A method for regenerating a dehydrogenation catalyst for a hydrogen storage organic liquid

Abstract

The application discloses a regeneration method for a hydrogen storage organic liquid dehydrogenation catalyst, and relates to the technical field of hydrogen storage catalysts.The method comprises the following steps: step S1: introducing the catalyst carrying the hydrogen storage organic liquid into a gas-liquid-solid three-phase separator; step S2: introducing the catalyst particles intercepted by a screen in the gas-liquid-solid three-phase separator into a catalyst regenerator; step S3 catalyst regeneration: performing high-temperature purging by using nitrogen, and introducing a regeneration gas to perform catalyst regeneration operation; step S4 catalyst reduction: introducing a reduction gas to reduce the catalyst; and step S5: transferring the regenerated catalyst into a hydrogen storage organic liquid dehydrogenation reactor in the form of nitrogen purging. The catalyst regeneration method has continuity, does not affect the production of hydrogen, and guarantees the continuous and stable supply of hydrogen. The catalyst regeneration method can realize the separation of the hydrogen storage organic liquid from the catalyst, and reduces the consumption cost of the hydrogen storage organic liquid.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen storage catalysts, and particularly relates to a regeneration method for a hydrogen storage organic liquid dehydrogenation catalyst. BACKGROUND

[0002] Hydrogen, as a clean fuel, is an extremely important energy carrier connecting renewable energy conversion and application, and is one of the most convenient and effective ways for renewable energy to go from the source to daily application. In order to alleviate global environmental and climate pressure, the emission control of carbon dioxide is becoming increasingly strict. Under the current "double carbon" background, the development and application of hydrogen energy is one of the key ways to solve the fossil energy crisis and the resulting climate, environmental and political problems.

[0003] The organic liquid hydrogen storage technology is to store hydrogen by means of hydrogenation reaction of certain unsaturated liquid organic matters such as olefins, alkynes or aromatic hydrocarbons, and to release hydrogen by dehydrogenation reaction. The dehydrogenation reaction of hydrogen storage organic liquid is a typical endothermic reaction, which needs to provide enough heat for the hydrogen storage organic liquid in the presence of a catalyst to drive the reaction to occur. In order to obtain sufficient conversion rate of hydrogen storage organic liquid and hydrogen release rate, a high reaction temperature is often required. High-temperature dehydrogenation will inevitably lead to excessive dehydrogenation and cracking reaction of the organic liquid, which not only leads to the decrease of hydrogen purity and the increase of total hydrocarbon content, but also accelerates the production of catalyst surface coking and carbon deposition, thereby leading to catalyst deactivation.

[0004] The active component of the hydrogen storage organic liquid dehydrogenation catalyst is generally a noble metal such as Pt, and the raw material cost is relatively high. In order to reduce the comprehensive cost, the deactivated catalyst needs to be regenerated. Considering that the main reason for catalyst deactivation is surface coking and carbon deposition, high-temperature coking can be used for catalyst regeneration. The off-line regeneration of the catalyst needs to replace the entire batch of deactivated catalyst with fresh catalyst, which greatly increases the production cost and safety risk. In addition, the dehydrogenation reaction of hydrogen storage organic liquid requires continuous and stable supply of hydrogen, and thus requires that the dehydrogenation reaction can be continuously and stably carried out, so that the catalyst regeneration method needs to have the characteristics of continuity and on-line to meet the needs of stable production.

[0005] The dehydrogenation reaction of hydrogen storage organic liquid involves gas, liquid and solid three-phase (gas and solid two-phase) contact and mass transfer under conventional reaction conditions. The hydrogen storage organic liquid is still liquid at the dehydrogenation reaction temperature range, and the catalyst is usually immersed in the hydrogen storage organic liquid in solid form. The catalyst regeneration is generally high-temperature carbon burning, and excessive residual hydrogen storage organic liquid will inevitably cause hydrogen storage organic liquid loss. In order to reduce the cost of hydrogen storage organic liquid loss, the catalyst needs to be separated from the hydrogen storage organic liquid before regeneration. SUMMARY

[0006] The present application aims to provide a regeneration method for hydrogen storage organic liquid dehydrogenation catalyst to solve the problems in the background art.

[0007] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0008] A regeneration method for hydrogen storage organic liquid dehydrogenation catalyst, comprising the following steps:

[0009] Step S1: The catalyst discharged from the hydrogen storage organic liquid dehydrogenation reactor and carrying the hydrogen storage organic liquid is introduced into the gas-liquid-solid three-phase separator, and the catalyst particles are intercepted by the screen in the gas-liquid-solid three-phase separator;

[0010] Step S2: The catalyst particles intercepted by the screen in the gas-liquid-solid three-phase separator are introduced into the catalyst regenerator and subjected to catalyst regeneration operation;

[0011] Step S3 catalyst regeneration: high-temperature purging is performed by using nitrogen, and after the purging is completed, the regeneration gas is introduced from the gas inlet at the top of the catalyst regenerator to perform catalyst regeneration operation;

[0012] Step S4 catalyst reduction: the reduction gas is introduced from the gas inlet at the top of the catalyst regenerator to reduce the catalyst;

[0013] Step S5: The regenerated catalyst is transferred to the hydrogen storage organic liquid dehydrogenation reactor in the form of nitrogen purging.

[0014] On the basis of the above technical solutions, the present application further provides the following optional technical solutions:

[0015] In an optional solution: the hydrogen storage organic liquid dehydrogenation reactor discharges the catalyst continuously or intermittently, and the discharge amount of the catalyst is controlled by the catalyst discharge valve arranged at the bottom of the hydrogen storage organic liquid dehydrogenation reactor, wherein the flow of the catalyst carrying the hydrogen storage organic liquid is less than half of the flow of the hydrogen storage organic liquid inlet at the lower part of the hydrogen storage organic liquid dehydrogenation reactor.

[0016] In an optional solution: the gas-liquid-solid three-phase separator has a gas outlet pipeline at the top, the hydrogen gas flowing into the gas-liquid-solid three-phase separator is subjected to gas-liquid separation in the gas-liquid-solid three-phase separator and flows out from the gas outlet pipeline, and the gas outlet pipeline is combined with the reactor gas outlet pipeline at the top of the hydrogen storage organic liquid dehydrogenation reactor.

[0017] In an optional solution: the catalyst particles intercepted by the screen in the gas-liquid-solid three-phase separator flow into the catalyst regenerator through the catalyst outlet pipe, and the control valve at the catalyst outlet pipe is in a closed state during the catalyst regeneration operation of the catalyst regenerator.

[0018] In an alternative, in step S3, the catalyst is regenerated, and nitrogen is introduced from the gas inlet at the top of the catalyst regenerator, the gas space velocity of the nitrogen blowing is 1000h -1 -1000000h -1 , the nitrogen blowing temperature is 80-500℃, and the nitrogen blowing time is 0.5-100h.

[0019] In an alternative, the regeneration gas is a mixed gas with an oxygen volume concentration of 1-100%, the gas space velocity of the regeneration gas is 1000h -1 -1000000h -1 , the catalyst regeneration temperature is 200-800℃, and the catalyst regeneration time is 0.5-100h.

[0020] In an alternative, in step S4, the catalyst is reduced, the reducing gas is a mixed gas with a hydrogen volume concentration of 1-100%, the gas space velocity of the reducing gas is 1000h -1 -1000000h -1 , the catalyst reduction temperature is 150-800℃, and the catalyst reduction time is 0.5-100h.

[0021] In an alternative, in step S5, after the reduction is completed, pure hydrogen is introduced from the gas inlet at the top of the catalyst regenerator for blowing, and after the hydrogen blowing is completed, the catalyst in the catalyst regenerator flows into the catalyst storage tank through the catalyst outlet.

[0022] Compared with the prior art, the present application has the following advantages:

[0023] 1. The method of the present application solves the regeneration of the dehydrogenated catalyst of the hydrogen storage organic liquid to restore the activity of the catalyst and prolong the service life of the catalyst.

[0024] 2. The catalyst regeneration method has the characteristics of continuity and on-line, does not affect the production of hydrogen, and ensures the continuous and stable supply of hydrogen; the catalyst regeneration method can realize the maximum separation of the hydrogen storage organic liquid and the catalyst, and reduce the consumption cost of the hydrogen storage organic liquid.

[0025] 3. The implementation of the present application can realize the regeneration of the catalyst under the premise of ensuring the continuous and stable supply of hydrogen, and does not affect the key indicators such as the hydrogen supply rate, purity, and dehydrogenation degree of the hydrogen storage organic liquid, and the influence on the downstream hydrogen end is minimized. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The figure is a schematic diagram of the on-line continuous regeneration method of the hydrogen storage organic liquid dehydrogenation catalyst of the present application.

[0027] Figure 2Schematic diagram of the catalyst supplement inlet for the catalyst without reduction of the present application.

[0028] Figure 3 Schematic diagram of the catalyst supplement inlet for the catalyst requiring reduction of the present application.

[0029] Figure 4 Schematic diagram of the structure of the movable catalyst storage tank of the present application.

[0030] Figure 5 Schematic diagram of the structure of the movable sub-catalyst storage tank of the present application.

[0031] Figure 6 Schematic diagram of the structure of the catalyst transfer from the gas purge to the reactor of the present application

[0032] Figure legend: hydrogen storage organic liquid dehydrogenation reactor 1, gas-liquid-solid three-phase separator 3, catalyst discharge valve 4, hydrogen storage organic liquid inlet 5, hydrogen storage organic liquid outlet 6, gas outlet pipeline 7, reactor gas outlet pipeline 8, screen 9, sub-hydrogen storage organic liquid outlet 10, filter 11, catalyst outflow pipe 12, catalyst regenerator 13, control valve 14, gas inlet 15, purge gas outlet 16, catalyst outlet 17, regeneration waste gas outlet 18, valve I 19, valve II 20, valve III 21, gas-liquid separator 22, organic liquid outlet 23, sub-filter 24, waste gas outlet 25, catalyst storage tank 26, sub-catalyst storage tank 26b, catalyst supplement inlet 27, valve I 28, sub-valve I 28b, valve II 29, sub-valve II 29b, valve III 30, first quick connector 31-1, sub-first quick connector 31-1b, second quick connector 31-2, third quick connector 32-1, fourth quick connector 32-2, sub-fourth quick connector 32-2b, catalyst storage tank lower nitrogen inlet 33, valve IV 34, valve V 35, valve VI 36, catalyst buffer tank 37, valve VII 38, valve VIII 39, valve IX 40, buffer tank hydrogen inlet 41, buffer tank waste gas outlet 42, buffer tank catalyst outlet 43. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the present application more clear and explicit, the present application is further described in detail below in combination with the drawings and examples; in the drawings or description, similar or identical parts use the same reference signs, and in practical application, the shape, thickness or height of each component can be enlarged or reduced. The listed examples of the present application are only used to illustrate the present application, and are not used to limit the scope of the present application. Any obvious modification or change made to the present application does not deviate from the spirit and scope of the present application.

[0034] The present application provides an online and continuous regeneration method of hydrogen storage organic liquid dehydrogenation catalyst, which is realized by the following technical solutions:

[0035] The dehydrogenation catalyst can be a platinum-based catalyst, a chromium-based catalyst, a nickel-based catalyst, a zinc-based catalyst, a rhodium-based catalyst, a ruthenium-based catalyst, a palladium-based catalyst, a gallium-based catalyst, a tin-based catalyst, or an iridium-based catalyst.

[0036] The catalyst has a spherical particle shape, and the particle size can be between 0.1 mm and 20 mm.

[0037] The hydrogen storage organic liquid can be a biphenyl-based organic liquid, a carbazole-based organic liquid, a benzyl benzene-based organic liquid, a benzyl toluene-based organic liquid, a naphthalene or anthracene-based organic liquid, a toluene-based organic liquid, or a composite-based organic liquid.

[0038] The method of the present application is shown in Figure 1 .

[0039] The catalyst flows into the gas-liquid-solid three-phase separator 3 from the hydrogen storage organic liquid dehydrogenation reactor 1 through the catalyst discharge pipeline 2 at the lower part of the reactor by gravity.

[0040] The catalyst discharge from the hydrogen storage organic liquid dehydrogenation reactor 1 can be continuous, and part of the hydrogen storage organic liquid will flow into the gas-liquid-solid three-phase separator 3 at the same time. The amount of catalyst discharged can be controlled by the catalyst discharge valve 4 at the lower part of the hydrogen storage organic liquid dehydrogenation reactor 1, and the flow rate of the catalyst carrying the hydrogen storage organic liquid is less than half of the flow rate of the hydrogen storage organic liquid inlet 5 at the lower part of the hydrogen storage organic liquid dehydrogenation reactor 1; preferably, the flow rate of the catalyst carrying the hydrogen storage organic liquid is less than one-fifth of the flow rate of the hydrogen storage organic liquid inlet 5; further preferably, the flow rate of the catalyst carrying the hydrogen storage organic liquid is less than one-tenth of the flow rate of the hydrogen storage organic liquid inlet 5; more preferably, the flow rate of the catalyst carrying the hydrogen storage organic liquid is less than one-fiftieth of the flow rate of the hydrogen storage organic liquid inlet 5.

[0041] The catalyst can also be discharged intermittently from the hydrogen storage organic liquid dehydrogenation reactor 1, and the catalyst discharge is controlled by the catalyst discharge valve 4. According to the deactivation rate of the catalyst, the time interval of the catalyst discharge can be any time interval between 1 minute and 30 days, and the time of each catalyst discharge can be any time between 1 minute and 30 days. The flow of the hydrogen storage organic liquid carried by the catalyst during the catalyst discharge is less than half of the flow of the hydrogen storage organic liquid at the inlet 5 when the catalyst is not discharged; preferably, the flow of the hydrogen storage organic liquid carried by the catalyst during the catalyst discharge is less than one-fifth of the flow of the hydrogen storage organic liquid at the inlet 5 when the catalyst is not discharged; further preferably, the flow of the hydrogen storage organic liquid carried by the catalyst during the catalyst discharge is less than one-tenth of the flow of the hydrogen storage organic liquid at the inlet 5 when the catalyst is not discharged; and more preferably, the flow of the hydrogen storage organic liquid carried by the catalyst during the catalyst discharge is less than one-fiftieth of the flow of the hydrogen storage organic liquid at the inlet 5 when the catalyst is not discharged.

[0042] When the catalyst is discharged, the flow of the hydrogen storage organic liquid at the inlet 5 is increased, and the flow of the hydrogen storage organic liquid at the outlet 6 of the upper part of the hydrogen storage organic liquid dehydrogenation reactor 1 is equal to the flow of the hydrogen storage organic liquid at the inlet 5 when the catalyst is not discharged.

[0043] The upper part of the gas-liquid-solid three-phase separator 3 is provided with a gas outlet pipeline 7. The hydrogen gas flowing into the gas-liquid-solid three-phase separator 3 is separated into gas and liquid in the gas-liquid-solid three-phase separator 3, and flows out from the gas outlet pipeline 7, and is combined with the reactor gas outlet pipeline 8 at the upper part of the reactor.

[0044] The gas-liquid-solid three-phase separator 3 is internally provided with a screen 9 for solid-liquid separation. The catalyst particles are intercepted on the screen 9, and the hydrogen storage organic liquid carried by the catalyst flows into the lower part of the gas-liquid-solid three-phase separator 3 under the action of gravity, and flows out through the auxiliary hydrogen storage organic liquid outlet 10 at the lower part of the gas-liquid-solid three-phase separator 3.

[0045] The auxiliary hydrogen storage organic liquid outlet 10 is provided with a filter 11 at the rear end. The filter 11 can filter the fine catalyst particles suspended in the hydrogen storage organic liquid, and the filter element of the filter 11 is designed to be replaceable.

[0046] The hydrogen storage organic liquid flowing through the filter 11 is combined with the hydrogen storage organic liquid flowing out from the outlet 6.

[0047] The catalyst intercepted by the screen 9 in the gas-liquid-solid three-phase separator 3 flows into the catalyst regenerator 13 through the catalyst outlet pipe 12.

[0048] The catalyst regenerator 13 is designed for intermittent regeneration. The cumulative amount of catalyst in the catalyst regenerator 13 is between 0% and 100%, and the catalyst regeneration operation is performed; preferably, the cumulative amount of catalyst is between 30% and 100%, and the catalyst regeneration operation is performed; further preferably, the cumulative amount of catalyst is between 50% and 100%, and the regeneration operation is performed; further preferably, the cumulative amount of catalyst is between 80% and 100%, and the regeneration operation is performed.

[0049] During the catalyst regeneration operation, the control valve 14 located at the catalyst outflow pipe 12 is in a closed state.

[0050] The catalyst is regenerated by first purging with nitrogen at high temperature. Nitrogen is introduced from the air inlet 15 on the catalyst regenerator 13. The gas space velocity of nitrogen purge is 1000h -1 -1000000h -1 ;

[0051] Preferably, the gas space velocity of nitrogen purge is 5000h -1 -1000000h -1 ; Further preferably, the gas space velocity of the nitrogen purge is 10000h -1 -100000h -1 ; Further preferably, the gas space velocity of the nitrogen purge is 50000h -1 -100000h -1 The nitrogen purge temperature is 20℃-600℃;

[0052] Preferably, the nitrogen purge temperature is 80°C-500°C;

[0053] Further preferably, the nitrogen purge temperature is 150°C-450°C;

[0054] More preferably, the nitrogen purge temperature is 200° C.-400° C. The nitrogen purge time is 0.5 h-100 h; preferably, the nitrogen purge time is 1 h-80 h;

[0055] More preferably, the nitrogen purge time is 2 hours to 60 hours; even more preferably, the nitrogen purge time is 5 hours to 50 hours.

[0056] The purged nitrogen enters the gas-liquid separator 22 through the purge gas outlet 16 at the bottom of the regenerator 13 and carries the hydrogen storage organic liquid adsorbed in the catalyst. At this time, valve I 19 is opened, valve II 20 is closed, and valve III 21 is closed.

[0057] The nitrogen and the hydrogen storage organic liquid are separated in the gas-liquid separator 22 , and the hydrogen storage organic liquid flows out through the organic liquid outlet 23 at the lower part of the gas-liquid separator 22 .

[0058] The hydrogen storage organic liquid outlet 23 is provided with a secondary filter 24 at the rear end, which can filter the fine catalyst particles suspended in the hydrogen storage organic liquid. The filtering element of the secondary filter 24 is designed to be replaceable.

[0059] The hydrogen storage organic liquid flowing through the secondary filter 24 is combined with the hydrogen storage organic liquid flowing out of the hydrogen storage organic liquid outlet 6.

[0060] The nitrogen gas in the gas-liquid separator 22 is discharged through the waste gas outlet 25 at the upper part of the gas-liquid separator 22.

[0061] After the purging is completed, the regenerated gas is introduced through the upper gas inlet 15 of the catalyst regenerator 13 to perform the catalyst regeneration operation.

[0062] The regenerated gas can be a mixed gas with an oxygen gas volume concentration of 1% to 100%, or can be air. Preferably, the oxygen gas volume concentration is 5% to 100%; further preferably, the oxygen gas volume concentration is 20% to 100%; and more preferably, the oxygen gas volume concentration is 50% to 100%. The second component of the mixed gas can be nitrogen, helium, or argon, and is preferably nitrogen.

[0063] The gas space velocity of the regenerated gas is 1000h -1 -1000000h -1 ; preferably, the gas space velocity of the regenerated gas is 5000h -1 -1000000h -1 ; further preferably, the gas space velocity of the regenerated gas is 10000h -1 -100000h -1 ; and more preferably, the gas space velocity of the regenerated gas is 50000h -1 -100000h -1 .

[0064] The catalyst regeneration temperature is 200°C to 800°C; preferably, the catalyst regeneration temperature is 300°C to 700°C; further preferably, the catalyst regeneration temperature is 350°C to 650°C; and more preferably, the catalyst regeneration temperature is 400°C to 600°C. The catalyst regeneration time is 0.5h to 100h;

[0065] Preferably, the catalyst regeneration time is 1h to 80h; further preferably, the catalyst regeneration time is 2h to 60h; and more preferably, the catalyst regeneration time is 5h to 50h.

[0066] The regenerated waste gas is discharged through the lower regenerated waste gas outlet 18 of the catalyst regenerator and combined with the waste gas outlet 25.

[0067] During the catalyst regeneration, the valve I 19 is closed, the valve II 20 is closed, and the valve III 21 is opened.

[0068] After catalyst regeneration, the catalyst needs to be reduced, or not.

[0069] Catalyst reduction, the catalyst is reduced by introducing reducing gas from the upper inlet 15 of the catalyst regenerator.

[0070] The reducing gas can be a mixed gas with a hydrogen volume concentration of 1%-100%; preferably, the hydrogen volume concentration is 5%-100%; further preferably, the hydrogen volume concentration is 20%-100%; more preferably, the hydrogen volume concentration is 50%-100%. The second component of the mixed gas can be nitrogen, helium, argon, preferably nitrogen.

[0071] The gas space velocity of the reducing gas is 1000h -1 -1000000h -1 ; preferably, the gas space velocity of the reducing gas is 5000h -1 -1000000h -1 ; further preferably, the gas space velocity of the reducing gas is 10000h -1 -100000h -1 ; more preferably, the gas space velocity of the reducing gas is 50000h -1 -100000h -1 .

[0072] The catalyst reduction temperature is 150°C-800°C; preferably, the catalyst reduction temperature is 200°C-600°C; further preferably, the catalyst reduction temperature is 200°C-500°C; more preferably, the catalyst reduction temperature is 250°C-450°C.

[0073] The catalyst reduction time is 0.5h-100h; preferably, the catalyst reduction time is 1h-80h; further preferably, the catalyst reduction time is 2h-60h; more preferably, the catalyst reduction time is 5h-50h.

[0074] After reduction is completed, pure hydrogen is introduced from the upper inlet 15 of the catalyst regenerator for purging, and the reducing gas in the regenerator is replaced with pure hydrogen; if the catalyst is reduced with pure hydrogen, this step of purging can be omitted.

[0075] If the catalyst is not reduced, nitrogen is introduced from the upper inlet 15 of the catalyst regenerator for purging, and the reducing gas in the regenerator is replaced with nitrogen. Pure hydrogen is introduced from the upper inlet 15 of the catalyst regenerator for purging, and the nitrogen in the regenerator is replaced with pure hydrogen.

[0076] After the hydrogen purge is completed, the catalyst in the catalyst regenerator 13 flows into the catalyst storage tank 26 via the catalyst outlet 17, at this time the valve I 19 is closed, the valve II 20 is opened, and the valve III 21 is closed.

[0077] For catalysts that do not need to be reduced, such as Figure 2 As shown, a supplementary catalyst inlet 27 is arranged above the catalyst storage tank, and fresh catalyst can be used to supplement the system catalyst from this place.

[0078] For catalysts that need to be reduced, such as Figure 3 As shown, a supplementary catalyst inlet 28 is arranged above the catalyst regenerator, and after the catalyst regeneration and nitrogen purge are completed, fresh catalyst can be used to supplement the system catalyst from this place, and then the catalyst reduction treatment is performed.

[0079] The regenerated catalyst is stored in the catalyst storage tank 26, and needs to be moved to the organic liquid dehydrogenation reactor 1. The transfer of the catalyst can be achieved by mechanical means, and the catalyst storage tank 26 is transferred to the upper side of the hydrogen storage organic liquid dehydrogenation reactor 1. The regenerated catalyst will flow into the hydrogen storage organic liquid dehydrogenation reactor 1 by gravity.

[0080] The catalyst storage tank and the associated valve pipeline have two sets of the same design. During the production of hydrogen by hydrogen storage organic liquid dehydrogenation, one set of catalyst storage tank system is always located above the hydrogen storage organic liquid dehydrogenation reactor 1 to supplement the catalyst for the hydrogen storage organic liquid dehydrogenation reactor 1. At the same time, one set of catalyst storage tank system is always located below the catalyst regenerator 13 to receive the regenerated catalyst. The other set of catalyst storage tank system with the same design has equipment numbers ending with the letter b. The structure of the catalyst storage tank 26 is shown in Figure 4 、 Figure 5 .

[0081] When the catalyst storage tank 26 is transferred, the valve 20 is closed, the valve I 28 is closed, the valve II 29 is closed, and the first quick connector 31-1 and the second quick connector 31-2 are separated. At this time, the catalyst storage tank 26 and the associated valve pipeline can be taken out from below the regenerator 13.

[0082] The separated catalyst storage tank 26 and the associated valve pipeline can be moved to the upper side of the organic liquid dehydrogenation reactor 1 via a mechanical arm or via a mechanical track, the third quick connector 32-1 and the fourth quick connector 32-2 are connected, the valve II 29 is opened, and the valve III 30 is opened. The regenerated catalyst can flow from the catalyst storage tank 26 into the hydrogen storage organic liquid dehydrogenation reactor 1 by gravity.

[0083] When the sub-catalyst storage tank 26b above the hydrogen storage organic liquid dehydrogenation reactor 1 is transferred, the sub-valve I 28b is in the closed state, the sub-valve II 29b is closed, the valve III 30 is closed, the third quick connector 32-1 and the fourth quick connector 32-2b are separated, and the sub-catalyst storage tank 26b and the associated valve pipeline can be removed from above the organic liquid dehydrogenation reactor 1.

[0084] The separated sub-catalyst storage tank 26b and the associated valve pipeline can be moved to below the catalyst regenerator 13 by a mechanical arm or by a mechanical track, the sub-first quick connector 31-1b and the second quick connector 31-2 are connected, the valve 20 is opened, and the valve I 28 is opened. After regeneration, the catalyst can flow into the sub-catalyst storage tank 26b through the catalyst outlet 17.

[0085] After the regeneration of the catalyst stored in the catalyst storage tank 26, it needs to be moved to the organic liquid dehydrogenation reactor 1, and the transfer of the catalyst can also be achieved by gas purging.

[0086] The transfer of the regenerated catalyst in the catalyst storage tank 26 can be achieved by nitrogen purging, as shown in the schematic diagram. Figure 6

[0087] Nitrogen is introduced into the catalyst storage tank 26 through the nitrogen inlet 33 below the catalyst storage tank, at this time the valve 20 is closed, the valve IV 34 is opened, the valve V 35 is opened, and the valve VI 36 is opened.

[0088] The regenerated catalyst in the catalyst storage tank 26 is transferred to the catalyst buffer tank 37 under the action of nitrogen purging, and nitrogen is discharged from the buffer tank waste gas outlet 42 at the upper part of the catalyst buffer tank.

[0089] After the regenerated catalyst is transferred to the catalyst buffer tank 37, hydrogen needs to be purged to replace the nitrogen in the catalyst buffer tank 37. The valve VI 36 is closed, the valve VII 38 is closed, the valve VIII 39 is opened, the valve IX 40 is opened, and hydrogen is introduced into the catalyst buffer tank 37 through the buffer tank hydrogen inlet 41. After purging, the gas is discharged from the buffer tank waste gas outlet 42 at the upper part of the catalyst buffer tank.

[0090] According to the production requirements, the catalyst in the catalyst buffer tank 37 can flow into the hydrogen storage organic liquid dehydrogenation reactor 1 by gravity through the buffer tank catalyst outlet 43, and the flow rate, flow interval and flow time of the catalyst can be controlled by the valve VII 38.

[0091] Example 1

[0092] The hydrogen storage organic liquid dehydrogenation catalyst is a platinum-based catalyst Pt / Al2O3, and the catalyst is in the form of 2-3mm pellets. The hydrogen storage organic liquid is triphenyl.

[0093] ​The catalyst carrying hydrogen storage organic liquid is continuously discharged from the hydrogen storage organic liquid dehydrogenation reactor 1, and the flow rate of the catalyst carrying hydrogen storage organic liquid is 1% of the flow rate of the hydrogen storage organic liquid inlet 5 at the lower part of the reactor. The accumulation amount of the catalyst in the catalyst regenerator 13 is 70%, and the catalyst regeneration operation is performed.

[0094] The catalyst regeneration is first performed by high-temperature nitrogen purging, the gas space velocity of the nitrogen purging is 20000h -1 -1, the nitrogen purging temperature is 300°C, and the nitrogen purging time is 2h.

[0095] After the purging is completed, the regeneration gas is introduced from the upper gas inlet 15 of the catalyst regenerator to perform the catalyst regeneration operation. The regeneration gas is air. The gas space velocity of the regeneration gas is 10000h -1 -1, the catalyst regeneration temperature is 450°C, and the catalyst regeneration time is 4h.

[0096] After the catalyst regeneration, the catalyst needs to be reduced, and the reduction gas is introduced from the upper gas inlet 15 of the catalyst regenerator to reduce the catalyst. The reduction gas is hydrogen / nitrogen mixed gas with a hydrogen volume concentration of 10%, the gas space velocity of the reduction gas is 5000h -1 -1, the catalyst reduction temperature is 250°C, and the catalyst reduction time is 3h.

[0097] The regenerated catalyst is moved to the organic liquid dehydrogenation reactor 1 in the form of nitrogen purging. The reaction performance is listed in Table 1.

[0098] Example 2

[0099] The hydrogen storage organic liquid dehydrogenation catalyst is a platinum-based catalyst Pt / Al2O3, the catalyst form is 1-2mm small balls, and the hydrogen storage organic liquid is dibenzyl toluene.

[0100] The catalyst carrying hydrogen storage organic liquid is intermittently discharged from the hydrogen storage organic liquid dehydrogenation reactor 1, and the catalyst is discharged once every 6h, each time for 1h. The flow rate of the catalyst carrying hydrogen storage organic liquid is 10% of the flow rate of the hydrogen storage organic liquid inlet 5 at the lower part of the reactor. The accumulation amount of the catalyst in the catalyst regenerator 13 is 90%, and the catalyst regeneration operation is performed. The catalyst regeneration is first performed by high-temperature nitrogen purging, the gas space velocity of the nitrogen purging is 50000h -1 -1, the nitrogen purging temperature is 350°C, and the nitrogen purging time is 1h. After the purging is completed, the regeneration gas is introduced from the upper gas inlet 15 of the catalyst regenerator to perform the catalyst regeneration operation. The regeneration gas is air. The gas space velocity of the regeneration gas is 5000h -1 -1, the catalyst regeneration temperature is 350°C, and the catalyst regeneration time is 8h.

[0101] After catalyst regeneration, the catalyst needs to be reduced. The reduction gas is introduced from the upper gas inlet 15 of the catalyst regenerator to reduce the catalyst. The reduction gas is hydrogen, and the gas space velocity of the reduction gas is 20000h -1 , the catalyst reduction temperature is 300°C, and the catalyst reduction time is 5h. The regenerated catalyst is moved to the organic liquid dehydrogenation reactor 1 in the form of nitrogen sweeping. The reaction performance is listed in Table 1.

[0102] Example 3

[0103] The hydrogen storage organic liquid dehydrogenation catalyst is a chromium-based catalyst Cr / Al2O3, and the catalyst form is 4-5mm pellets. The hydrogen storage organic liquid is toluene. The catalyst carrying hydrogen storage organic liquid is intermittently discharged in the dehydrogenation reactor 1, and the catalyst is discharged every 3h, and each time the catalyst is discharged for 0.5h. The flow rate of the catalyst carrying hydrogen storage organic liquid is one tenth of the flow rate of the hydrogen storage organic liquid inlet 5 at the lower part of the reactor. The catalyst accumulates in the catalyst regenerator 13 at 100%, and catalyst regeneration is performed. Catalyst regeneration, first high-temperature nitrogen sweeping is performed, and the gas space velocity of nitrogen sweeping is 10000h -1 , the nitrogen sweeping temperature is 250°C, and the nitrogen sweeping time is 2h. After sweeping, the regeneration gas is introduced from the upper gas inlet 15 of the catalyst regenerator to regenerate the catalyst. The regeneration gas is oxygen. The gas space velocity of the regeneration gas is 20000h -1 , the catalyst regeneration temperature is 550°C, and the catalyst regeneration time is 2h. After catalyst regeneration, the catalyst needs to be reduced, and the reduction gas is introduced from the upper gas inlet 15 of the catalyst regenerator to reduce the catalyst. The reduction gas is hydrogen gas with a hydrogen volume concentration of 50%, and the gas space velocity of the reduction gas is 100000h -1 , the catalyst reduction temperature is 500°C, and the catalyst reduction time is 1h. The regenerated catalyst is moved to the organic liquid dehydrogenation reactor 1 in the form of nitrogen sweeping. The reaction performance is listed in Table 1.

[0104] Example 4

[0105] The hydrogen storage organic liquid dehydrogenation catalyst is a platinum-based catalyst Pt / Al2O3, and the catalyst form is 2-3mm pellets. The hydrogen storage organic liquid is naphthalene. The catalyst carrying hydrogen storage organic liquid is intermittently discharged in the dehydrogenation reactor 1, and the catalyst is discharged every 12h, and each time the catalyst is discharged for 2h. The flow rate of the catalyst carrying hydrogen storage organic liquid is one twentieth of the flow rate of the hydrogen storage organic liquid inlet 5 at the lower part of the reactor. The catalyst accumulates in the catalyst regenerator 13 at 50%, and catalyst regeneration is performed. Catalyst regeneration, first high-temperature nitrogen sweeping is performed, and the gas space velocity of nitrogen sweeping is 5000h -1, the nitrogen purging temperature is 450℃, and the nitrogen purging time is 10h. After the purging, the regeneration gas is introduced into the catalyst regenerator through the upper gas inlet 15 for the catalyst regeneration. The regeneration gas is oxygen. The gas space velocity of the regeneration gas is 20000h -1 , the catalyst regeneration temperature is 450℃, and the catalyst regeneration time is 12h. After the catalyst regeneration, the catalyst needs to be reduced. The reducing gas is introduced into the catalyst through the upper gas inlet 15 of the catalyst regenerator for the reduction of the catalyst. The reducing gas is hydrogen / nitrogen mixed gas with a hydrogen volume concentration of 20%, and the gas space velocity of the reducing gas is 5000h -1 , the catalyst reduction temperature is 200℃, and the catalyst reduction time is 20h. The regenerated catalyst is moved to the organic liquid dehydrogenation reactor 1 in the form of nitrogen purging. The reaction performance is listed in Table 1.

[0106] The reaction performance shown in Table 1 shows that the method described in the present application can realize continuous and stable regeneration of the catalyst, and the catalytic dehydrogenation reaction performance of the hydrogen storage organic liquid is relatively stable.

[0107] Reaction results of Examples 1-4 in Table 1

[0108]

[0109]

[0110] The above is only a specific implementation of the present disclosure, but the protection scope of the present disclosure is not limited to this. Any person skilled in the art can easily think of changes or replacements within the technical range disclosed in the present disclosure, which should be covered within the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure should be subject to the protection scope of the claims.

Claims

1. A method for regenerating a hydrogen storage organic liquid dehydrogenation catalyst, characterized in that: The following steps are involved: Step S1: draining the catalyst carrying the hydrogen storage organic liquid discharged from the hydrogen storage organic liquid dehydrogenation reactor into a gas-liquid-solid three-phase separator, and trapping the catalyst particles by a screen in the gas-liquid-solid three-phase separator; Step S2: introducing the catalyst particles trapped by the screen in the gas-liquid-solid three-phase separator into the catalyst regenerator and performing a catalyst regeneration operation; the catalyst particles trapped by the screen in the gas-liquid-solid three-phase separator flow into the catalyst regenerator through the catalyst outflow pipe. During the catalyst regeneration operation, the control valve located at the catalyst outflow pipe is in a closed state; Step S3: Catalyst regeneration: nitrogen is used for high-temperature purge. After the purge is completed, regeneration gas is introduced from the air inlet on the top of the catalyst regenerator to perform catalyst regeneration operation. During the high-temperature nitrogen purge, nitrogen is introduced from the air inlet on the top of the catalyst regenerator. The gas space velocity of the nitrogen purge is 1000 h -1 -1000000 h -1 , nitrogen purge temperature is 80 ℃-500 ℃, and nitrogen purge time is 0.5 h-100 h; Step S4: Catalyst reduction: Reduce the catalyst by introducing reducing gas from the air inlet at the top of the catalyst regenerator; the reducing gas is a mixed gas with a hydrogen volume concentration of 1%-100%, and the gas space velocity of the reducing gas is 1000 h -1 -1000000h -1 ; The catalyst reduction temperature is 150 ℃-800 ℃; The catalyst reduction time is 0.5 h-100 h; Step S5: The regenerated catalyst is transferred to a hydrogen storage organic liquid dehydrogenation reactor in the form of nitrogen purge.

2. The regeneration method for the hydrogen storage organic liquid dehydrogenation catalyst according to claim 1, characterized in that: The catalyst is discharged from the hydrogen storage organic liquid dehydrogenation reactor in a continuous or intermittent manner. The discharge amount of the catalyst is controlled by a catalyst discharge valve provided at the bottom of the hydrogen storage organic liquid dehydrogenation reactor 1, wherein the flow rate of the hydrogen storage organic liquid carried by the catalyst is less than half of the flow rate of the hydrogen storage organic liquid inlet at the lower part of the hydrogen storage organic liquid dehydrogenation reactor.

3. The regeneration method for the hydrogen storage organic liquid dehydrogenation catalyst according to claim 1, characterized in that: The top of the gas-liquid-solid three-phase separator is provided with a gas outlet pipeline. The hydrogen flowing into the gas-liquid-solid three-phase separator is separated into gas and liquid in the gas-liquid-solid three-phase separator and flows out from the gas outlet pipeline to merge with the reactor gas outlet pipeline at the top of the hydrogen storage organic liquid dehydrogenation reactor.

4. The regeneration method for the hydrogen storage organic liquid dehydrogenation catalyst according to claim 1, characterized in that: The regeneration gas is a mixed gas with an oxygen volume concentration of 1%-100%. -1 -1000000 h -1 ; The catalyst regeneration temperature is 200 ℃-800 ℃; The catalyst regeneration time is 0.5 h-100 h.

5. The regeneration method for the hydrogen storage organic liquid dehydrogenation catalyst according to claim 1, characterized in that: In step S5, after the reduction is completed, pure hydrogen is introduced from the air inlet at the top of the catalyst regenerator for purging. After the hydrogen purging is completed, the catalyst in the catalyst regenerator flows into the catalyst storage tank through the catalyst outlet.

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