Method and device for inactivating active metal catalyst in situ

Abstract

The invention relates to the technical field of chemical production, in particular to an active metal catalyst in-situ inactivation method and a device thereof.According to the method, online / in-situ inactivation of an active metal catalyst is achieved in the mode that oxygen circulation reaction is conducted firstly and then water circulation reaction is conducted; the risk that the catalyst still having activity catches fire when encountering water and air in the agent unloading process is avoided, and the stability and safety of agent unloading are improved; meanwhile, according to the method provided by the invention, the inactivation process is milder, and the problems that hydrogen is generated by direct water injection, catalyst hardening, gelatinization and the like are increased, and catalyst unloading difficulty and safety are increased are avoided.

Description

Technical Field

[0001] The invention relates to the technical field of chemical production, and in particular to a method for in-situ deactivation of an active metal catalyst and a device for in-situ deactivation of an active metal catalyst. Background Art

[0002] Propylene dimerization is an important way to produce fine chemicals. Its dimerization product 4-methyl-1-pentene is an important branched α-olefin, which can be polymerized with ethylene to produce linear low-density polyethylene (LLDPE) with excellent performance. Compared with traditional polyolefins, it has superior toughness, low-temperature resistance, tear strength and other characteristics. In addition, it can also self-polymerize to produce thermoplastic poly-4-methyl-1-pentene (PMP), which has excellent light resistance and heat resistance.

[0003] The industrial production of 4-methyl-1-pentene has begun abroad since the 1960s. The catalyst used in the production is a single alkali metal or a catalyst mixed with multiple alkali metals. The solid base catalyst mainly uses alkali metals as active components and shows ultra-high dimerization selectivity in the propylene dimerization reaction. At the same time, the selectivity of a single dimerization product can be improved by rationally designing the catalyst. There are literature reports that the use of sodium potassium alloy as the active component of the catalyst can achieve a conversion rate of more than 20% in the propylene dimerization reaction, and the dimerization selectivity can reach more than 95%.

[0004] Since the solid base catalyst in the propylene dimerization reaction is an active metal catalyst, it usually contains alkali metal elements such as Na and K, which are extremely sensitive to water and oxygen in the air. The catalyst preparation and transfer process involves strict anhydrous and oxygen-free operation. The water and oxygen contents are kept below 1ppm and 8ppm respectively, and the operating cost is high. When the active metal catalyst reaches the end of its service life and needs to be replaced with a new agent, unloading the agent is a difficult problem. Considering that the active metal may still have a certain activity, the use of anhydrous and oxygen-free operation has high operating costs and difficulties, and is also prone to fire and other accidents, posing a great safety risk. The laboratory generally transfers the active metal catalyst in an anhydrous and oxygen-free environment and soaks it in a heptane solvent, and then introduces propylene glycol to deactivate the catalyst. However, the amount of catalyst used in the laboratory is small, and this deactivation measure is not reasonable in industrial applications, and may also bring new safety and environmental risks due to the additional introduction of organic chemicals.

[0005] US4982043A filed by Phillips Company discloses mixing inert components into active metal catalysts to avoid dangerous contact with air during loading. US4988658A and US5057639A disclose mixing inert glass beads into active metal catalysts. However, the above prior art does not consider the deactivation treatment of active metal catalysts before unloading.

[0006] CN109321274A adopts a one-step process to recover paraffin from Fischer-Tropsch wax residue and passivate the process of deactivating catalyst at the same time, mixes Fischer-Tropsch wax residue with a composite solvent, the composite solvent is composed of a hydrocarbon solvent, water and a pore-breaking agent, and obtains a passivated deactivated catalyst and a paraffin solution by heating and heat preservation, and then solid-liquid separation. CN101405307A discloses a method for deactivating the continuous catalytic olefin gathering reaction of Ziegler-Natta or metallocene catalysts, and a certain amount of deactivator is injected into the reactor, and the deactivator is a mixture of water and isopropanol. CN1032335A applied by BP Company proposes to deactivate the dimerization catalyst by water treatment, and the dimerization catalyst is nickel acetylacetonate / tricyclohexylphosphine / ethylaluminum dichloride. The above-mentioned prior art is all directed to the normal operation process of the slurry bed or homogeneous bed process of continuously adding and discharging the catalyst with the reaction material, which is significantly different from the unloading operation of the catalyst shutdown and agent change process with a certain life in the fixed bed process.

[0007] Although the prior art involves active metal catalysts with strong reducing properties, due to the application of different process and environment or reactor, the control method and deactivation time of such catalysts in situ by water treatment in the prior art are not applicable to fixed bed reactors. In addition, directly or simply using reactor water injection to deactivate the alkali metal catalyst in the fixed bed will produce hydrogen, increase the problems of catalyst agglomeration and gelatinization, and increase the difficulty and safety risk of unloading. Summary of the invention

[0008] The purpose of the present invention is to overcome the above-mentioned technical problems and provide a method for in-situ deactivation of an active metal catalyst and a device for in-situ deactivation of an active metal catalyst. The method avoids the risk of ignition of the active metal catalyst when it comes into contact with water and air during unloading, thereby improving the stability and safety of unloading.

[0009] In order to achieve the above object, the first aspect of the present invention provides a method for in-situ deactivation of an active metal catalyst, the method comprising:

[0010] (1) contacting an active metal catalyst with a first inert gas containing oxygen and performing an oxygen circulation reaction to obtain an intermediate product and a first circulating stream; subjecting the first circulating stream to first cooling and first liquid separation in sequence, and obtaining at least a portion of the first gas after first compression, and then returning and mixing with the first inert gas;

[0011] (2) when the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, introducing inert gas so that the oxygen content in the first gas is ≤10 ppm, stopping the oxygen circulation reaction, and subjecting the intermediate product to a water circulation reaction; otherwise, repeating step (1);

[0012] (3) contacting the intermediate product with a second inert gas containing water and performing the water circulation reaction, and the obtained second circulating stream is subjected to a second cooling and a second liquid separation in sequence, and at least a portion of the obtained second gas is subjected to a second compression and then returned and mixed with the second inert gas;

[0013] (4) When the hydrogen content in the second gas is ≤10 ppm and the water content is ≥the water content in the second inert gas, the water circulation reaction is stopped to obtain an in-situ deactivated catalyst.

[0014] Preferably, the catalyst bed temperature difference of the oxygen circulation reaction is Satisfies formula I:

[0015]

[0016] in, is the catalyst bed temperature difference of the oxygen circulation reaction, °C; M i is the active metal M in the active metal catalyst; i is the type of the active metal M and is a natural number; For the lively metal M i Heat of reaction with oxygen to form oxides, kcal / mol; is the loading amount of active metal Mi in the fresh active metal catalyst, kg; δ is the activity of the active metal catalyst, %; is the molar mass of the active metal Mi, g / mol; C p is the specific heat capacity of the first inert gas, kcal / (kg·℃); is the oxygen content in the first inert gas, wt%.

[0017] Preferably, the catalyst bed temperature difference of the water circulation reaction is Satisfies formula II:

[0018]

[0019] in, is the catalyst bed temperature difference of the water circulation reaction, ℃; M i is the active metal M in the active metal catalyst; i is the type of the active metal M and is a natural number; is the active metal M in the intermediate product i The heat of reaction of the oxide with water to form the hydroxide, kcal / mol; is the active metal M in the fresh active metal catalyst i The loading amount, kg; δ is the activity of the active metal catalyst, %; is the molar mass of the active metal Mi, g / mol; C' pis the specific heat capacity of the second inert gas, kcal / (kg·℃); is the water content in the second inert gas, wt%.

[0020] Preferably, the catalyst bed temperature difference of the oxygen circulation reaction is Catalyst bed temperature difference for water circulation reaction Each independently satisfies 0-100°C, preferably 0-50°C.

[0021] The second aspect of the present invention provides an in-situ deactivation device for an active metal catalyst, the device comprising: a reactor, a condenser, a liquid separation tank and a compressor connected in sequence, and an oxygen delivery pipeline, a water delivery pipeline and an inert gas delivery pipeline are arranged on the pipeline connecting the compressor and the reactor;

[0022] The reactor is provided with a catalyst bed filled with active metal catalyst; the inlet pipe connected to the reactor is provided with a first gas detection point; the pipe connecting the liquid separation tank and the compressor is provided with a second gas detection point;

[0023] Among them, a control unit is provided on the pipeline connecting the first gas detection point and the second gas detection point, so that the device has a first working state and a second working state. The first working state is that the oxygen delivery pipeline is in an open state and the water delivery pipeline is in a closed state, and the second working state is that the water delivery pipeline is in an open state and the oxygen delivery pipeline is in a closed state.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) The method provided by the present invention adopts the method of first oxygen circulation reaction and then water circulation reaction to achieve online / in-situ deactivation of active metal catalysts, avoiding the risk of ignition of active catalysts in the process of unloading due to contact with water and air, and improving the stability and safety of unloading. At the same time, the method provided by the present invention makes the deactivation process more moderate, avoids direct water injection to generate hydrogen, increase catalyst agglomeration, gelatinization, etc., and increase the difficulty and safety of unloading.

[0026] (2) The method provided by the present invention further realizes the regulation of the catalyst bed temperature difference by limiting the catalyst bed temperature difference of the oxygen circulation reaction and the catalyst bed temperature difference of the water circulation reaction to satisfy formula (I) and (II) respectively;

[0027] (3) The method provided by the present invention has a simple process, is easy to operate industrially, and has good industrial application prospects. At the same time, the device provided by the present invention realizes the switching of different working states of the device through a control unit, thereby reducing the footprint of the device and reducing costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic diagram of the structure of a device for in-situ deactivation of an active metal catalyst provided by the present invention;

[0029] Figure 2 It is a schematic diagram of a device for in-situ deactivation of an active metal catalyst provided by the present invention having a first working state;

[0030] Figure 3 It is a schematic diagram of a second working state of a device for in-situ deactivation of an active metal catalyst provided by the present invention.

[0031] Description of Reference Numerals

[0032] I, reactor; II, condenser; III, liquid separation tank; IV, compressor; V, control unit;

[0033] A1, first gas detection point; A2, second gas detection point; T1, first temperature measurement point; T2, second temperature measurement point; PC, pressure controller; M, compressor motor;

[0034] 01. Oxygen delivery pipeline; 02. Water delivery pipeline; 03. Inert gas delivery pipeline; 04. Catalyst bed; 05. Gas discharge pipeline; 06. Reaction raw material delivery pipeline; 07. Reaction product delivery pipeline; 1. Oxygen-containing gas; 2. Water; 3. Inert gas; 4. First inert gas containing oxygen; 5. First circulating stream; 6. First gas; 6-i. Part of the first gas; 6-ii. The remaining part of the first gas; 7. First compressed gas; 8. First cooled material; 9. First liquid;

[0035] 11. A second inert gas containing water; 12. A second circulating flow; 13. A second gas; 13-i. A portion of the second gas; 13-ii. A remaining portion of the second gas; 14. A second compressed gas; 15. A second cooled material; 16. A second liquid. DETAILED DESCRIPTION

[0036] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0037] In the present invention, unless otherwise specified, "first" and "second" do not indicate a sequence or limit to each material or step, but are only used to distinguish or indicate that they are not the same material or step. For example, "first" and "second" in "first cooling" and "second cooling" are only used to indicate that they are not the same cooling; similarly, "first" and "second" in "first circulating logistics" and "second circulating logistics" are only used to indicate different circulating logistics.

[0038] In the present invention, unless otherwise specified, the "top" of a container refers to the position of 0-10% from top to bottom of the container; the "upper part" of a container refers to the position of 10-40% from top to bottom of the container; the "middle part" of a container refers to the position of 40-60% from top to bottom of the container; the "lower part" of a container refers to the position of 60-90% from top to bottom of the container; and the "bottom" of a container refers to the position of 90-100% from top to bottom of the container.

[0039] The first aspect of the present invention provides a method for in-situ deactivation of an active metal catalyst, the method comprising:

[0040] (1) contacting an active metal catalyst with a first inert gas containing oxygen and performing an oxygen circulation reaction to obtain an intermediate product and a first circulating stream; subjecting the first circulating stream to first cooling and first liquid separation in sequence, and obtaining at least a portion of the first gas after first compression, and then returning and mixing with the first inert gas;

[0041] (2) when the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, introducing inert gas so that the oxygen content in the first gas is ≤10 ppm, stopping the oxygen circulation reaction, and subjecting the intermediate product to a water circulation reaction; otherwise, repeating step (1);

[0042] (3) contacting the intermediate product with a second inert gas containing water and performing the water circulation reaction, and the obtained second circulating stream is subjected to a second cooling and a second liquid separation in sequence, and at least a portion of the obtained second gas is subjected to a second compression and then returned and mixed with the second inert gas;

[0043] (4) When the hydrogen content in the second gas is ≤10 ppm and the water content is ≥the water content in the second inert gas, the water circulation reaction is stopped to obtain an in-situ deactivated catalyst.

[0044] In the present invention, unless otherwise specified, the oxygen content in the first gas and the oxygen content in the first inert gas are used as judgment criteria for the oxygen cycle reaction. When the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, the oxygen cycle reaction is terminated by default; when the oxygen content in the first gas is < the oxygen content in the first inert gas, the oxygen cycle reaction is repeated.

[0045] In the present invention, only when the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, the inert gas is introduced until the oxygen content in the first gas is ≤10ppm, the oxygen circulation reaction is stopped, and the second inert gas containing water is introduced to carry out the water circulation reaction.

[0046] In the present invention, unless otherwise specified, the hydrogen content and water content in the second gas, and the water content in the second inert gas are used as criteria for judging the water circulation reaction. Only when the hydrogen content in the second gas is ≤10ppm and the water content is ≥the water content in the second inert gas, it is assumed that all the active metals in the active metal catalyst are deactivated, the water circulation reaction is stopped, and an in-situ deactivated catalyst is obtained.

[0047] In some embodiments of the present invention, preferably, the catalyst bed temperature difference of the oxygen circulation reaction is Satisfies formula I:

[0048]

[0049] in, is the catalyst bed temperature difference of the oxygen circulation reaction, °C; M i is the active metal M in the active metal catalyst, i is the type of the active metal M and is a natural number; is the heat of reaction of active metal M with oxygen to form oxide, kcal / mol; is the active metal M in the fresh active metal catalyst i The loading amount, kg; δ is the activity of the active metal catalyst, %; is the molar mass of the active metal Mi, g / mol; C p is the specific heat capacity of the first inert gas, kcal / (kg·℃); is the oxygen content in the first inert gas, wt%.

[0050] In the present invention, in Formula I, Relative to 1 mol of active metal M i The heat of reaction with oxygen to form oxides, the active metal M in the active metal catalyst i Heat of reaction; C p The sum of the specific heat capacities of oxygen and the inert gas in the first inert gas = (volume content of oxygen in the first inert gas × molar specific heat of oxygen + volume content of inert gas in the first inert gas × molar specific heat of inert gas) / (volume content of oxygen in the first inert gas × molar mass of oxygen + volume content of inert gas in the first inert gas × molar mass of inert gas).

[0051] In one embodiment of the present invention, in formula I, when M in the active metal catalyst is selected from Na and K, the catalyst bed temperature difference of the oxygen circulation reaction is satisfy:

[0052]

[0053] In some embodiments of the present invention, preferably, the catalyst bed temperature difference of the water circulation reaction is Satisfies formula II:

[0054]

[0055] in, is the catalyst bed temperature difference of the water circulation reaction, ℃; M i is the active metal M in the active metal catalyst, i is the type of the active metal M and is a natural number; is the active metal M in the intermediate product i The heat of reaction of the oxide with water to form the hydroxide, kcal / mol; is the active metal M in the fresh active metal catalyst i The loading amount, kg; δ is the activity of the active metal catalyst, %; is the molar mass of the active metal Mi, g / mol; C' p is the specific heat capacity of the second inert gas, kcal / (kg·℃); is the water content in the second inert gas, wt%.

[0056] In the present invention, in Formula II, Relative to 1 mol of active metal M i The heat of reaction of the oxide with water to form hydroxide, the active metal M in the intermediate product i Oxide reaction heat; C' p The sum of the specific heat capacities of water and the inert gas in the second inert gas = (volume content of water in the second inert gas × molar specific heat of water + volume content of inert gas in the second inert gas × molar specific heat of inert gas) / (volume content of water in the second inert gas × molar mass of water + volume content of inert gas in the second inert gas × molar mass of inert gas).

[0057] In one embodiment of the present invention, in formula II, when M in the active metal catalyst is selected from Na and K, the catalyst bed temperature difference of the water circulation reaction is satisfy:

[0058]

[0059] In some embodiments of the present invention, preferably, the catalyst bed temperature difference of the oxygen circulation reaction is Catalyst bed temperature difference for water circulation reaction Each independently satisfies 0-100°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 80°C, 100°C, and any value in the range consisting of any two values, preferably 0-50°C.

[0060] In some embodiments of the present invention, it is further preferred that the catalyst bed temperature difference of the oxygen circulation reaction is <The catalyst bed temperature difference of the water circulation reaction

[0061] In some embodiments of the present invention, preferably, the active metal M in the active metal catalyst is selected from metals with stronger reducing properties than hydrogen in the periodic table, preferably selected from at least one of sodium (Na), metallic potassium (K), metallic lithium (Li), rubidium (Rb), cesium (Cs), magnesium (Mg), aluminum (Al), zinc (Zn), iron (Fe), tin (Sn), lead (Pb), nickel (Ni), copper (Cu), platinum (Pt) and palladium (Pd), more preferably selected from sodium (Na) and / or metallic potassium (K).

[0062] In some embodiments of the present invention, preferably, the loading amount of the active metal in the active metal catalyst is 0.5-20 wt %, preferably 0.5-10 wt %.

[0063] In the present invention, the source of the active metal catalyst has a wide selection range, as long as the active metal catalyst meets the above definition. Preferably, the active metal catalyst is selected from the catalyst for preparing 4-methyl-1-pentene by propylene dimerization.

[0064] In some embodiments of the present invention, preferably, the activity δ of the active metal catalyst is 0-100%, preferably 0-80%. In the present invention, the activity δ is the relative activity based on 100% of the fresh active metal catalyst.

[0065] In the present invention, unless otherwise specified, the oxygen-containing first inert gas is composed of oxygen and an inert gas; the water-containing second inert gas is composed of water and an inert gas. In the present invention, the inert gas includes but is not limited to nitrogen, helium, argon, neon, etc., preferably nitrogen.

[0066] In some embodiments of the present invention, preferably, the oxygen content in the first inert gas is 0.1-1wt%; the water content in the second inert gas 0.1-1wt%.

[0067] In the present invention, the oxygen cycle reaction is intended to contact the oxygen-containing first inert gas with the active metal in the active metal catalyst and perform an oxygen cycle reaction, so that the active metal is converted into a metal oxide, and an intermediate product and a first circulating flow containing an inert gas and oxygen are obtained. Preferably, in step (1), the conditions of the oxygen cycle reaction include: an inlet temperature of 40-100°C, preferably 40-60°C; a gas-to-agent ratio of 50-3000, preferably 300-1000; an inlet pressure of 0.05-11MPa, preferably 0.05-5MPa; a time of 0.5-48h, preferably 4-24h; wherein the gas-to-agent ratio is the ratio of the volume of the first inert gas to the loading volume of the active metal catalyst. In the present invention, pressure parameters are all gauge pressures.

[0068] In some embodiments of the present invention, preferably, during the oxygen circulation reaction, the amount of oxygen used is 1-10% of the loading mass of the active metal catalyst, for example, 1%, 2%, 3%, 5%, 8%, 10%, and any value in the range of any two values, preferably 2-5%, in units of mass kg / kg. The preferred conditions are adopted so that all the active metal in the active metal catalyst is converted into metal oxide.

[0069] In the present invention, the amount of oxygen used is 0.01-0.1 kg, preferably 0.02-0.05 kg, relative to 1 kg of the loaded mass of the active metal catalyst.

[0070] In the present invention, the first cooling is to reduce the temperature of the first circulating stream. Preferably, the temperature of the first cooled stream is 40-60°C and the pressure is 0-11 MPa.

[0071] In the present invention, the first liquid separation is intended to separate the first cooled logistics into gas and liquid to obtain a first gas and a first liquid.

[0072] In some embodiments of the present invention, preferably, when the pressure of the first gas is ≤ P1, and P1 = the outlet pressure of the first cooling, the first gas is subjected to the first compression; otherwise, part of the first gas is subjected to the first compression.

[0073] In some embodiments of the present invention, preferably, the temperature of the first compressed gas is 40-60° C. and the pressure is 0.05-11 MPa.

[0074] In the present invention, based on the oxygen content in the first gas and the oxygen content in the first inert gas, it is determined whether to perform an oxygen cycle reaction or a water cycle reaction. When the oxygen content in the first gas is less than the oxygen content in the first inert gas, an oxygen cycle reaction is performed, that is, step (1) is repeated until the oxygen content in the first gas is greater than or equal to the oxygen content in the first inert gas, an inert gas is introduced so that the oxygen content in the first gas is less than or equal to 10 ppm, the oxygen cycle reaction is stopped, and a water cycle reaction is performed, that is, step (2) is performed.

[0075] In the present invention, the water circulation reaction is intended to contact the second inert gas containing water with the metal oxide in the intermediate product and carry out a water circulation reaction, so that the metal oxide is converted into a metal hydroxide, and an in-situ deactivated catalyst and a second circulating flow containing an inert gas and water are obtained. Preferably, in step (3), the conditions of the water circulation reaction include: an inlet temperature of 40-100°C, preferably 40-60°C; a gas-to-agent ratio of 50-3000, preferably 300-1000; an inlet pressure of 0.05-11MPa, preferably 0.05-5MPa; a time of 0.5-48h, preferably 4-24h; wherein the gas-to-agent ratio is the ratio of the volume of the second inert gas to the loading volume of the active metal catalyst.

[0076] In some embodiments of the present invention, preferably, during the water circulation reaction, the amount of water used is 1-20% of the loading mass of the active metal catalyst, for example, 1%, 2%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, and any value in the range of any two values, preferably 2-8%, in units of mass kg / kg. The preferred conditions are adopted so that all the metal oxides in the intermediate product are converted into metal hydroxides.

[0077] In the present invention, the amount of water used is 0.01-0.2 kg, preferably 0.02-0.08 kg, relative to 1 kg of the loaded mass of the active metal catalyst.

[0078] In some embodiments of the present invention, preferably, water in the second inert gas exists in gaseous and / or liquid form.

[0079] In the present invention, the second cooling is intended to reduce the temperature of the second circulating stream. Preferably, the temperature of the second cooled stream is 40-60°C and the pressure is 0-11 MPa.

[0080] In the present invention, the second liquid separation is intended to separate the second cooled logistics into gas and liquid to obtain a second gas and a second liquid.

[0081] In some embodiments of the present invention, preferably, when the pressure of the second gas is ≤ P2, and P2 = the outlet pressure of the second cooling, the second gas is subjected to the second compression; otherwise, part of the second gas is subjected to the second compression.

[0082] In some embodiments of the present invention, preferably, the temperature of the second compressed gas is 40-60° C. and the pressure is 0.05-11 MPa.

[0083] In a specific embodiment of the present invention, when the hydrogen content in the second gas is ≤10ppm and the water content is ≥the water content in the second inert gas, it indicates that the active metal in the active metal catalyst is completely in situ deactivated to obtain an in situ deactivated catalyst.

[0084] In some embodiments of the present invention, preferably, in step (4), when the hydrogen content in the second gas is greater than 10 ppm, part of the second gas is discharged and inert gas is supplemented until the pressure of the second gas = P2 and the hydrogen content in the second gas is ≤10 ppm; step (1) is repeated until the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, part of the first gas is discharged and inert gas is supplemented until the pressure of the first gas is ≥ P1 and the oxygen content in the first gas is ≤10 ppm; step (3) is repeated until the hydrogen content in the second gas is ≤10 ppm and the water content is ≥ the water content in the second inert gas, thereby obtaining the in situ deactivated catalyst.

[0085] In some embodiments of the present invention, preferably, in step (4), when the hydrogen content in the second gas is ≤10 ppm and the water content is <the water content in the second inert gas, step (3) is repeated until the water content in the second gas is ≥the water content in the second inert gas to obtain the in situ deactivated catalyst.

[0086] The second aspect of the present invention provides a schematic structural diagram of a device for in-situ deactivation of an active metal catalyst. Figure 1 As shown by Figure 1 It can be seen that the device includes: a reactor I, a condenser II, a liquid separator III and a compressor IV connected in sequence, and an oxygen delivery pipeline 01, a water delivery pipeline 02 and an inert gas delivery pipeline 03 are arranged on the pipeline connecting the compressor IV and the reactor I;

[0087] The reactor I is provided with a catalyst bed 04 filled with an active metal catalyst; a first gas detection point A1 is provided on the inlet pipe connected to the reactor I; a second gas detection point A2 is provided on the pipe connecting the liquid separation tank III and the compressor IV;

[0088] Among them, a control unit V is provided on the pipeline connecting the first gas detection point A1 and the second gas detection point A2, so that the device has a first working state and a second working state. The first working state is that the oxygen delivery pipeline 01 is in an open state and the water delivery pipeline 02 is in a closed state, and the second working state is that the water delivery pipeline 02 is in an open state and the oxygen delivery pipeline 01 is in a closed state.

[0089] In the present invention, unless otherwise specified, the first working state and the second working state are not performed simultaneously; the first working state is that the oxygen delivery pipeline 01 is in an open state and the water delivery pipeline 02 is in a closed state, that is, the first working state is an oxygen circulation reaction; the second working state is that the water delivery pipeline 02 is in an open state and the oxygen delivery pipeline 01 is in a closed state, that is, the second working state is a water circulation reaction.

[0090] In the present invention, preferably, Figure 2 As shown, when the device is in the first working state, the oxygen-containing first inert gas 4 enters the reactor I, contacts the active metal catalyst and undergoes an oxygen circulation reaction to obtain an intermediate product and a first circulating flow 5; the first circulating flow 5 successively enters the condenser II and the separator III for a first cooling and a first separation, and at least a portion of the first gas 6 obtained enters the compressor IV for a first pressurization, and the obtained first compressed gas 7 returns to the reactor I.

[0091] In the present invention, preferably, Figure 3 As shown, when the device is in the second working state, the water-containing second inert gas 11 enters the reactor I, contacts the intermediate product and undergoes a water circulation reaction, and the obtained second circulating flow 12 enters the condenser II and the separator III in sequence for second cooling and second separation, and at least part of the obtained second gas 13 enters the compressor IV for second pressurization, and the obtained second compressed gas 14 returns to the reactor I.

[0092] In the present invention, preferably, when the oxygen content of the second gas detection point A2 is less than the oxygen content of the first gas detection point A1, the control unit V puts the device in the first working state; when the oxygen content of the second gas detection point A2 is greater than or equal to the oxygen content of the first gas detection point A1, an inert gas is introduced so that the oxygen content of the second gas detection point A2 is ≤10ppm, and the control unit V puts the device in the second working state.

[0093] In the present invention, preferably, when the hydrogen content of the second gas detection point A2 is greater than 10ppm, the control unit V puts the device in the first working state; when the hydrogen content of the second gas detection point A2 is ≤10ppm, and the water content of the second gas detection point A2 is less than the water content of the first gas detection point A1, the control unit V puts the device in the second working state; when the hydrogen content of the second gas detection point A2 is ≤10ppm, and the water content of the second gas detection point A2 is ≥ the water content of the first gas detection point A1, an in-situ deactivated catalyst is obtained.

[0094] In a specific embodiment of the present invention, when the device is in a first working state, such as Figure 2 As shown, the oxygen delivery pipeline 01 and the inert gas delivery pipeline 03 are opened, and the water delivery pipeline 02 is closed, so that the oxygen-containing first inert gas 4 enters the reactor I for oxygen circulation reaction, the obtained first circulating stream 5 enters the condenser II for first cooling, the obtained first cooled material 8 enters the liquid separator III for first liquid separation, and the first gas 6 and the first liquid 9 are obtained, and at least part of the first gas 6 enters the compressor IV for first compression, and the obtained first compressed gas 7 is returned to the reactor I;

[0095] The oxygen content of the first gas detection point A1 and the second gas detection point A2 is detected at regular intervals (for example, 1 hour). When the oxygen content in the first gas 6 is less than the oxygen content in the first inert gas 4, the first working state is repeated; when the oxygen content in the first gas 6 is greater than or equal to the oxygen content in the first inert gas 4, an inert gas is introduced so that the oxygen content in the first gas 6 is less than or equal to 10 ppm, and the control unit V puts the device in the second working state;

[0096] like Figure 3 As shown, the water delivery pipeline 02 and the inert gas delivery pipeline 03 are opened, and the oxygen delivery pipeline 01 is closed, so that the second inert gas 11 containing water enters the reactor I for water circulation reaction, and the obtained second circulating stream 12 enters the condenser II for second cooling, and the obtained second cooled material 15 enters the liquid separator III for second liquid separation to obtain the second gas 13 and the second liquid 16, and at least part of the second gas 13 enters the compressor IV for second compression to obtain the second compressed gas 14 and return to the reactor I;

[0097] Detect the hydrogen content and water content of the second gas detection point A2 and the first gas detection point A1 at regular intervals (for example, 1 hour). When the hydrogen content in the second gas 13 is ≤10ppm and the water content is ≥the water content in the second inert gas 11, close the water delivery pipeline 02 and the inert gas delivery pipeline 03 to obtain an in-situ deactivated catalyst.

[0098] When the hydrogen content in the second gas 13 is ≤10ppm, and the water content is <the water content in the second inert gas 11, repeat the above-mentioned second working state; when the hydrogen content in the second gas 13 is >10ppm, discharge part of the second gas 13 and replenish inert gas until the second gas pressure = P2 and the hydrogen content in the second gas is ≤10ppm; repeat the above-mentioned first working state until the oxygen content in the first gas 6 is ≥the oxygen content in the first inert gas 4, discharge part of the first gas 6, and replenish inert gas until the first gas pressure = P1 and the oxygen content in the first gas 6 is ≤10ppm; regulate the device to be in the second working state until the hydrogen content in the second gas 13 is ≤10ppm, and the water content is ≥the water content in the second inert gas 11, and obtain the in-situ deactivated catalyst.

[0099] In some embodiments of the present invention, preferably, Figure 1 As shown, the top and bottom of the catalyst bed 04 are respectively connected to a first temperature measuring point T1 and a second temperature measuring point T2, which are used to control the oxygen content in the first inert gas (4) and the water content in the second inert gas (11).

[0100] In the present invention, when the device is in the first working state, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is less than the temperature difference of the catalyst bed of the oxygen circulation reaction, Maintain the oxygen content in the first inert gas; when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1)> the catalyst bed temperature difference of the oxygen circulation reaction The oxygen content in the first inert gas is reduced.

[0101] In the present invention, when the device is in the second working state, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is less than the catalyst bed temperature difference of the water circulation reaction, Maintain the water content in the second inert gas; when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1)> the catalyst bed temperature difference of the water circulation reaction Reduce the water content in the second inert gas.

[0102] In some embodiments of the present invention, preferably, Figure 1 As shown, a pressure controller PC is provided on the pipeline connecting the top of the liquid separator III and the inert gas delivery pipeline 03, and a gas discharge pipeline 05 is also connected to the pipeline connecting the liquid separator III and the compressor IV, which is used to detect the top gas pressure of the liquid separator III and regulate at least part of the top gas to enter the compressor IV.

[0103] In the present invention, if Figure 2As shown, when the device is in the first working state, that is, the oxygen cycle reaction is carried out, the pressure of the pressure controller PC is detected, and when the pressure of the first gas 6 is ≤ P1, the first gas 6 enters the compressor IV, otherwise, part of the first gas 6-i enters the compressor IV; or Figure 3 As shown, when the device is in the second working state, that is, when the water circulation reaction is carried out, the pressure of the pressure controller PC is detected, and when the pressure of the second gas 13 is ≤P2, the second gas 13 enters the compressor IV, otherwise, part of the second gas 13-i enters the compressor IV.

[0104] In some embodiments of the present invention, preferably, Figure 1 As shown, a reaction raw material delivery pipeline 06 and a reaction product delivery pipeline 07 are respectively provided at the top and the bottom of the reactor 1.

[0105] The present invention will be described in detail below through examples.

[0106] In the examples and comparative examples, the inert gas is selected from nitrogen.

[0107] Example 1

[0108] Device for in-situ deactivation of active metal catalysts Figure 1-3 As shown, the device includes: a reactor I, a condenser II, a liquid separator III and a compressor IV connected in sequence, and an oxygen delivery pipeline 01, a water delivery pipeline 02 and an inert gas delivery pipeline 03 are arranged on the pipeline connecting the compressor IV and the reactor I;

[0109] A catalyst bed 04 filled with active metal catalyst is arranged in the reactor I, and the top and bottom of the catalyst bed 04 are respectively connected to the first temperature measuring point T1 and the second temperature measuring point T2; a first gas detection point A1 is arranged above the reactor I; a second gas detection point A2 is arranged on the pipeline connecting the liquid separator tank III and the compressor IV; a control unit V is arranged on the pipeline connecting the first gas detection point A1 and the second gas detection point A2; a pressure controller PC is arranged on the pipeline connecting the top of the liquid separator tank III and the inert gas delivery pipeline 03, and a gas discharge pipeline 05 is also connected to the pipeline connecting the liquid separator tank III and the compressor IV.

[0110] The method for in-situ deactivation of the active metal catalyst is carried out in the above-mentioned device, and the method comprises:

[0111] (1) Open the oxygen delivery pipeline 01, close the water delivery pipeline, contact the above-mentioned active metal catalyst (loading mass is 25 kg, the active metals are Na and K, and the mass ratio of Na and K is 1:2, the total loading amount of active metals is 5wt%, and the activity is 100%) with the first oxygen-containing inert gas (oxygen content is 0.14wt%) and carry out oxygen circulation reaction (inlet temperature is 57°C, gas-to-agent ratio is 600, inlet pressure is 0.3MPa, and time is 12h) to obtain an intermediate product and a first circulating stream; subject the above-mentioned first circulating stream to a first cooling process, and the first cooled stream (temperature is 40°C, pressure is 0.25MPa) is subjected to a first liquid separation to obtain a first gas (temperature is 40°C, pressure is 0.25MPa); since the pressure of the first gas is ≤P1 (0.25MPa), the first gas is subjected to a first compression process, and the first compressed gas (temperature is 57°C, pressure is 0.3MPa) is returned to the first inert gas;

[0112] In the above oxygen cycle reaction, the amount of oxygen used is 1% of the loading mass of the above active metal catalyst, measured in kg / kg; the catalyst bed temperature difference of the above oxygen cycle reaction is

[0113] During the oxygen cycle reaction, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is ≤1.85°C, the oxygen content in the first inert gas is maintained; otherwise, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is greater than 1.85°C, the oxygen content in the first inert gas is reduced;

[0114] (2) During the oxygen circulation reaction, the oxygen content at the first gas detection point A1 and the second gas detection point A2 is detected every 1 h. When the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, the inert gas is introduced so that the oxygen content in the first gas is ≤10 ppm, the oxygen circulation pipeline is closed, and the water circulation pipeline is opened;

[0115] (3) contacting the intermediate product with a second inert gas containing water (water content of 0.16 wt%) and performing a water circulation reaction (inlet temperature of 57° C., gas-to-agent ratio of 600, inlet pressure of 0.3 MPa, time of 12 h) to obtain an in-situ deactivated catalyst and a second circulating stream; subjecting the second circulating stream to a second cooling step, and obtaining a second cooled stream (temperature of 40° C., pressure of 0.25 MPa), and performing a second liquid separation step to obtain a second gas (temperature of 40° C., pressure of 0.25 MPa); since the pressure of the second gas is ≤ P2 (0.25 MPa), subjecting the second gas to a second compression step, and obtaining a second compressed gas (temperature of 57° C., pressure of 0.3 MPa) is returned to the second inert gas;

[0116] In the process of the water circulation reaction, the amount of water used is 1% of the loading mass of the active metal catalyst, measured in kg / kg; the temperature difference of the catalyst bed of the oxygen circulation reaction is

[0117] During the water circulation reaction, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is ≤30.20°C, the water content in the second inert gas is maintained; otherwise, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is greater than 30.20°C, the water content in the second inert gas is reduced;

[0118] (4) During the water circulation reaction, the hydrogen content of the second gas detection point A2 and the water content of the first gas detection point A1 and the second gas detection point A2 are detected every 1 h. If the hydrogen content in the second gas is greater than 10 ppm, it means that the active metal is not completely converted. The water delivery pipeline is closed, part of the second gas is discharged, and inert gas is supplemented until the second gas pressure is maintained at 0.25 MPa and the hydrogen content in the second gas is ≤10 ppm. Then the oxygen delivery pipeline is opened, and step (1) is repeated until the oxygen content in the first gas is greater than or equal to the oxygen content in the first inert gas. The oxygen circulation delivery pipeline is closed, part of the first gas is discharged, and inert gas is supplemented until the first gas pressure is maintained at 0.25 MPa and the oxygen content in the first gas is less than or equal to 10 ppm. Then the water circulation delivery pipeline is opened, and step (3) is repeated until the hydrogen content in the second gas is less than or equal to 10 ppm and the water content is greater than or equal to the water content in the second inert gas. The water delivery pipeline and the inert gas delivery pipeline are closed to obtain an in-situ deactivated catalyst.

[0119] The catalyst bed temperature difference during the oxygen cycle reaction for 12 hours is The catalyst bed temperature difference of the above water circulation reaction for 12 hours is 1.85℃. It is 30.20℃.

[0120] Example 2

[0121] According to the device of embodiment 1;

[0122] According to the method of Example 1, the difference is that

[0123] In step (1),

[0124] The active metal of the active metal catalyst is Na, and the loading amount of Na is 10wt%, and the activity is 90%;

[0125] The conditions of the oxygen cycle reaction included: inlet temperature of 57 °C, gas-to-agent ratio of 800, inlet pressure of 0.3 MPa, and time of 16 h;

[0126] During the oxygen circulation reaction, the amount of oxygen used is 3% of the loading mass of the active metal catalyst, measured in kg / kg; the oxygen content in the first inert gas is 0.19wt%;

[0127] Catalyst bed temperature difference for oxygen cycle reaction satisfy:

[0128]

[0129] During the oxygen cycle reaction, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is ≤4.44°C, the oxygen content in the first inert gas is maintained; otherwise, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is greater than 4.44°C, the oxygen content in the first inert gas is reduced;

[0130] In step (3),

[0131] The conditions of the water circulation reaction included: inlet temperature of 57 °C, gas-to-agent ratio of 800, inlet pressure of 0.3 MPa, and time of 16 h;

[0132] The amount of water used is 3% of the loading mass of the above-mentioned active metal catalyst, measured in mass units of kg / kg; the water content in the second inert gas is 0.22wt%; the catalyst bed temperature difference of the above-mentioned oxygen circulation reaction is satisfy:

[0133]

[0134] During the water circulation reaction, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is ≤19.32°C, the water content in the second inert gas is maintained; otherwise, when the temperature difference of (the second temperature measuring point T2-the first temperature measuring point T1) is greater than 19.32°C, the water content in the second inert gas is reduced;

[0135] The other conditions were the same, and an in-situ deactivated catalyst was obtained.

[0136] The catalyst bed temperature difference during the oxygen cycle reaction for 16 hours is The catalyst bed temperature difference of the above water circulation reaction for 16 hours is 4.44℃. It is 19.32℃.

[0137] Comparative Example 1

[0138] According to the device of embodiment 1;

[0139] According to the method of Example 1, except that the method is carried out in the above-mentioned device;

[0140] Without step (1) and step (2), without oxygen circulation reaction, the active metal catalyst is directly contacted with the second inert gas containing water (water content is 0.31wt%) to carry out water circulation reaction, and the amount of water used is 3% of the loading mass of the above-mentioned active metal catalyst, measured in mass unit kg / kg, and other conditions are the same, to obtain an in-situ deactivated catalyst.

[0141] Among them, when the second gas detection point detects a hydrogen content of >10ppm during the deactivation process, part of the second gas is discharged and inert gas is supplemented until the second gas pressure is maintained at 0.25MPa and the hydrogen content in the second gas is ≤10ppm; at the end of the deactivation, it can be seen that the catalyst bed is severely gelatinized. In order to improve the safety of operation and avoid the accumulation of hydrogen in the reaction system, the deactivation process requires multiple discharges of part of the hydrogen-containing gas.

[0142] Compared with Comparative Example 1, Example 1-2 adopts the method of first oxygen circulation reaction and then water circulation reaction, thereby realizing online / in-situ deactivation of active metal catalysts, avoiding the risk of ignition of active catalysts in contact with water and air during the unloading process, and improving the stability and safety of the unloading; at the same time, through formulas (I) and (II), the temperature difference of the catalyst bed can be regulated.

[0143] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for in-situ deactivation of an active metal catalyst, characterized in that: The method includes: (1) contacting an active metal catalyst with a first inert gas containing oxygen and performing an oxygen circulation reaction to obtain an intermediate product and a first circulating stream; subjecting the first circulating stream to first cooling and first liquid separation in sequence, and obtaining at least a portion of the first gas after first compression, and then returning and mixing with the first inert gas; (2) when the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, introducing inert gas so that the oxygen content in the first gas is ≤10 ppm, stopping the oxygen circulation reaction, and subjecting the intermediate product to a water circulation reaction; otherwise, repeating step (1); (3) contacting the intermediate product with a second inert gas containing water and performing the water circulation reaction, and the obtained second circulating stream is subjected to a second cooling and a second liquid separation in sequence, and at least a portion of the obtained second gas is subjected to a second compression and then returned and mixed with the second inert gas; (4) When the hydrogen content in the second gas is ≤10 ppm and the water content is ≥the water content in the second inert gas, the water circulation reaction is stopped to obtain an in-situ deactivated catalyst.

2. The method according to claim 1, wherein: The catalyst bed temperature difference of the oxygen circulation reaction Satisfies formula I: in, is the catalyst bed temperature difference of the oxygen circulation reaction, °C; M i is the active metal M in the active metal catalyst, i is the type of the active metal M and is a natural number; For the lively metal M i Heat of reaction with oxygen to form oxides, kcal / mol; is the active metal M in the fresh active metal catalyst i The loading amount, kg; δ is the activity of the active metal catalyst, %; For the lively metal M i Molar mass, g / mol; C p is the specific heat capacity of the first inert gas, kcal / (kg·℃); is the oxygen content in the first inert gas, wt%; And / or, the catalyst bed temperature difference of the water circulation reaction Satisfies formula II: in, is the catalyst bed temperature difference of the water circulation reaction, ℃; M i is the active metal M in the active metal catalyst, i is the type of the active metal M and is a natural number; is the active metal M in the intermediate product i The heat of reaction of the oxide with water to form the hydroxide, kcal / mol; is the active metal M in the fresh active metal catalyst i The loading amount, kg; δ is the activity of the active metal catalyst, %; For the lively metal M i Molar mass, g / mol; C' p is the specific heat capacity of the second inert gas, kcal / (kg·℃); is the water content in the second inert gas, wt%.

3. The method according to claim 2, wherein: The catalyst bed temperature difference of the oxygen circulation reaction Catalyst bed temperature difference for water circulation reaction Each independently satisfies 0-100°C, preferably 0-50°C; And / or, the catalyst bed temperature difference of the oxygen circulation reaction <The catalyst bed temperature difference of the water circulation reaction 4. The method according to claim 2 or 3, wherein: The active metal M in the active metal catalyst is selected from metals with stronger reducing properties than hydrogen in the periodic table, preferably at least one selected from sodium (Na), potassium (K), lithium (Li), rubidium (Rb), cesium (Cs), magnesium (Mg), aluminum (Al), zinc (Zn), iron (Fe), tin (Sn), lead (Pb), nickel (Ni) and palladium (Pd), more preferably sodium (Na) and / or potassium (K); and / or, the active metal loading in the active metal catalyst is 0.5-20wt%, preferably 0.5-10wt%; And / or, the active metal catalyst is selected from the catalyst for preparing 4-methyl-1-pentene by propylene dimerization; and / or, the activity δ of the active metal catalyst is 0-100%, preferably 0-80%; And / or, the oxygen content in the first inert gas is 0.1-1wt%; And / or, the water content in the second inert gas is 0.1-1wt%.

5. The method according to any one of claims 1 to 4, wherein: The conditions of the oxygen circulation reaction and the water circulation reaction independently include: an inlet temperature of 40-100°C, preferably 40-60°C; a gas-to-agent ratio of 50-3000, preferably 300-1000; an inlet pressure of 0.05-11MPa, preferably 0.05-5MPa; a time of 0.5-48h, preferably 4-24h; wherein the gas-to-agent ratio is the ratio of the volume of the first inert gas / the second inert gas to the loading volume of the active metal catalyst; and / or, during the oxygen circulation reaction, the amount of oxygen used is 1-10%, preferably 2-5%, of the loading mass of the active metal catalyst, in units of mass kg / kg; And / or, during the water circulation reaction, the amount of water used is 1-20%, preferably 2-8%, of the loading mass of the active metal catalyst, in units of mass kg / kg; And / or, the water in the second inert gas exists in gaseous and / or liquid form.

6. The method according to any one of claims 1 to 5, wherein: When the pressure of the first gas is ≤ P1, and P1 = the outlet pressure of the first cooling, the first gas is subjected to the first compression; otherwise, part of the first gas is subjected to the first compression; and / or, when the pressure of the second gas is ≤ P2, and P2 = the outlet pressure of the second cooling, the second gas is subjected to the second compression; otherwise, part of the second gas is subjected to the second compression; and / or, the temperature of the first cooled logistics is 40-60° C. and the pressure is 0-11 MPa; and / or, the temperature of the second cooled logistics is 40-60° C. and the pressure is 0-11 MPa; and / or, the temperature of the first compressed gas is 40-60° C. and the pressure is 0.05-11 MPa; And / or, the temperature of the second compressed gas is 40-60° C. and the pressure is 0.05-11 MPa.

7. The method according to claim 6, wherein: In step (4), when the hydrogen content in the second gas is greater than 10 ppm, part of the second gas is discharged and inert gas is added until the pressure of the second gas is equal to P2 and the hydrogen content in the second gas is less than or equal to 10 ppm; step (1) is repeated until the oxygen content in the first gas is greater than or equal to the oxygen content in the first inert gas, part of the first gas is discharged and inert gas is added until the pressure of the first gas is equal to P1 and the oxygen content in the first gas is less than or equal to 10 ppm; step (3) is repeated until the hydrogen content in the second gas is less than or equal to 10 ppm and the water content is greater than or equal to the water content in the second inert gas, thereby obtaining the in-situ deactivated catalyst; or, When the hydrogen content in the second gas is ≤10ppm and the water content is <the water content in the second inert gas, repeat step (3) until the water content in the second gas is ≥the water content in the second inert gas to obtain the in-situ deactivated catalyst.

8. A device for in-situ deactivation of an active metal catalyst, characterized in that: The device comprises: a reactor (I), a condenser (II), a liquid separator (III) and a compressor (IV) connected in sequence, and an oxygen delivery pipeline (01), a water delivery pipeline (02) and an inert gas delivery pipeline (03) are arranged on the pipeline connecting the compressor (IV) and the reactor (I); The reactor (I) is provided with a catalyst bed (04) filled with an active metal catalyst; a first gas detection point (A1) is provided on the inlet pipe connected to the reactor (I); a second gas detection point (A2) is provided on the pipe connecting the liquid separation tank (III) and the compressor (IV); A control unit (V) is provided on the pipeline connecting the first gas detection point (A1) and the second gas detection point (A2), so that the device has a first working state and a second working state, the first working state is that the oxygen delivery pipeline (01) is in an open state and the water delivery pipeline (02) is in a closed state, and the second working state is that the water delivery pipeline (02) is in an open state and the oxygen delivery pipeline (01) is in a closed state.

9. The device according to claim 8, wherein: When the device is in a first working state, the oxygen-containing first inert gas (4) enters the reactor (I), contacts the active metal catalyst and undergoes an oxygen circulation reaction to obtain an intermediate product and a first circulating stream (5); the first circulating stream (5) enters the condenser (II) and the liquid separator (III) in sequence to undergo a first cooling and a first liquid separation, and at least a portion of the obtained first gas (6) enters the compressor (IV) to undergo a first pressurization, and the obtained first compressed gas (7) returns to the reactor (I); And / or, when the device is in the second working state, the water-containing second inert gas (11) enters the reactor (I), contacts with the intermediate product and undergoes a water circulation reaction, and the obtained second circulating stream (12) enters the condenser (II) and the liquid separator (III) in sequence for second cooling and second liquid separation, and at least part of the obtained second gas (13) enters the compressor (IV) for second pressurization, and the obtained second compressed gas (14) returns to the reactor (I); And / or, when the oxygen content at the second gas detection point (A2) is less than the oxygen content at the first gas detection point (A1), the control unit (V) puts the device in the first working state; when the oxygen content at the second gas detection point (A2) is greater than or equal to the oxygen content at the first gas detection point (A1), an inert gas is introduced so that the oxygen content at the second gas detection point (A2) is less than or equal to 10 ppm, and the control unit (V) puts the device in the second working state; And / or, when the hydrogen content of the second gas detection point (A2) is greater than 10ppm, the control unit (V) puts the device in the first working state; when the hydrogen content of the second gas detection point (A2) is ≤10ppm, and the water content of the second gas detection point (A2) is less than the water content of the first gas detection point (A1), the control unit (V) puts the device in the second working state; when the hydrogen content of the second gas detection point (A2) is ≤10ppm, and the water content of the second gas detection point (A2) is ≥ the water content of the first gas detection point (A1), an in-situ deactivated catalyst is obtained.

10. The device according to claim 9, wherein: The top and bottom of the catalyst bed (04) are respectively connected to a first temperature measuring point (T1) and a second temperature measuring point (T2), which are used to control the oxygen content in the first inert gas (4) and the water content in the second inert gas (11); And / or, a pressure controller (PC) is provided on the pipeline connecting the top of the liquid separator (III) and the inert gas delivery pipeline (03), and a gas discharge pipeline (05) is also connected to the pipeline connecting the liquid separator (III) and the compressor (IV), for detecting the gas pressure at the top of the liquid separator (III) and regulating at least part of the top gas to enter the compressor (IV); And / or, a reaction raw material delivery pipeline (06) and a reaction product delivery pipeline (07) are respectively provided at the top and the bottom of the reactor (I).

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