Method and device for in-situ deactivation of active metal catalyst

Abstract

The present application relates to the technical field of chemical production, in particular to a method and device for in-situ deactivation of a live metal catalyst, the method provided by the present application adopts a mode of first oxygen circulation reaction and then water circulation reaction, realizes online / in-situ deactivation of the live metal catalyst, avoids the risk of fire caused by the catalyst still active in the process of unloading meeting water and air, and improves the stability and safety of unloading; meanwhile, the method provided by the present application makes the deactivation process more moderate, avoids the generation of hydrogen by direct water injection, increases the problems such as catalyst caking and pasting, and increases the difficulty and safety problems of unloading.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical production, in particular to a method for in-situ deactivation of a live metal catalyst and a device for in-situ deactivation of a live metal catalyst. BACKGROUND

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

[0003] Foreign countries have begun industrial production of 4-methyl-1-pentene since the 1960s. The catalyst used in production is a single alkali metal or a mixed catalyst of multiple alkali metals. The solid base catalyst mainly uses alkali metal as the active component, which shows ultra-high dimerization selectivity in propylene dimerization reaction. At the same time, by reasonable design of the catalyst, the selectivity of single dimerization product can be improved. There are documents reporting that using sodium-potassium alloy as the active component of the catalyst, the prepared catalyst can achieve a conversion rate of more than 20% in propylene dimerization reaction, and the dimerization selectivity can reach more than 95%.

[0004] Since the solid base catalyst in propylene dimerization reaction is a live 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 preparation and transfer process of the catalyst involves strict water-free and oxygen-free operation, and the water and oxygen contents are maintained below 1 ppm and 8 ppm respectively, which has a high operation cost. When the live metal catalyst reaches the service life and needs to be replaced with a new one, the catalyst unloading is a difficult problem. Considering that the live metal may still have a certain activity, the water-free and oxygen-free operation has a high operation cost and is difficult to operate, and it is also easy to cause fire accidents and other accidents, which has a great safety risk. In the laboratory, the live metal catalyst is generally transferred and soaked in heptane solvent in a water-free and oxygen-free environment, and then propylene glycol is introduced to deactivate the catalyst. However, the amount of catalyst used in the laboratory is small, and such deactivation measures are not reasonable in industrial application, and may also bring new safety and environmental protection risks due to the introduction of additional organic chemicals.

[0005] US4982043A applied by Phillips Company discloses mixing inert components when loading the live metal catalyst to avoid danger caused by contact with air during loading. US4988658A and US5057639A disclose mixing inert glass beads when loading the live metal catalyst. However, the above prior art does not consider the deactivation treatment of the live metal catalyst before unloading.

[0006] CN109321274A adopts a one-step process to recycle paraffin from Fischer-Tropsch wax residue and simultaneously passivate and deactivate the catalyst. The Fischer-Tropsch wax residue is mixed with a composite solvent, which is composed of a hydrocarbon solvent, water, and a pore-breaking agent. The catalyst and paraffin solution are obtained by heating and heat preservation, and then solid-liquid separation is performed. CN101405307A discloses a method for deactivating the continuous catalytic olefin polymerization reaction of a Ziegler-Natta or metallocene catalyst. A certain amount of deactivator is injected into the reactor. The deactivator is a mixture of water and isopropyl alcohol. CN1032335A applied by BP Company proposes to deactivate the dimerization catalyst by water treatment. 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 in which the catalyst is continuously added and discharged with the reaction mass. It is significantly different from the unloading operation of the catalyst shutdown process with a certain life span in the fixed bed process.

[0007] While existing technologies involve active metal catalysts with strong reducing properties, the control methods and deactivation timelines for in-situ deactivation of these catalysts via water treatment are unsuitable for fixed-bed reactors due to the different process, environment, and reactor requirements. Furthermore, direct or simple deactivation of alkali metal catalysts in a fixed bed by injecting water into the reactor generates hydrogen, which can increase catalyst agglomeration and gelatinization, making unloading more difficult and posing safety risks. 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. This 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 a first cooling step and a first liquid separation step, and subjecting at least a portion of the obtained first gas to a first compression step, which is then returned and mixed with the first inert gas;

[0011] (2) When the oxygen content in the first gas is greater than or equal to the oxygen content in the first inert gas, introduce inert gas so that the oxygen content in the first gas is less than or equal to 10 ppm, stop the oxygen circulation reaction, and subject the intermediate product to a water circulation reaction; otherwise, repeat step (1);

[0012] (3) contacting the intermediate product with a second inert gas containing water and performing the water circulation reaction; the obtained second circulating stream is subjected to a second cooling and a second liquid separation in sequence; at least a portion of the obtained second gas is subjected to a second compression and then returned to be 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, ℃; 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·°C); 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 Heat of reaction of the oxide with water to form 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·°C); 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 with water circulation reaction Each independently satisfies 0-100°C, preferably 0-50°C.

[0021] A 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 separator, and a compressor connected in sequence, and an oxygen delivery pipeline, a water delivery pipeline, and an inert gas delivery pipeline provided on a pipeline connecting the compressor and the reactor;

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

[0023] In which, 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 when they come into contact with water and air during the unloading process, and improving the stability and safety of the unloading process; 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 and gelatinization, and increase the difficulty and safety of unloading;

[0026] (2) The method provided by the present invention further achieves 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 the control unit, thereby reducing the footprint of the device and lowering costs. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

[0031] Description of Reference Numerals

[0032] I. Reactor; II. Condenser; III. Separating 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 exhaust pipeline; 06. Reaction raw material delivery pipeline; 07. Reaction product delivery pipeline; 1. Oxygen-containing gas; 2. Water; 3. Inert gas; 4. First oxygen-containing inert gas; 5. First circulating stream; 6. First gas; 6-i. Part of the first gas; 6-ii. 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 stream; 13. A second gas; 13-i. A portion of the second gas; 13-ii. The 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 of the ranges and any values ​​disclosed herein 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 endpoints of each range, the endpoints of each range and 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 to be specifically disclosed herein.

[0037] In the present invention, unless otherwise specified, the terms "first" and "second" do not indicate a sequential order or limit the materials or steps involved. They are used only to distinguish or indicate that they are not the same material or step. For example, the terms "first" and "second" in "first cooling" and "second cooling" are used only to indicate that they are not the same cooling process; similarly, the terms "first" and "second" in "first circulating stream" and "second circulating stream" are used only to indicate that they are different circulating streams.

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

[0039] A 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 a first cooling step and a first liquid separation step, and subjecting at least a portion of the obtained first gas to a first compression step, which is then returned and mixed with the first inert gas;

[0041] (2) When the oxygen content in the first gas is greater than or equal to the oxygen content in the first inert gas, introduce inert gas so that the oxygen content in the first gas is less than or equal to 10 ppm, stop the oxygen circulation reaction, and subject the intermediate product to a water circulation reaction; otherwise, repeat step (1);

[0042] (3) contacting the intermediate product with a second inert gas containing water and performing the water circulation reaction; the obtained second circulating stream is subjected to a second cooling and a second liquid separation in sequence; at least a portion of the obtained second gas is subjected to a second compression and then returned to be 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, further 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, as well as 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, ℃; 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 the active metal M 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, %; 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·°C); 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 Reaction heat; 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 Heat of reaction of the oxide with water to form 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·°C); 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 and 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 with 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 range of options, as long as the active metal catalyst meets the above-mentioned 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 circulation reaction is intended to contact the first inert gas containing oxygen with the active metal in the active metal catalyst and carry out an oxygen circulation reaction, so that the active metal is converted into a metal oxide, and an intermediate product and a first circulating stream containing an inert gas and oxygen are obtained. Preferably, in step (1), the conditions of the oxygen 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 first inert gas to the loading volume of the active metal catalyst. In the present invention, the 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 loaded mass of the active metal catalyst, for example, 1%, 2%, 3%, 5%, 8%, 10%, or any value within a range consisting of any two of these values, preferably 2-5%, expressed in kg / kg. The preferred conditions are such that the active metal in the active metal catalyst is completely 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 application, based on the oxygen content in the first gas and the oxygen content in the first inert gas, it is determined whether to carry out an oxygen cycle reaction or a water cycle reaction. When the oxygen content in the first gas < the oxygen content in the first inert gas, the oxygen cycle reaction is carried out, i.e., step (1) is repeated, until when the oxygen content in the first gas ≥ the oxygen content in the first inert gas, the inert gas is introduced so that the oxygen content in the first gas ≤ 10 ppm, the oxygen cycle reaction is stopped, and the water cycle reaction is carried out, i.e., step (2) is carried out.

[0075] In the present application, the water cycle reaction aims to contact the water-containing second inert gas and the metal oxide in the intermediate product and carry out the water cycle reaction, so that the metal oxide is converted into metal hydroxide, obtaining an in-situ inactivated catalyst and a second circulating stream containing inert gas and water. Preferably, in step (3), the conditions of the water 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 0.05-11 MPa, preferably 0.05-5 MPa; a time of 0.5-48 h, preferably 4-24 h; wherein the gas-to-agent ratio is the ratio of the volume of the second inert gas to the packing volume of the active metal catalyst.

[0076] In some embodiments of the present application, preferably, during the water cycle reaction, the water usage is 1-20% of the packing mass of the active metal catalyst, for example, 1%, 2%, 3%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, and any value in the range between any two numerical values, preferably 2-8%, in units of kg / kg. Preferred conditions are adopted so that the metal oxide in the intermediate product is completely converted into metal hydroxide.

[0077] In the present application, the water usage is 0.01-0.2 kg, preferably 0.02-0.08 kg, relative to 1 kg of the packing mass of the active metal catalyst.

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

[0079] In the present application, the second cooling aims 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 application, the second liquid separation aims to separate the second cooled stream into 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 ≤10 ppm 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, thereby obtaining 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 provided on the pipeline connecting the compressor IV and the reactor I;

[0087] The reactor I is provided with a catalyst bed O4 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 separator III and the compressor IV;

[0088] In which, 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 stream 5; the first circulating stream 5 sequentially enters the condenser II and the separator III for a first cooling and a first separation, and at least a portion of the obtained first gas 6 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 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.

[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 into 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 less than or equal to 10ppm, and the control unit V puts the device into the second working state.

[0093] In the present application, preferably, when the hydrogen content of the second gas detection point A2 is > 10 ppm, the regulating unit V makes the device in the first working state; when the hydrogen content of the second gas detection point A2 is ≤ 10 ppm, and the water content of the second gas detection point A2 is < the water content of the first gas detection point A1, the regulating unit V makes the device in the second working state; when the hydrogen content of the second gas detection point A2 is ≤ 10 ppm, and the water content of the second gas detection point A2 is ≥ the water content of the first gas detection point A1, the catalyst in situ inactivated is obtained.

[0094] In one specific embodiment of the present application, when the device is in the first working state, as shown in the figure, 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 to carry out the oxygen circulation reaction, the obtained first circulation stream 5 enters the condenser II to carry out the first cooling, and the obtained first cooled material 8 enters the liquid separator III to carry out the first liquid separation, to obtain the first gas 6 and the first liquid 9, and at least part of the first gas 6 enters the compressor IV to carry out the first compression, and the obtained first compressed gas 7 returns to the reactor I; Figure 2

[0095] Every certain time (for example, 1 h), the oxygen content of the first gas detection point A1 and the second gas detection point A2 is detected, when the oxygen content in the first gas 6 is < the oxygen content in the first inert gas 4, the above-mentioned first working state is repeated; when the oxygen content in the first gas 6 is ≥ the oxygen content in the first inert gas 4, the inert gas is introduced, so that the oxygen content in the first gas 6 is ≤ 10 ppm, and the regulating unit V makes the device in the second working state;

[0096] As shown in the figure, 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 water-containing second inert gas 11 enters the reactor I to carry out the water circulation reaction, the obtained second circulation stream 12 enters the condenser II to carry out the second cooling, the obtained second cooled material 15 enters the liquid separator III to carry out the 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 to carry out the second compression, and the obtained second compressed gas 14 returns to the reactor I; Figure 3 Every certain time (for example, 1 h), the hydrogen content and the water content of the second gas detection point A2, and the first gas detection point A1 are detected, when the hydrogen content in the second gas 13 is ≤ 10 ppm, and the water content is ≥ the water content in the second inert gas 11, the water delivery pipeline 02 and the inert gas delivery pipeline 03 are closed, and the catalyst in situ inactivated is obtained;

[0097]

[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, the above-mentioned second working state is repeated; when the hydrogen content in the second gas 13 is >10ppm, part of the second gas 13 is discharged and inert gas is replenished until the second gas pressure = P2 and the hydrogen content in the second gas is ≤10ppm; the above-mentioned first working state is repeated until the oxygen content in the first gas 6 is ≥the oxygen content in the first inert gas 4, part of the first gas 6 is discharged and inert gas is replenished until the first gas pressure = P1 and the oxygen content in the first gas 6 is ≤10ppm; the device is regulated 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, thereby obtaining 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 the first temperature measuring point T1 and the second temperature measuring point T2, which are used to regulate 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 Reduce the oxygen content in the first inert gas.

[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 temperature difference of the catalyst bed 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 pipe connecting the top of the separatory tank III and the inert gas delivery pipeline 03, and a gas discharge pipeline 05 is also connected to the pipe connecting the separatory tank III and the compressor IV, which is used to detect the gas pressure at the top of the separatory tank III and regulate at least part of the top gas to enter the compressor IV.

[0103] In the present invention, Figure 2As shown, when the device is in the first working state, that is, the oxygen circulation 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. 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, the top and bottom of the reactor 1 are respectively provided with a reaction raw material delivery pipeline 06 and a reaction product delivery pipeline 07.

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

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

[0107] Example 1

[0108] Devices for in-situ deactivation of active metal catalysts such as 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 provided on the pipeline connecting the compressor IV and the reactor I;

[0109] A catalyst bed 04 filled with an active metal catalyst is provided 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 provided above the reactor I; a second gas detection point A2 is provided on the pipeline connecting the liquid separator 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; 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.

[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, and 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 the active metals is 5 wt%, and the activity is 100%) with the first oxygen-containing inert gas (oxygen content is 0.14 wt%) and carry out an oxygen circulation reaction (inlet temperature is 57 ° C, gas-to-agent ratio is 600, inlet pressure is 0.3 MPa, and time is 12 h) to obtain an intermediate product and a first circulating stream; the above-mentioned first circulating stream is subjected to a first cooling, and the obtained first cooled stream (temperature is 40 ° C, pressure is 0.25 MPa) is subjected to a first liquid separation to obtain a first gas (temperature is 40 ° C, pressure is 0.25 MPa); since the pressure of the first gas is ≤ P1 (0.25 MPa), the first gas is subjected to a first compression, and the obtained first compressed gas (temperature is 57 ° C, pressure is 0.3 MPa) is returned to the first inert gas;

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

[0113] During the oxygen circulation reaction, when the temperature difference between the second temperature measurement point T2 and the first temperature measurement point T1 is less than or equal to 1.85° C., the oxygen content in the first inert gas is maintained; otherwise, when the temperature difference between the second temperature measurement point T2 and the first temperature measurement 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 greater than or equal to the oxygen content in the first inert gas, the inert gas is introduced until the oxygen content in the first gas is less than or equal to 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 conducting 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 subjecting the obtained second cooled stream (temperature of 40° C., pressure of 0.25 MPa) to 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), the second gas is subjected to a second compression step, and the obtained 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 in the oxygen circulation reaction is

[0117] During the water circulation reaction, when the temperature difference between the second temperature measurement point T2 and the first temperature measurement point T1 is less than or equal to 30.20° C., the water content in the second inert gas is maintained; otherwise, when the temperature difference between the second temperature measurement point T2 and the first temperature measurement 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 indicates 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 added 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 added until the first gas pressure is maintained at 0.25 MPa and the oxygen content in the first gas is ≤10 ppm. Then, the water circulation delivery pipeline is opened, and step (3) is repeated until the hydrogen content in the second gas is ≤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 12h oxygen cycle reaction is The catalyst bed temperature difference during the 12h water circulation reaction is 1.85℃. It is 30.20℃.

[0120] Example 2

[0121] According to the device of Example 1;

[0122] The method of Example 1 is as follows, except that

[0123] In step (1),

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

[0125] The conditions for 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] The oxygen amount in the oxygen circulation reaction is 3% of the loading mass of the active metal catalyst, in mass units kg / kg; the oxygen content in the first inert gas is 0.19 wt%;

[0127] The catalyst bed temperature difference in the oxygen circulation reaction Satisfies:

[0128]

[0129] In the above oxygen circulation reaction, when the temperature difference (second measuring point T2 - first measuring point T1) is ≤ 4.44℃, the oxygen content in the first inert gas is maintained; otherwise, when the temperature difference (second measuring point T2 - first measuring point T1) is > 4.44℃, the oxygen content in the first inert gas is reduced;

[0130] In step (3),

[0131] The conditions for the water circulation reaction include: an inlet temperature of 57℃, a gas agent ratio of 800, an inlet pressure of 0.3 MPa, and a time of 16 h;

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

[0133]

[0134] In the above water circulation reaction, when the temperature difference (second measuring point T2 - first measuring point T1) is ≤ 19.32℃, the water content in the second inert gas is maintained; otherwise, when the temperature difference (second measuring point T2 - first measuring point T1) is > 19.32℃, the water content in the second inert gas is reduced;

[0135] The remaining conditions are the same, and an in-situ deactivated catalyst is obtained.

[0136] The catalyst bed temperature difference in the oxygen circulation reaction for 16 h is 4.44℃; the catalyst bed temperature difference in the water circulation reaction for 16 h is 19.32℃.

[0137] Comparative Example 1

[0138] The device according to Example 1 is used;

[0139] The method according to Example 1 is used, except that the method is performed in the above device;

[0140] ​​Without step (1) and step (2), without carrying out 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, calculated 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 greater than 10ppm during the deactivation process, part of the second gas is discharged and inert gas is added 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 the 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, which realizes the online / in-situ deactivation of the active metal catalyst, avoids the risk of ignition of the still active catalyst when it comes into contact with water and air during the unloading process, and improves the stability and safety of the unloading; at the same time, through formulas (I) and (II), the temperature difference of the catalyst bed is further controlled.

[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, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as the contents disclosed by the present invention and fall within the scope of protection 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 a first cooling step and a first liquid separation step, and subjecting at least a portion of the obtained first gas to a first compression step, which is then returned and mixed with the first inert gas; (2) When the oxygen content in the first gas is greater than or equal to the oxygen content in the first inert gas, introduce inert gas so that the oxygen content in the first gas is less than or equal to 10 ppm, stop the oxygen circulation reaction, and subject the intermediate product to a water circulation reaction; otherwise, repeat step (1); (3) contacting the intermediate product with a second inert gas containing water and performing the water circulation reaction; the obtained second circulating stream is subjected to a second cooling and a second liquid separation in sequence; at least a portion of the obtained second gas is subjected to a second compression and then returned to be 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, stopping the water circulation reaction to obtain an in-situ deactivated catalyst; Wherein, when the hydrogen content in the second gas is greater than 10ppm, 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 ≤10ppm; repeat step (1) until the oxygen content in the first gas is ≥ the oxygen content in the first inert gas, discharge part of the first gas and supplement inert gas until the pressure of the first gas is =P1 and the oxygen content in the first gas is ≤10ppm; repeat step (3) until the hydrogen content in the second gas is ≤10ppm and the water content is ≥ the water content in the second inert gas, to obtain the in situ deactivated catalyst, wherein P1 and P2 are the outlet pressures of the first cooling and second cooling, respectively.

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, ℃; 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 relative activity of the active metal catalyst based on 100% fresh 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·°C); 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 Heat of reaction of the oxide with water to form hydroxide, kcal / mol; is the active metal M in the fresh active metal catalyst i The loading amount, kg; δ is the relative activity of the active metal catalyst based on 100% fresh 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·°C); 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 with water circulation reaction Each independently meets 0-100℃; And / or, the catalyst bed temperature difference of the oxygen circulation reaction 4. The method according to claim 3, wherein: The catalyst bed temperature difference of the oxygen circulation reaction Catalyst bed temperature difference with water circulation reaction Each independently satisfies 0-50°C.

5. The method according to claim 2, wherein: The active metal M in the active metal catalyst is selected from metals in the periodic table that are more reducible than hydrogen, and is selected from at least one of sodium (Na), potassium (K), lithium (Li), rubidium (Rb), and cesium (Cs); and / or, the active metal loading in the active metal catalyst is 0.5-20 wt%; and / or, the activity δ of the active metal catalyst is 0-100%; 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%.

6. The method according to claim 5, wherein: The active metal M in the active metal catalyst is selected from sodium (Na) and / or potassium (K); and / or, the active metal loading in the active metal catalyst is 0.5-10 wt%; And / or, the activity δ of the active metal catalyst is 0-80%.

7. The method according to claim 1, wherein The conditions for the oxygen circulation reaction and the water circulation reaction independently include: an inlet temperature of 40-100° C.; a gas-to-agent ratio of 50-3000; an inlet pressure of 0.05-11 MPa; and a time of 0.5-48 hours. 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% of the loading mass of the active metal catalyst, measured in kg / kg; And / or, during the water circulation reaction, the amount of water used is 1-20% of the loading mass of the active metal catalyst, measured in kg / kg; And / or, water in the second inert gas exists in gaseous form.

8. The method according to claim 7, wherein: The conditions for the oxygen circulation reaction and the water circulation reaction independently include: an inlet temperature of 40-60° C.; a gas-to-catalyst ratio of 300-1000; an inlet pressure of 0.05-5 MPa; and a time of 4-24 hours. The gas-to-catalyst 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 2-5% of the loading mass of the active metal catalyst, measured in kg / kg; And / or, during the water circulation reaction, the amount of water used is 2-8% of the loading mass of the active metal catalyst, measured in kg / kg.

9. The method according to any one of claims 1 to 8, wherein: When the pressure of the first gas is less than or equal to P1, and P1 is equal to the outlet pressure of the first cooling device, the first gas is subjected to the first compression; otherwise, a portion 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.

10. The method according to claim 9, wherein: When the hydrogen content in the second gas is ≤10 ppm 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.

11. A device for in-situ deactivation of active metal catalysts, characterized in that: The method according to any one of claims 1 to 10 is carried out in the device, which 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 provided 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 separator (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.

12. The device according to claim 11, 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) sequentially enters the condenser (II) and the separator (III) 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) and undergoes 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 the intermediate product and undergoes a water circulation reaction, and the obtained second circulating stream (12) enters the condenser (II) and the 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) places 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) places the device in the second working state; And / or, when the hydrogen content of the second gas detection point (A2) is greater than 10 ppm, the control unit (V) puts the device into the first working state; when the hydrogen content of the second gas detection point (A2) is ≤10 ppm, 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 into the second working state; when the hydrogen content of the second gas detection point (A2) is ≤10 ppm, 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.

13. The device according to claim 12, 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), for regulating 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 separatory tank (III) and the inert gas delivery pipeline (03), and a gas discharge pipeline (05) is further connected to the pipeline connecting the separatory tank (III) and the compressor (IV), for detecting the gas pressure at the top of the separatory tank (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 bottom of the reactor (I).

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