CN212894540U - Preparation facilities of metal organic framework can be regulated and control to basicity - Google Patents

Abstract

The utility model provides a preparation device of an alkaline adjustable metal organic framework, which comprises a metal organic framework preparation unit, an alkaline ligand preparation unit and a ligand exchange kettle connected with the metal organic framework preparation unit and the alkaline ligand preparation unit; the metal organic framework preparation unit comprises a first storage tank, a second storage tank, a first reaction chamber, a first washing chamber and a first collection chamber which are connected with each other; the alkaline ligand preparation unit comprises a third storage tank, a fourth storage tank, a second reaction chamber, a second washing chamber and a second collection chamber which are connected with each other; the guide pipe at the discharge port of the first collection chamber is crossed with the guide pipe at the discharge port of the second collection chamber, and the crossed part is communicated with the feeding port at the top end of the ligand exchange kettle through the guide pipe. Wherein, a pH value reaction regulating and controlling device is arranged in the alkaline ligand preparation unit in the synthesis process, so that alkaline functional ligands with specified pH value ranges can be prepared, and metal organic frameworks with different alkaline functions can be prepared according to different alkaline functional ligands.

Description

Preparation facilities of metal organic framework can be regulated and control to basicity

Technical Field

The utility model belongs to metal organic framework material preparation facilities field, concretely relates to metal organic framework's preparation facilities can be regulated and control to basicity.

Background

Metal organic framework Materials (MOFs) generally refer to crystalline materials with periodic infinite network structures formed by self-assembly of metal ions or metal clusters and organic ligands, and are inorganic-organic hybrid systems, which have both the characteristics of organic polymers and inorganic compounds to show a plurality of unique characteristics, and thus are widely applied to the fields of energy production, green catalysis, and the like. Most importantly, the MOFs material has rich pore channels, ultrahigh specific surface area and a large number of modifiable sites, and can be used for designing and preparing the corresponding optimal material by aiming at the immobilization of metal ions by introducing corresponding functional groups into the MOFs, so that the MOFs material can be widely applied to the fields of magnetism, optics, adsorption, separation, catalysis, hydrogen storage catalysis and the like.

According to the prior art, basic functional groups are introduced into a metal organic framework in a certain way, and the functional metal organic framework is constructed, so that the service performance of the metal organic framework can be improved; meanwhile, the aperture, the morphology and the applicable field of the metal organic frameworks with different alkaline functions can be changed. However, in the prior art, a large-scale preparation device for the alkali function composite metal organic framework does not exist, and an alkali function modification process adopted at present does not have a preparation device with adjustable alkalinity, so that the preparation device for the alkali function composite metal organic framework is necessary.

Disclosure of Invention

To the above defect of prior art or improve the demand, the utility model provides a preparation facilities of metal organic framework can be regulated and control to basicity, this device can carry out the regulation and control of pH at synthetic in-process at basicity functional ligand to prepare out the basicity functional ligand of regulation pH value scope, and include a ligand exchange cauldron, it is provided with heating device and cooling device, and two kinds of devices can make the reaction go on in turn under normal atmospheric temperature and high temperature condition under the synergism. The device can be used for preparing the metal organic framework material with adjustable alkalinity.

In order to achieve the above object, according to the present invention, there is provided a device for preparing an alkali-controllable metal organic framework, comprising a metal organic framework preparing unit, an alkali ligand preparing unit, and a ligand exchange kettle connected to the metal organic framework preparing unit and the alkali ligand preparing unit;

the metal organic framework preparation unit comprises a first storage tank, a second storage tank, a first reaction chamber, a first washing chamber and a first collection chamber which are connected with each other; the discharge ports of the first storage tank and the second storage tank are respectively communicated with a feeding port at the top end of a first reaction chamber, the discharge port at the bottom end of the first reaction chamber is communicated with a first washing chamber, the discharge port of the first reaction chamber is communicated with a ligand exchange kettle, and the prepared metal organic framework solid phase liquid is input into the ligand exchange kettle;

the alkaline ligand preparation unit comprises a third storage tank, a fourth storage tank, a second reaction chamber, a second washing chamber and a second collection chamber which are connected with each other; the discharge ports of the third storage tank and the fourth storage tank are respectively communicated with a feeding port at the top end of a second reaction chamber, the discharge port at the bottom end of the second reaction chamber is communicated with a second washing chamber, the discharge port of the second reaction chamber is communicated with a ligand exchange kettle, and the prepared alkaline ligand solid-phase liquid is input into the ligand exchange kettle;

and the guide pipe at the discharge port of the first collection chamber is crossed with the guide pipe at the discharge port of the second collection chamber, and the crossed part is communicated with the feeding port at the top end of the ligand exchange kettle through the guide pipe.

Preferably, the fourth storage tank is provided with a dropping pump device at a feeding port communicated with the second reaction chamber, the inner cavity of the second reaction chamber is provided with a pH sensing device, and the dropping pump device and the pH sensing device are both electrically connected with an external dropping control unit.

Preferably, the ligand exchange kettle comprises a heating device and a cooling device, the heating device is embedded in the inner wall of the bottom of the ligand exchange kettle, and the cooling device is arranged on the outer wall of the ligand exchange kettle.

Preferably, the ligand exchange kettle further comprises a thermometer time control device, and the heating device and the cooling device are both connected with the thermometer time control device and are used for carrying out normal-temperature and high-temperature alternate reaction control.

Preferably, the cooling device is provided with two interfaces which are communicated with the outside of the ligand exchange kettle and are used for inputting/outputting cooling fluid.

Preferably, the temperature control device comprises a temperature sensing device and a timing control device, the temperature sensing device is arranged on the inner wall of the ligand exchange kettle, and the timing control device is arranged on the outer wall of the ligand exchange kettle.

Preferably, the timing control device includes a time display interface.

Preferably, the ligand exchange kettle further comprises a pressure control device, wherein the pressure control device penetrates through the outer wall of the ligand exchange kettle, one end of the pressure control device is arranged in the cavity of the ligand exchange kettle, and the other end of the pressure control device is arranged at the top end of the ligand exchange kettle.

Preferably, the discharge port of the ligand exchange kettle is connected with a washing and drying chamber, and the compounded product is washed and dried and then output.

Preferably, the first washing chamber, the second washing chamber and the washing and drying chamber are provided with liquid outlets which are connected with a waste liquid treatment pool.

Generally, through the utility model discloses above technical scheme who conceives compares with prior art, can gain following beneficial effect:

(1) the utility model provides a metal organic framework's preparation facilities can be regulated and control to basicity is provided with pH value reaction regulation and control device at synthetic in-process of basicity ligand synthesis unit, can prepare out the basicity functional ligand of regulation pH value scope, thereby prepares out the metal organic framework of different basicity functions according to basicity functional ligand difference.

(1) The utility model provides a metal organic framework's preparation facilities can be regulated and control to basicity, including a ligand exchange cauldron, it is provided with heating device and cooling device, and two kinds of devices can make the reaction go on in turn under normal atmospheric temperature and high temperature condition under the synergism.

(2) The utility model provides a preparation facilities of metal organic framework can be regulated and control to basicity can be suitable for the scale production of compound organic metal framework material of alkali function. The systematic device replaces manual experiment operation, so that the workload is reduced, and the process is more automatic.

Drawings

Fig. 1 is a schematic view of the overall structure of a device for manufacturing an alkali-controllable metal organic framework according to the present invention;

fig. 2 is a detailed schematic view of a fourth material storage tank and a second reaction chamber of a device for preparing an alkali-controllable metal organic framework according to the present invention;

FIG. 3 is a schematic diagram showing details of a ligand exchange kettle of an apparatus for preparing an alkali-controllable metal organic framework according to the present invention;

the same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:

the device comprises a first storage tank-1, a second storage tank-2, a first reaction chamber-3, a first collection chamber-4, a third storage tank-5, a fourth storage tank-6, a second reaction chamber-7, a second collection chamber-8, a ligand exchange kettle-9, a washing and drying chamber-10, a waste liquid treatment tank-11, a first washing chamber-12, a second washing chamber-13, a dropping pump device-601, a pH sensing device-602, a dropping control unit-603, a pressure control device-901, a heating device-902, a cooling device-903, a thermometer time control device-904, a temperature sensing device-905 and a timing control device-906.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Furthermore, the technical features mentioned in the embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

It should be noted that the term "first/second" in the present invention is used only for distinguishing similar objects, and does not represent a specific ordering for the objects, and it should be understood that "first/second" may be interchanged with a specific order or sequence if allowed. It should be understood that "first \ second" distinct objects may be interchanged under appropriate circumstances such that embodiments of the invention described herein may be practiced in sequences other than those described or illustrated herein.

As shown in fig. 1, according to the utility model relates to a specific embodiment, a metal organic framework's preparation facilities can be regulated and control to basicity, a be used for preparing alkali function composite metal organic framework, its synthesis flow includes at first preparing metal organic framework material and alkaline functional ligand, then carry out ligand exchange with this metal organic framework material and alkaline functional ligand's solution complex, wherein, alkaline functional ligand carries out the alkaline functional ligand of the regulation and control preparation certain pH value scope of pH value at synthetic in-process, need normal atmospheric temperature and high temperature reaction condition to carry out the alternation when carrying out ligand exchange simultaneously.

In this embodiment, a device for preparing an alkali-controllable metal organic framework includes a metal organic framework preparation unit, an alkali ligand preparation unit, and a ligand exchange kettle 9 connected to the metal organic framework preparation unit and the alkali ligand preparation unit;

further, the metal organic framework preparation unit comprises a first storage tank 1, a second storage tank 2, a first reaction chamber 3, a first washing chamber 12 and a first collection chamber 4 which are connected with each other; the discharge ports of the first storage tank 1 and the second storage tank 2 are respectively communicated with the feed port at the top end of the first reaction chamber 3, the discharge port at the bottom end of the first reaction chamber 3 is communicated with the first washing chamber 12, the discharge port of the first reaction chamber 3 is communicated with the ligand exchange kettle 9, and the prepared metal organic framework solid phase liquid is input into the ligand exchange kettle 9.

Furthermore, the first storage tank 1 and the second storage tank 2 are respectively communicated with the feeding port at the top end of the first reaction chamber 3 through the discharging port, so that the metal ion solution and the ligand are mixed in the first reaction chamber 3. The solvent for the reaction may be introduced through the inlet port of the sidewall of the first reaction chamber 3 or may be mixed with the ligand and the metal source, respectively, and flowed into the first reaction chamber 3. The ligand and the metal source react autonomously in the first reaction chamber 3 to produce a metal-organic framework material.

Further, the first storage tank 1 and the second storage tank 2 are used for storing and preparing the ligand and the metal ion solution, respectively. The ligand of the reaction includes one of terephthalic acid, trimesic acid, 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, 2-bromoterephthalic acid, 2, 5-dihydroxyterephthalic acid, 2,2 '-bipyridine-5, 5' -dicarboxylic acid, 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, azobenzene-4, 4-dicarboxylic acid, 2, 5-diaminoterephthalic acid, 4- (4-pyridyl) benzoic acid, and the like, but is not limited thereto. The metal ion solution of the reaction includes one of metals including nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, ferric nitrate, ferric chloride, ferric sulfate, ferric acetate, aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum acetate, manganese nitrate, manganese chloride, manganese sulfate, manganese acetate, titanium nitrate, titanium chloride, titanium sulfate, silver nitrate, and the like, but is not limited thereto. The solvents involved in the reaction include: methanol, ethanol, N-dimethylformamide solution, dichloromethane, dimethylsulfoxide, and the like, without being limited thereto.

Further, the alkaline ligand preparation unit comprises a third storage tank 5, a fourth storage tank 6, a second reaction chamber 7, a second washing chamber 13 and a first collection chamber 8 which are connected with each other; the discharge ports of the third storage tank 5 and the fourth storage tank 6 are respectively communicated with the feed port at the top end of the second reaction chamber 7, the discharge port at the bottom end of the second reaction chamber 7 is communicated with the second washing chamber 13, the discharge port of the second reaction chamber 7 is communicated with the ligand exchange kettle 9, and the prepared alkaline ligand solid phase liquid is input into the ligand exchange kettle 9.

Further, the third material storage tank 5 and the fourth material storage tank 6 are respectively communicated with the feeding port at the top end of the second reaction chamber 7 through the discharging port, so that the alkaline functional solution and the organic solvent are mixed in the second reaction chamber 7. The basic functional solution reacts with the organic solvent in the second reaction chamber 7 to generate a basic functional group ligand.

Further, the basic functional group ligand in the basic functional solution is preferably: n-methylcarbamoyl chloride, dimethylaminocarbonyl chloride, iminostilbenoyl chloride, dimethylaminothioformyl chloride, 1-phenyl-5-trifluoromethylpyrazole-4-carbonyl chloride, N-chloromethyl-N-phenylcarbamoylchloride, 2, 4-dichloro-5-pyrimidineoyl chloride, 5-bromo-2, 3-diaminofluorobenzene, 2-amino-3-chloropropane, 2-chloro-1-dimethylaminobutane, 2-chloro-1-dimethylaminopropane, 3-chloro-1-diethylaminopropane, dimethylaminochloroethane, dialkylaminoethyl-2-chloro, 3-fluoro-1-diethylaminopropane, 3-chloro-1-diethylaminobutane, tetrakis (difluoromethylaminomethylnitramino) ethane. Wherein the solvent for dissolving the basic functional group ligand comprises: methanol, ethanol, N-dimethylformamide solution, dichloromethane, dimethylsulfoxide, and the like, without being limited thereto.

Further, a guide pipe at the discharge port of the first collection chamber 4 is intersected with a guide pipe at the discharge port of the second collection chamber 8, and the intersection is communicated with a feeding port at the top end of the ligand exchange kettle 9 through a guide pipe.

Furthermore, the metal organic framework material prepared in the first reaction chamber 3 enters the first collection chamber 4, the basic functional ligand prepared in the second reaction chamber 7 enters the second collection chamber 8, and the two raw materials are input into the ligand exchange kettle 9 according to a certain proportion and can be mixed in advance in an input conduit.

In this embodiment, as shown in fig. 2, a dropping pump device 601 is disposed at the feeding port of the fourth material storage tank 6 and the communicating feeding port, a pH sensing device 602 is disposed in the inner cavity of the second reaction chamber 7, and both the dropping pump device 601 and the pH sensing device 602 are electrically connected to a dropping control unit 603 disposed outside the second reaction chamber 7.

Further, the reaction pH of the basic functional ligand in the second reaction chamber 7 is 8 to 12, and the prepared basic functional ligand and the metal organic framework material form a metal organic framework material with a basic function after ligand exchange, so that the pH of the prepared basic functional ligand determines the content of the basic functional group grafted on the basic functional ligand, and thus determines the basic function of the finally generated metal organic framework material with a basic function, which affects the pore size, morphology and the like of the metal organic framework with a basic function, so that the metal organic framework material with a basic function has different functional attributes. In order to better regulate and control the alkali function of the final product and thus control the product performance, in this embodiment, a pH sensing device 602 is provided to measure the pH of the raw material during the synthesis of the basic functional ligand, and at the same time, the basic functional solution is dripped into the second reaction chamber 7 through a dripping pump device 601, and the dripping pump device 601 and the pH sensing device 602 are electrically connected to a dripping control unit 603, and the dripping amount of the basic functional solution is controlled through the dripping control unit 603, so as to control the pH of the basic functional ligand.

Further, a certain pH reaction range is set in the dropping control unit 603, the basic functional solution is dropped into the second reaction chamber 7 through the dropping pump device 601 to react with the organic solution, the pH sensor device 602 monitors the pH of the reaction in the second reaction chamber 7 and feeds back the pH to the dropping control unit 603, and the dropping control unit 603 issues a titration instruction to the dropping pump device 902 according to the received pH to control the dropping speed of the dropping pump device 902 or stop dropping.

Further, the dropwise addition of the basic-functional solution into the second reaction chamber 7 by the dropwise addition pump means 601 also allows the reaction to proceed more sufficiently, thereby allowing the reaction to proceed more completely.

In the present embodiment, as shown in fig. 3, the ligand exchange kettle 9 includes a heating device 902 and a cooling device 903, the heating device 902 is embedded in the inner wall of the bottom of the ligand exchange kettle 9, and the cooling device 903 is provided on the outer wall of the ligand exchange kettle 9.

Further, the metal organic framework material and the alkaline functional ligand solution need to react under the condition of alternating between normal temperature and high temperature. In order to better control the back-and-forth conversion of the reaction temperature, a corresponding heating device 902 and a corresponding cooling device 903 are needed to regulate the normal temperature and the high temperature, and the two devices cooperate with each other in the operation process to ensure that the temperature in the ligand exchange kettle 9 is kept constant within a certain period of time. The normal temperature control temperature range is preferably 15-25 ℃, and the high temperature control temperature range is preferably 80-100 ℃.

Further, the cooling device 903 is provided with two ports for communicating with the outside of the ligand exchange tank 9 for inputting/outputting cooling fluid. The cooling fluid enters from the interface at the upper part of the cooling device 903 and exits from the interface at the lower part of the cooling device 903. The cooling fluid is preferably water.

Further, the ligand exchange kettle 9 further comprises a temperature controller 904, and the heating device 902 and the cooling device 903 are both connected with the temperature controller 904 for performing the normal temperature and high temperature alternating reaction control.

Further, the ligand exchange tank 9 is further provided with a temperature control device 904 which is connected to the heating device 902 and the cooling device 903 respectively, and the temperature control device 904 can be used for timing two different temperatures alternately, and when the timing reaction time of a certain temperature is reached, the heating device 902 and the cooling device 903 are controlled to be switched to the other temperature.

Further, the thermometer control device 904 includes a temperature sensing device 905 and a timing control device 906, the temperature sensing device 905 is disposed on the inner wall of the ligand exchange pot 9, and the timing control device 906 is disposed on the outer wall of the ligand exchange pot 9. The temperature sensing device 905 senses the temperature of the composite reaction and then feeds the temperature back to the timing control device 906, and the timing control device 906 controls the operation of the heating device 902 and the cooling device 903 according to the real-time temperature.

Further, the timing control device 906 includes a time display interface, which can perform timing display of temperature and time, and the display interface can be configured as a touch screen, through which a worker can perform setting of temperature and time.

Furthermore, a discharge port can be arranged below the ligand exchange kettle 9 for washing the ligand exchange kettle 9 or dredging in case of reaction accident.

Further, the ligand exchange kettle 9 further comprises a pressure control device 901, the pressure control device 901 penetrates through the outer wall of the ligand exchange kettle 9, one end of the pressure control device 901 is arranged in the cavity of the ligand exchange kettle 9, and the other end of the pressure control device 901 is arranged at the top end of the ligand exchange kettle 9. The device is used for controlling the protective air pressure, and avoids the reaction accident caused by too large air pressure or the failure of too small air pressure to play a protective role.

In the embodiment, a discharge port of the ligand exchange kettle 9 is connected with a washing and drying chamber 10, and the compounded product is washed, dried and output. The washing and drying chamber 10 is used for washing and drying the final product, and comprises a drying chamber and a filtrate chamber, and a filter membrane transmission device is arranged in the middle of the drying chamber and can transmit the washed and filtered product out from a discharge port.

In this embodiment, the first washing chamber 12, the second washing chamber 13, and the washing and drying chamber 10 are all provided with a liquid outlet connected to the waste liquid treatment tank 11. And (5) treating waste liquid.

In this embodiment, all the reaction apparatuses are made of a high temperature resistant and corrosion resistant material, and stirring apparatuses are provided in the reaction kettle 3 and the waste liquid treatment tank 8, and used for mixing reaction raw materials during product reaction or waste liquid treatment.

It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The preparation device of the metal organic framework with adjustable alkalinity is characterized by comprising a metal organic framework preparation unit, an alkaline ligand preparation unit and a ligand exchange kettle (9) connected with the metal organic framework preparation unit and the alkaline ligand preparation unit;

the metal organic framework preparation unit comprises a first storage tank (1), a second storage tank (2), a first reaction chamber (3), a first washing chamber (12) and a first collection chamber (4) which are connected with each other; the discharge ports of the first storage tank (1) and the second storage tank (2) are respectively communicated with a feeding port at the top end of the first reaction chamber (3), the discharge port at the bottom end of the first reaction chamber (3) is communicated with the first washing chamber (12), the discharge port of the first reaction chamber (3) is communicated with the ligand exchange kettle (9), and the prepared metal organic framework solid phase liquid is input into the ligand exchange kettle (9);

the alkaline ligand preparation unit comprises a third storage tank (5), a fourth storage tank (6), a second reaction chamber (7), a second washing chamber (13) and a second collection chamber (8) which are connected with each other; the discharge ports of the third storage tank (5) and the fourth storage tank (6) are respectively communicated with a feeding port at the top end of the second reaction chamber (7), the discharge port at the bottom end of the second reaction chamber (7) is communicated with the second washing chamber (13), the discharge port of the second reaction chamber (7) is communicated with the ligand exchange kettle (9), and the prepared alkaline ligand solid-phase liquid is input into the ligand exchange kettle (9);

and a guide pipe at the discharge port of the first collection chamber (4) is crossed with a guide pipe at the discharge port of the second collection chamber (8), and the crossed part is communicated with a feeding port at the top end of the ligand exchange kettle (9) through a guide pipe.

2. The apparatus for preparing the alkali-controllable metal-organic framework according to claim 1, wherein a feeding port of the fourth storage tank (6) communicated with the second reaction chamber (7) is provided with a dropping pump device (601), an inner cavity of the second reaction chamber (7) is provided with a pH sensing device (602), and both the dropping pump device (601) and the pH sensing device (602) are electrically connected with an external dropping control unit (603).

3. The apparatus for preparing an alkali-controllable metal-organic framework according to claim 1, wherein the ligand exchange kettle (9) comprises a heating device (902) and a cooling device (903), the heating device (902) is embedded in the inner wall of the bottom of the ligand exchange kettle (9), and the cooling device (903) is disposed on the outer wall of the ligand exchange kettle (9).

4. The apparatus for preparing an alkali-controllable metal-organic framework as claimed in claim 3, wherein the ligand exchange kettle (9) further comprises a temperature controller (904), and the heating device (902) and the cooling device (903) are both connected to the temperature controller (904) for performing the reaction control of alternating between normal temperature and high temperature.

5. The apparatus for preparing an alkali controllable metal organic framework according to claim 4, wherein the cooling device (903) is provided with two ports for communicating with the outside of the ligand exchange kettle (9) for inputting/outputting cooling fluid.

6. The apparatus for preparing an alkali controllable metal organic framework as claimed in claim 4, wherein the temperature controller (904) comprises a temperature sensor (905) and a timing controller (906), the temperature sensor (905) is disposed on an inner wall of the ligand exchange kettle (9), and the timing controller (906) is disposed on an outer wall of the ligand exchange kettle (9).

7. The apparatus of claim 6, wherein the timing control device (906) comprises a time display interface.

8. The apparatus for preparing the alkali-controllable metal-organic framework according to claim 1, wherein the ligand exchange kettle (9) further comprises a pressure control device (901), the pressure control device (901) penetrates through the outer wall of the ligand exchange kettle (9), one end of the pressure control device is disposed in the cavity of the ligand exchange kettle (9), and the other end of the pressure control device is disposed at the top end of the ligand exchange kettle (9).

9. The apparatus for preparing the alkali-controllable metal-organic framework according to claim 1, wherein a discharge port of the ligand exchange kettle (9) is connected to a washing and drying chamber (10), and the washing and drying chamber (10) is used for washing and drying the compounded product and then outputting the washed and dried product.

10. The apparatus for preparing an alkali-controllable metal-organic framework according to claim 9, wherein the first washing chamber (12), the second washing chamber (13) and the washing and drying chamber (10) are provided with liquid outlets connected to a waste liquid treatment tank (11).

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