel. Each of the multi chamber storage vessels (301, 302, 303,...) is in a functional connection with a hydraulic liquid supply vessel (15) whereby the functional connection is equipped with a hydraulic main line (11) and three hydraulic side lines (401 , 402, 403, ...). The hydraulic liquid supply vessel (15) is equipped with a high precision balance. The junction of the connection between the main line (11) and the side lines (401, 402, 403, ...) is formed as splitter (60). The hydraulic main line (11) comprises a high pressure pump and each hydraulic side line (401 , 402, 403,...) comprises a throttle (501, 502, 503,...).

Figure 3 shows a schematic diagram which corresponds to the embodiment of Fig. 2, whereby the splitter (60) is designed as selection valve (62).

Figure 4 shows a schematic diagram which corresponds to the embodiment of the dosage system of Fig. 3, whereby each hydraulic side line (401, 402, 403,...) is equipped with a separate pressure sensor (701, 702, 703, ...) which are arranged down stream of the throttles (501, 502, 503, ...).

Figure 5 shows a schematic diagram of an embodiment of the dosage system which corresponds to the embodiment which is shown in Fig. 4 whereby the means for the transfer of the hydraulic liquid comprise a high pressure supply line (16) which is attached to the hydraulic liquid supply vessel (15) and a flow controller (59) which is arranged in the hydraulic main line (11).

Figure 6 shows a schematic diagram of an embodiment of the dosage system which corresponds to the embodiment which is shown in Fig. 5 whereby the throttles (501 , 502, 503,...) which are shown in the hydraulic side lines (401, 402, 403, ...) are replace by flow controllers (50i, 50N, 50iii,...).

Figure 7 shows a schematic diagram of an embodiment of the dosage system which corresponds to the embodiment which is shown in Fig. 6 (i.e. the hydraulic side lines (401, 402, 403, ...) are equipped with flow meters (50i, 50N, 50iii,...)) whereby the vessels are designed as three different vessel arrangements which comprise three serial vessels (101a, 101b, 101c), two serial vessels (102a, 102b) and one single vessel (103a).

Figure 8 shows a schematic diagram of an embodiment of the dosage system which corresponds to the embodiment which is shown in Fig. 5 whereby the multi chamber storage vessels (301, 302, 303,...) are arranged in a common heating zone and hte reaction vessels are arranged in another heating zone.

Figure 9 shows a schematic diagram of an embodiment of the dosage system which is equipped with multi-chamber storage vessels (301 ) which are equipped with means for refilling of the storage vessel. The means are given by feed supply vessels (17) which are in functional connection with the multi-chamber storage vessels (301) whereby the functional connection comprise a pump and a flow meter or pressure indicator. The 3-way switch valve (63) provides the connection to the feed supply line. The refilling of the multi-chamber storage vessels (301) is carried out simultaneously with the release of hydraulic liquid from the multi-chamber storage vessels (301) which is conducted by the operating the 3-way valves (63) which are in functional connection with the hydraulic oil receiver (15). The refilling of the multi-chamber storage vessels (301) is controlled by a flowmeter or pressure indicator (51) to avoid an overload. Reference numerals

11 hydraulic line / hydraulic main line

12 high pressure pump, preferably HPLC

13 low pressure pump

14 high precision balance

15 hydraulic liquid supply

16 pressure line 17 feed supply

50 flow controller, preferably coriolis flow meter

50i, 50N, 50iii,... - flow controller, preferably coriolis flow meter

51 flow meter or pressure indicator 60 splitter 62 selection valve, multi-port valve

63 3-way valve

101 , 102, 103,... - vessels 101a, 101b, 101c,...- vessels in serial arrangement XXXa, XXXb,... - vessels in a serial arrangement 201 , 202, 203,... - transfer lines 301 , 302, 203,... - multi chamber storage device, preferably two chamber storage device 401 , 402, 403,... - hydraulic side lines 501 , 502, 503,... - throttle, restrictor, capillary 701 , 702, 703,... - pressure sensor 801 , 802, 803,... - gas supply line 901 , 902, 903,... - liquid condensor