Oxychlorination reactor and oxychlorination method for continuous reforming spent agent, regenerator and method for continuous reforming spent agent

Abstract

The present invention relates to the technical field of continuous reforming catalyst regeneration, and in particular to an oxychlorination reactor and an oxychlorination method for a continuously reforming spent catalyst, and a regenerator and a regeneration method for a continuously reforming spent catalyst. The oxychlorination reactor provided by the present invention reduces the airflow resistance of the catalyst bed and makes the oxychlorination gas more evenly distributed by limiting the catalyst bed to an axial annular arrangement and combining the flow direction of the oxychlorination gas, thereby improving the oxychlorination effect of the continuously reforming spent catalyst; the oxychlorination method of the continuously reforming spent catalyst is carried out in the above reactor, which can effectively improve the chlorine content and active component dispersion of the oxychlorination regeneration catalyst.

Description

Technical Field

[0001] The present invention relates to the technical field of continuous reforming catalyst regeneration, and in particular to an oxychlorination reactor and an oxychlorination method for continuously reforming spent catalyst, and a regenerator and a regeneration method for continuously reforming spent catalyst. Background Art

[0002] Continuous reforming catalyst has two kinds of active centers, namely metal active center and acid active center. The metal active center of the catalyst is provided by the active component (for example, Pt) loaded on the carrier (for example, alumina), and the acid active center is provided by Cl loaded on the alumina carrier, and the Cl content of the catalyst is usually between 1-1.3 weight %. During the production operation, the acidic center Cl will be lost, and the metal center Pt will reunite. Therefore, it is necessary to supplement and adjust the chloride during the catalyst regeneration process to maintain the acidic function. At the same time, the metal Pt reunited on the catalyst is dispersed by oxychlorination, and finally the best matching of the metal function and the acid function of the catalyst is achieved, ensuring the good activity of the catalyst. The chloride adjustment reaction is as follows:

[0003] (1) Chloride compound (tetrachloroethylene) + O2 → HCl + CO2 + H2O

[0004] (2)

[0005] (3)

[0006] (4)

[0007] The existing continuous reforming catalyst chlorination renewal is carried out in the oxychlorination section of the regenerator. The general structure of the oxychlorination section is as follows: Figure 3 As shown, the charred reforming catalyst flows downward through the columnar oxychlorination section bed, and the heated chloride and air are mixed and then reversely contact the catalyst. The columnar catalyst bed has the following disadvantages: (1) The bed thickness is large, and the resistance to the passage of the chlorination gas flow is large; (2) The gas flow distribution is uneven, and the oxychlorination effect of the catalyst is not exactly the same; (3) The bed heat transfer effect is poor, the catalyst bed temperature is low, and the temperature distribution is uneven, which affects the oxychlorination effect of the catalyst.

[0008] Therefore, there is an urgent need for a new oxychlorination reactor for continuous reforming of spent catalyst. Summary of the invention

[0009] The purpose of the present invention is to overcome the problems of large airflow resistance, uneven airflow distribution, and uneven oxychlorination effect in the oxychlorination section of the existing continuous reforming spent agent, and to provide an oxychlorination reactor and oxychlorination method for continuous reforming spent agent, a regenerator and regeneration method for continuous reforming spent agent. The reactor significantly reduces the oxychlorination gas resistance by limiting the axial annular arrangement of the catalyst bed, and the radial flow of the oxychlorination gas through the catalyst bed, so that the oxychlorination gas is evenly distributed, thereby improving the oxychlorination effect of the continuous reforming spent agent.

[0010] In order to achieve the above-mentioned object, the first aspect of the present invention provides an oxychlorination reactor for continuous reforming of spent catalyst, the reactor comprising a shell, the shell being provided with a gas discharge pipe; the shell being provided with a catalyst bed arranged in an annular manner around the central axis of the shell, the catalyst bed being filled with a coke regeneration catalyst, and the interior of the shell being divided into a gas feed zone and a gas discharge zone; the gas feed zone is a zone formed by the outer side surface of the catalyst bed and the inner wall of the shell, and the gas discharge zone is a zone surrounded by the inner side surface of the catalyst bed;

[0011] The gas feed zone is used to make the oxychlorination gas flow downward and radially through the catalyst bed to contact and react with the coke regeneration catalyst, and the obtained gas product is collected in the gas discharge zone and discharged through the gas discharge pipe.

[0012] The second aspect of the present invention provides a method for oxychlorination of a continuously reforming spent agent, which method is carried out in the reactor provided in the first aspect.

[0013] Preferably, the method comprises: introducing oxychlorination gas into a gas feed zone in the reactor, and the oxychlorination gas flows downward and radially through a catalyst bed in the reactor, contacts and reacts with a charred regenerated catalyst loaded in the catalyst bed, and obtains an oxychlorination regenerated catalyst and a gas product; wherein the gas product is collected in a gas discharge zone in the reactor and discharged through a gas discharge pipe; wherein the charred regenerated catalyst is obtained by charring a continuously reforming spent catalyst.

[0014] The third aspect of the present invention provides a regenerator for continuous reforming of spent catalyst, the regenerator is divided into a charring zone, an oxychlorination zone, a drying zone and a cooling zone from top to bottom; wherein the oxychlorination zone is the reactor provided in the first aspect.

[0015] A fourth aspect of the present invention provides a method for regenerating a spent agent in a continuous reforming process, wherein the method is carried out in the regenerator provided in the third aspect.

[0016] Preferably, the method comprises: subjecting the continuous reforming spent agent to charring treatment, oxychlorination treatment, drying treatment and cooling treatment in sequence to obtain the continuous reforming regenerated agent.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] (1) The oxychlorination reactor provided by the present invention reduces the gas flow resistance of the catalyst bed and makes the oxychlorination gas more evenly distributed by limiting the catalyst bed to an axial annular arrangement and combining the flow direction of the oxychlorination gas, thereby improving the oxychlorination effect of the spent catalyst in the continuous reforming process;

[0019] (2) The oxychlorination method of the continuous reforming spent catalyst is carried out in the above reactor, which can effectively increase the chlorine content and active component dispersion of the oxychlorination regeneration catalyst; at the same time, it can effectively reduce the amount of oxychlorination gas added, save costs, and facilitate industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a structural schematic diagram of an oxychlorination reactor for continuous reforming of spent catalyst provided by the present invention;

[0021] Figure 2 It is a schematic diagram of a top view of an oxychlorination reactor for continuous reforming of spent catalyst provided by the present invention;

[0022] Figure 3 It is a schematic diagram of the structure of a traditional oxychlorination reactor.

[0023] Description of Reference Numerals

[0024] 1. Shell 2. Gas discharge pipe 3. Catalyst bed

[0025] 4. Gas feed zone 5. Gas discharge zone 6. External side of catalyst bed

[0026] 7. Inner side of catalyst bed 8. Upper plate surface of catalyst bed 9. Lower plate surface of catalyst bed

[0027] 10. Catalyst feed pipe 11. Catalyst discharge pipe 12. Gas inlet

[0028] 13. Gas distributor 14. Annular baffle 15. Baffle DETAILED DESCRIPTION

[0029] 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.

[0030] In the present invention, unless otherwise specified, the "top" of a container refers to the 0-10% position of the container from top to bottom; the "upper part" of a container refers to the 10-40% position of the container from top to bottom; the "middle part" of a container refers to the 40-60% position of the container from top to bottom; the "lower part" of a container refers to the 60-90% position of the container from top to bottom; and the "bottom" of a container refers to the 90-100% position of the container from top to bottom.

[0031] The first aspect of the present invention provides an oxychlorination reactor for continuous reforming of spent catalyst, the reactor comprising a shell, the shell being provided with a gas discharge pipe; the shell being provided with a catalyst bed arranged in an annular manner around the central axis of the shell, the catalyst bed being filled with a coke regeneration catalyst, and the interior of the shell being divided into a gas feed zone and a gas discharge zone; the gas feed zone is a zone formed by the outer side surface of the catalyst bed and the inner wall of the shell, and the gas discharge zone is a zone surrounded by the inner side surface of the catalyst bed;

[0032] The gas feed zone is used to make the oxychlorination gas flow downward and radially through the catalyst bed to contact and react with the coke regeneration catalyst, and the obtained gas product is collected in the gas discharge zone and discharged through the gas discharge pipe.

[0033] The inventors of the present invention have found that: by changing the catalyst bed in the oxychlorination section of the continuous reforming spent catalyst from a columnar shape to a double mesh arranged in an annular shape, and combining the oxychlorination gas to radially pass through the catalyst bed, contacting and reacting with the burnt regenerated catalyst loaded in the catalyst bed, compared with the thickness of the axial catalyst bed, due to the small radial thickness of the catalyst bed, the airflow resistance is also greatly reduced, the airflow distribution is more uniform, the heat carried in the airflow can more easily increase the temperature of the catalyst bed, and at the same time, the temperature of the catalyst bed is more uniform, the chlorine is applied to the catalyst faster and more evenly, the metal center dispersion effect is better, and the chlorine injection amount is lower.

[0034] In the present invention, unless otherwise specified, the charred regenerated catalyst is obtained by charring the spent catalyst of the continuous reforming system, in order to reduce the amount of carbon deposits of the spent catalyst of the continuous reforming system.

[0035] According to the present invention, preferably, the catalyst bed is provided with an upper plate surface and a lower plate surface, both of which are plate surfaces through which gas cannot pass; the catalyst bed is provided with an inner side surface and an outer side surface, both of which are mesh surfaces through which gas can pass. This arrangement can ensure that the oxychlorination gas flows downward and radially through the catalyst bed.

[0036] According to the present invention, preferably, the lower plate surfaces independently extend along the radial direction of the shell to connect with the inner wall of the shell. This arrangement can ensure that the oxychlorination gas flows downward and radially passes through the catalyst bed.

[0037] According to the present invention, preferably, the upper plate surface and the lower plate surface are each independently provided with at least one catalyst feed pipe and at least one catalyst discharge pipe; further preferably, the catalyst feed pipe and the catalyst discharge pipe are respectively provided on the upper plate surface and the lower plate surface. In the present invention, the catalyst feed pipe is used to introduce the charred regeneration catalyst into the catalyst bed, and the catalyst discharge pipe is used to lead the oxychlorination regeneration catalyst out of the catalyst bed.

[0038] In some embodiments of the present invention, preferably, the ratio of the radius of the catalyst feed pipe and the catalyst discharge pipe to the radial thickness of the catalyst bed is independently 0.05-0.3:1, for example, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.3:1, and any value in the range of any two numerical values, preferably 0.1-0.2:1.

[0039] In the present invention, unless otherwise specified, the radial thickness of the catalyst bed refers to the difference between the major radius and the minor radius of the catalyst bed on the same horizontal plane, that is, the difference between the outer radius of the catalyst bed and the inner radius of the catalyst bed on the same horizontal plane.

[0040] In some embodiments of the present invention, preferably, the ratio of the radial thickness of the catalyst bed to the radius of the shell is 0.2-0.8:1, for example, 0.2:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, and any value in the range of any two values, preferably 0.4-0.6:1. When the ratio of the two is lower than 0.2, the oxychlorination gas flows smoothly, but the flow of the upper charred catalyst downward is limited due to the thinning of the radial thickness of the catalyst bed, the flow resistance increases, and the flow rate is limited, which also limits the normal charring cycle of the catalyst; when the ratio of the two is greater than 0.8, the resistance of the oxychlorination gas flow through the catalyst bed increases, and the oxychlorination effect becomes worse.

[0041] In the present invention, there is no specific limitation on the height of the catalyst bed, as long as the radial thickness of the catalyst bed meets the above limitation.

[0042] According to the present invention, preferably, the gas discharge pipe is connected to the upper plate surface of the catalyst bed, and the outer diameter of the gas discharge pipe is ≥ the radial width of the gas discharge zone along the shell; further preferably, the outer diameter of the gas discharge pipe is = the radial width of the gas discharge zone along the shell.

[0043] In some embodiments of the present invention, preferably, the ratio of the width of the gas discharge zone along the radial direction of the shell to the radius of the shell is 0.1-0.4:1, for example, 0.1:1, 0.2:1, 0.25:1, 0.3:1, 0.4:1, and any value in the range consisting of any two values, preferably 0.2-0.3:1.

[0044] According to the present invention, preferably, the side wall of the shell is provided with a gas inlet for introducing the oxychlorination gas into the gas feed zone; further preferably, the gas inlet is higher than the upper plate surface of the catalyst bed. Such a configuration facilitates uniform distribution of the oxychlorination gas from top to bottom.

[0045] According to the present invention, preferably, the catalyst bed is used to contact the burnt regenerated catalyst with oxychlorination gas and react to obtain oxychlorination regenerated catalyst and gas product.

[0046] In some embodiments of the present invention, preferably, there is a gap between the outer side surface of the catalyst bed and the inner wall of the shell.

[0047] In some embodiments of the present invention, preferably, the ratio of the width of the gap along the radial direction of the shell to the radius of the shell is 0.1-0.4:1, for example, 0.1:1, 0.2:1, 0.25:1, 0.3:1, 0.4:1, and any value in the range of any two values, preferably 0.2-0.3:1. When the ratio of the two is less than 0.1, the radial velocity of the airflow is large, the catalyst near the outer mesh wall is blown away, a cavity is formed, the catalyst is severely worn, and the oxychlorination effect is poor; when the ratio of the two is greater than 0.4, the radial pressure of the airflow through the bed is insufficient, and the airflow cannot pass through the catalyst bed quickly, and the oxychlorination effect becomes poor.

[0048] The present invention provides a structural schematic diagram of an oxychlorination reactor for continuous reforming of spent catalyst. Figure 1-2 As shown by Figure 1-2 It can be seen that the reactor includes a shell 1, on which a gas discharge pipe 2 is arranged; a catalyst bed 3 arranged in an annular manner around the central axis of the shell is arranged inside the shell 1, and the catalyst bed 3 is filled with a coke regeneration catalyst, and the inside of the shell 1 is divided into a gas feed zone 4 and a gas discharge zone 5; the gas feed zone 4 is a zone formed by the outer side surface 6 of the catalyst bed and the inner wall of the shell 1, and the gas discharge zone 5 is a zone surrounded by the inner side surface 7 of the catalyst bed;

[0049] The gas feed zone 4 is used to flow the oxychlorination gas downward and radially through the catalyst bed 3 to contact and react with the coke regeneration catalyst, and the obtained gas product is collected in the gas discharge zone 5 and then discharged through the gas discharge pipe 2;

[0050] The catalyst bed 3 is provided with an upper plate surface 8 and a lower plate surface 9, both of which are plate surfaces through which gas cannot pass; the catalyst bed 3 is provided with an inner side surface 7 and an outer side surface 6, both of which are mesh surfaces through which gas can pass; the upper plate surface 8 and the lower plate surface 9 are each independently provided with at least one catalyst feed pipe 10 and at least one catalyst discharge pipe 11; the gas discharge pipe 2 is connected to the upper plate surface 8 of the catalyst bed, and the outer diameter of the gas discharge pipe 2 is equal to the radial width of the gas discharge zone 5 along the shell;

[0051] The side wall of the shell 1 is provided with a gas inlet 12 which is higher than the upper plate surface 8 of the catalyst bed.

[0052] According to a particularly preferred embodiment of the present invention, the reactor comprises a shell, on which a gas discharge pipe is arranged; a catalyst bed arranged in an annular manner around the central axis of the shell is arranged inside the shell, the catalyst bed is filled with a coke regeneration catalyst, and the interior of the shell is divided into a gas feed zone and a gas discharge zone; the gas feed zone is an area formed by the outer side surface of the catalyst bed and the inner wall of the shell, and the gas discharge zone is an area surrounded by the inner side surface of the catalyst bed;

[0053] The gas feed zone is used to flow the oxychlorination gas downward and radially through the catalyst bed to contact and react with the coke regeneration catalyst, and the obtained gas product is discharged through the gas discharge pipe after being collected in the gas discharge zone;

[0054] The catalyst bed is provided with an upper plate surface and a lower plate surface, both of which are plate surfaces through which gas cannot pass; the catalyst bed is provided with an inner side surface and an outer side surface, both of which are mesh surfaces through which gas can pass; the gas discharge pipe is connected to the upper plate surface of the catalyst bed, and the outer diameter of the gas discharge pipe is equal to the radial width of the gas discharge area along the shell;

[0055] Wherein, the ratio of the radial thickness of the catalyst bed to the radius of the shell is 0.4-0.6:1.

[0056] The second aspect of the present invention provides a method for oxychlorination of a continuously reforming spent agent, which method is carried out in the reactor provided in the first aspect.

[0057] In some embodiments of the present invention, preferably, the method comprises: introducing oxychlorination gas into the gas feed zone in the reactor, and the oxychlorination gas flows downward and radially through the catalyst bed in the reactor, contacts and reacts with the charred regenerated catalyst loaded in the catalyst bed, and obtains oxychlorination regenerated catalyst and gas product; wherein the gas product is collected in the gas discharge zone in the reactor and discharged through the gas discharge pipe; wherein the charred regenerated catalyst is obtained by charring the spent catalyst of the continuous reforming reactor.

[0058] In some embodiments of the present invention, preferably, the temperature of the oxychlorination gas is 480-530°C, for example, 480°C, 500°C, 510°C, 530°C, and any value in the range consisting of any two values, preferably 500-510°C.

[0059] In the present invention, the oxychlorination gas mainly contains oxygen, nitrogen and chloride, and other impurities are all at the ppm level. Preferably, the chlorine content in the oxychlorination gas is 0.1-1% by weight, preferably 0.2-0.8% by weight; the oxygen content is 15-30% by weight, preferably 20-25% by weight.

[0060] In the present invention, unless otherwise specified, the spent continuous reforming catalyst is a deactivated continuous reforming catalyst.

[0061] In some embodiments of the present invention, preferably, the carbon deposit amount of the continuous reforming spent agent is 2-7% by weight, preferably 3-5% by weight; the chlorine content is 0.8-1.2% by weight, preferably 0.9-1.1% by weight; and the active component content is 0.2-0.4% by weight, preferably 0.25-0.35% by weight.

[0062] In the present invention, the active component includes but is not limited to Pt.

[0063] In some embodiments of the present invention, preferably, the carbon deposit amount of the burnt regenerated catalyst is less than 0.2% by weight.

[0064] In the present invention, unless otherwise specified, the carbon deposition amount parameter is measured by the sulfur-carbon instrument charring method (Q / SH 3360317-2020); the chlorine content parameter is measured by the automatic potentiometric titration method (Q / SH 3360 320-2020); the active component content parameter is measured by the spectrophotometric method (NB / SH T 0570-2017); the active component dispersion is measured by the hydrogen-oxygen titration method (TPT, oxidizing the metal Pt on the surface of the catalyst, and then introducing hydrogen to reduce the oxidized Pt obtained previously, and calculating the Pt dispersion based on the amount of hydrogen consumed); the specific surface area parameter is measured by the nitrogen adsorption method (ASTM D4567-2003 (2008)).

[0065] In the present invention, the reaction conditions have a wide range of selection. Preferably, the temperature is 480-530°C, preferably 500-510°C; the gas-to-agent ratio is 600-1500:1, preferably 800-1000:1; the time is 2-6h, preferably 3-5h. The gas-to-agent ratio refers to the ratio of oxychlorination gas in mL to the regenerated catalyst in g after charring.

[0066] In some embodiments of the present invention, preferably, the chlorine content of the oxychlorination regeneration catalyst is 0.9-1.3% by weight, preferably 1-1.2% by weight; the active component dispersion is 0.8-1%, preferably 0.9-1%; the specific surface area is 180-220m 2 / g, preferably 190-210m 2 / g.

[0067] The third aspect of the present invention provides a regenerator for continuous reforming of spent catalyst, the regenerator is divided into a charring zone, an oxychlorination zone, a drying zone and a cooling zone from top to bottom; wherein the oxychlorination zone is the reactor provided in the first aspect.

[0068] In the present invention, unless otherwise specified, the outlet of the charring zone is connected to the catalyst feed pipe in the oxychlorination reactor provided by the present invention, so as to introduce the charring regenerated catalyst into the catalyst bed; the catalyst discharge pipe in the oxychlorination reactor is connected to the inlet of the drying zone, so as to dry the oxychlorination regenerated catalyst.

[0069] In the present invention, unless otherwise specified, the charring zone is intended to contact the continuously reforming spent catalyst with an oxygen-containing gas and remove the carbon deposits of the continuously reforming spent catalyst to obtain a charred regenerated catalyst; the oxychlorination zone is intended to contact and react the charred regenerated catalyst with an oxychlorination gas to increase the chlorine content and the dispersion of active components in the charred regenerated catalyst to obtain an oxychlorination regenerated catalyst; the drying zone is intended to dry the oxychlorination regenerated catalyst at a high temperature to remove water and residual chlorine on the surface to obtain a dried regenerated catalyst; the cooling zone is intended to reduce the temperature of the dried regenerated catalyst to obtain a continuous reforming regenerated agent.

[0070] A fourth aspect of the present invention provides a method for regenerating a spent agent in a continuous reforming process, wherein the method is carried out in the regenerator provided in the third aspect.

[0071] In some embodiments of the present invention, preferably, the method comprises: subjecting the spent continuous reforming agent to charring treatment, oxychlorination treatment, drying treatment and cooling treatment in sequence to obtain a regenerated continuous reforming agent.

[0072] In the present invention, unless otherwise specified, the types of the spent agent for continuous reforming and the parameter limitations thereof are in accordance with the above-mentioned limitations, and the present invention will not elaborate on them herein.

[0073] In some embodiments of the present invention, preferably, the charring treatment process includes: contacting the continuous reforming spent catalyst with an oxygen-containing gas and charring it to obtain a charred regenerated catalyst; wherein the oxygen content in the oxygen-containing gas is preferably 0.5-1 volume %; the charring conditions preferably include: a temperature of 500-580°C and a time of 2-4h.

[0074] In some embodiments of the present invention, preferably, the oxychlorination treatment process comprises: contacting the charred regenerated catalyst with an oxychlorination gas and reacting to obtain an oxychlorination regenerated catalyst. The type of oxychlorination gas and the reaction conditions are in accordance with the above-mentioned definitions, and the present invention will not elaborate on them here.

[0075] In some embodiments of the present invention, preferably, the drying process comprises: drying the oxychlorination regeneration catalyst preferably at 550-560° C. for 2-4 hours to obtain a dry regeneration catalyst.

[0076] In some embodiments of the present invention, preferably, the cooling process includes: contacting the dried regenerated catalyst with a cooling medium and exchanging heat to obtain a regenerated catalyst at 100-200° C. The cooling medium includes but is not limited to air, water, etc.

[0077] The present invention will be described in detail below through examples.

[0078] In the oxychlorination reactor ( Figure 1-2), the reactor comprises a shell 1, on which a gas discharge pipe 2 is arranged; a catalyst bed 3 arranged in an annular manner around the central axis of the shell is arranged inside the shell 1, the catalyst bed 3 is filled with a charred regeneration catalyst, and the inside of the shell 1 is divided into a gas feed zone 4 and a gas discharge zone 5; the gas feed zone 4 is a zone formed by the outer side surface 6 of the catalyst bed and the inner wall of the shell 1, and the gas discharge zone 5 is a zone surrounded by the inner side surface 7 of the catalyst bed; wherein the gas feed zone 4 is used to flow the oxychlorination gas downward and radially through the catalyst bed 3, contact with the charred regeneration catalyst and react, to obtain The gaseous products are collected in the gas discharge area 5 and discharged through the gas discharge pipe 2; wherein, the catalyst bed 3 is provided with an upper plate surface 8 and a lower plate surface 9, both of which are plate surfaces that gas cannot pass through; the catalyst bed 3 is provided with an inner side surface 7 and an outer side surface 6, both of which are mesh surfaces that gas can pass through; the upper plate surface 8 and the lower plate surface 9 are each independently provided with 7 catalyst feed pipes 10 and 7 catalyst discharge pipes 11; the gas discharge pipe 2 is connected to the upper plate surface 8 of the catalyst bed, and the outer diameter of the gas discharge pipe 2 is equal to the radial width of the gas discharge area 5 along the shell; wherein, the side wall of the shell 1 is provided with a gas inlet 12 higher than the upper plate surface 8 of the catalyst bed.

[0079] Comparative Examples 1-6 In a conventional oxychlorination reactor ( Figure 3 ), the burnt regenerated catalyst flows downward through the columnar catalyst bed 3, the heated (500°C) chloride-containing and air mixed gas flows from bottom to top after passing through the gas inlet 12 and the gas distributor 13, and after being turned back by the baffle plate 15, it passes through the catalyst bed 3 from bottom to top, and contacts the burnt regenerated catalyst flowing downward in reverse direction, the temperature of the catalyst bed is mainly controlled by the heat carried by the chlorination gas flow, due to the large thickness of the bed layer, large air flow resistance and uneven distribution, resulting in uneven temperature distribution of the catalyst bed, and the bed temperature is not easy to increase (the temperature of the oxychlorination bed layer of the industrial device is usually (about 450-480°C), the catalyst oxychlorination effect is affected, and a higher chlorine injection amount is required to increase the chlorine content of the catalyst. The chlorine injection amount of the domestic catalyst is usually: 0.06-0.08% of the catalyst circulation amount, and the chlorine injection amount required for the foreign catalyst is higher.

[0080] Example 1

[0081] The continuous reforming spent catalyst A (coking amount of 5.1 wt%, Cl content of 1.03 wt%, active component Pt content of 0.28 wt%) was contacted with an oxygen-containing gas (oxygen content of 0.85 vol%) and charred to obtain a charred regenerated catalyst A (coking amount of 0.02 wt%), the charring temperature was 550°C, and the charring time was 2 h;

[0082] 100g of burnt regenerated catalyst A was loaded into Figure 1In the catalyst bed of the reactor shown, 500°C oxychlorination gas (Cl content of 0.02 wt.%, oxygen content of 23.2 wt.%) is introduced into the gas feed zone of the reactor, the oxychlorination gas flows downward and radially flows through the catalyst bed, contacts with the burnt regenerated catalyst A and reacts, and the reaction conditions include: temperature of 500°C; gas-to-agent ratio of 1000:1; time of 2h, and the obtained oxychlorination regenerated catalyst S1 and gaseous products; the oxychlorination regenerated catalyst S1 is led out through the catalyst discharge pipe, and the gaseous products are collected in the gas discharge zone of the reactor and discharged through the gas discharge pipe.

[0083] In the oxychlorination reactor, the ratio of the radius of the catalyst feed pipe and the catalyst discharge pipe to the radial thickness of the catalyst bed is independently 0.15:1; the ratio of the radial thickness of the catalyst bed to the radius of the shell is 0.5:1; the ratio of the radial width of the gas discharge zone along the shell to the radius of the shell is 0.25:1; there is a gap between the outer side surface of the catalyst bed and the inner wall of the shell, and the ratio of the radial width of the gap to the radius of the shell is 0.25:1.

[0084] The physical properties of the oxychlorination regeneration catalyst S1 are listed in Table 1.

[0085] Table 1

[0086]

[0087] Comparative Example 1

[0088] The method of Example 1 was followed, except that 100 g of the charred regenerated catalyst A was loaded into Figure 2 In the catalyst bed of the reactor shown, the remaining steps are the same to obtain the oxychlorination regeneration catalyst DS1.

[0089] Among them, the physical properties of the oxychlorination regeneration catalyst DS1 are listed in Table 1.

[0090] Example 2

[0091] The method of Example 1 is followed, except that the reaction time is replaced with 4 hours, and the remaining steps are the same to obtain the oxychlorination regeneration catalyst S2.

[0092] Among them, the physical properties of the oxychlorination regeneration catalyst S2 are listed in Table 2.

[0093] Table 2

[0094]

[0095] Comparative Example 2

[0096] The method of Example 2 was followed, except that 100 g of the charred regenerated catalyst A was loaded into Figure 2In the catalyst bed of the reactor shown, the remaining steps are the same to obtain the oxychlorination regeneration catalyst DS2.

[0097] Among them, the physical properties of the oxychlorination regeneration catalyst DS2 are listed in Table 2.

[0098] Example 3

[0099] The method of Example 1 is followed, except that the reaction time is replaced with 6 hours, and the remaining steps are the same to obtain the oxychlorination regeneration catalyst S3.

[0100] Among them, the physical properties of the oxychlorination regeneration catalyst S3 are listed in Table 3.

[0101] Table 3

[0102]

[0103]

[0104] Comparative Example 3

[0105] The method of Example 3 was followed, except that 100 g of the charred regenerated catalyst A was loaded into Figure 2 In the catalyst bed of the reactor shown, the remaining steps are the same to obtain the oxychlorination regeneration catalyst DS3.

[0106] Among them, the physical properties of the oxychlorination regeneration catalyst DS3 are listed in Table 3.

[0107] Example 4

[0108] The continuous reforming spent catalyst B (coking amount of 4.8 wt%, Cl content of 0.94 wt%, active component Pt content of 0.28 wt%) was contacted with an oxygen-containing gas (oxygen content of 0.8 volume %) and charred to obtain a charred regenerated catalyst B (coking amount of 0.01 wt%), the charring temperature was 535° C., and the charring time was 2 h;

[0109] 100g of burnt regenerated catalyst B was loaded into Figure 1 In the catalyst bed of the reactor shown, 500°C oxychlorination gas (Cl content of 1% by weight, oxygen content of 22.8% by weight) is introduced into the gas feed zone of the reactor, and the oxychlorination gas flows downward and radially flows through the catalyst bed, contacts with the burnt regenerated catalyst B and reacts. The reaction conditions include: temperature of 500°C; gas-to-agent ratio of 1000:1; time of 2h, and the obtained oxychlorination regenerated catalyst S4 and gaseous products; the oxychlorination regenerated catalyst S4 is led out through the catalyst discharge pipe, and the gaseous products are collected in the gas discharge zone of the reactor and discharged through the gas discharge pipe.

[0110] In the oxychlorination reactor, the ratio of the radius of the catalyst feed pipe and the catalyst discharge pipe to the radial thickness of the catalyst bed is independently 0.2:1; the ratio of the radial thickness of the catalyst bed to the radius of the shell is 0.6:1; the ratio of the radial width of the gas discharge zone to the radius of the shell is 0.2:1; there is a gap between the outer side surface of the catalyst bed and the inner wall of the shell, and the ratio of the radial width of the gap to the radius of the shell is 0.2:1.

[0111] Among them, the physical properties of the oxychlorination regeneration catalyst S4 are listed in Table 4.

[0112] Table 4

[0113]

[0114] Comparative Example 4

[0115] The method of Example 4 was followed, except that 100 g of the charred regenerated catalyst B was loaded into Figure 2 In the catalyst bed of the reactor shown, the remaining steps are the same to obtain the oxychlorination regeneration catalyst DS4.

[0116] Among them, the physical properties of the oxychlorination regeneration catalyst DS4 are listed in Table 4.

[0117] Example 5

[0118] The method of Example 4 is followed, except that the reaction time is replaced with 4 hours, and the remaining steps are the same to obtain oxychlorination regeneration catalyst S5.

[0119] Among them, the physical properties of the oxychlorination regeneration catalyst S5 are listed in Table 5.

[0120] Table 5

[0121]

[0122] Comparative Example 5

[0123] The method of Example 5 was followed, except that 100 g of the charred regenerated catalyst B was loaded into Figure 2 In the catalyst bed of the reactor shown, the remaining steps are the same to obtain the oxychlorination regeneration catalyst DS5.

[0124] Among them, the physical properties of the oxychlorination regeneration catalyst DS5 are listed in Table 5.

[0125] Example 6

[0126] The method of Example 4 is followed, except that the reaction time is replaced with 6 hours, and the remaining steps are the same to obtain the oxychlorination regeneration catalyst S6.

[0127] Among them, the physical properties of the oxychlorination regeneration catalyst S6 are listed in Table 6.

[0128] Table 6

[0129]

[0130] Comparative Example 6

[0131] The method of Example 6 was followed, except that 100 g of the charred regenerated catalyst B was loaded into Figure 2 In the catalyst bed of the reactor shown, the remaining steps are the same to obtain the oxychlorination regeneration catalyst DS6.

[0132] Among them, the physical properties of the oxychlorination regeneration catalyst DS6 are listed in Table 6.

[0133] Compared with Comparative Examples 1-6, the oxychlorination regeneration catalysts prepared by the oxychlorination reactor provided by the present invention in Examples 1-6 have higher chlorine content and Pt dispersion, and the chlorine content and oxygen content in the oxychlorination gas can be adjusted to achieve the controllability of the chlorine content and Pt dispersion in the oxychlorination regeneration catalyst. At the same time, the oxychlorination reactor provided by the present invention can optimize the gas flow distribution and temperature distribution of the catalyst bed, enhance the oxychlorination effect of the catalyst, improve the reaction activity of the catalyst, and significantly reduce the amount of chloride used, saving capital investment.

[0134] 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 oxychlorination of a spent catalyst for continuous reforming, the method being carried out in an oxychlorination reactor for continuous reforming spent catalyst, characterized in that: The reactor comprises a shell, on which a gas discharge pipe is arranged; a catalyst bed is arranged in an annular manner around the central axis of the shell inside the shell, the catalyst bed is filled with a coke regeneration catalyst with a carbon deposition amount of less than 0.2% by weight, and the inside of the shell is divided into a gas feed zone and a gas discharge zone; the gas feed zone is a zone formed by the outer side surface of the catalyst bed and the inner wall of the shell, and the gas discharge zone is a zone surrounded by the inner side surface of the catalyst bed; the ratio of the width of the gas discharge zone along the radial direction of the shell to the radius of the shell is 0.2-0.3:1; The gas feed zone is used to flow the oxychlorination gas downward and radially through the catalyst bed to contact and react with the coke regeneration catalyst, and the obtained gas product is discharged through the gas discharge pipe after being collected in the gas discharge zone; Wherein, the gas discharge pipe is connected to the upper plate surface of the catalyst bed, and the outer diameter of the gas discharge pipe is greater than or equal to the radial width of the gas discharge zone along the shell; wherein the side wall of the shell is provided with a gas inlet for allowing the oxychlorination gas to enter the gas feed zone; Wherein, the gas inlet is higher than the upper plate surface of the catalyst bed; Wherein, the gas inlet is arranged below the gas discharge pipe; The reaction conditions include: temperature of 480-530°C; gas-to-agent ratio of 600-1500:1; time of 2-6h; gas-to-agent ratio refers to the ratio of oxychlorination gas in mL to charred regenerated catalyst in g; the temperature of the oxychlorination gas is 480-530°C; the chlorine content in the oxychlorination gas is 0.1-1% by weight; the oxygen content is 15-30% by weight; Wherein, the ratio of the radial thickness of the catalyst bed to the radius of the shell is 0.4-0.6:1; There is a gap between the outer side of the catalyst bed and the inner wall of the shell; the ratio of the width of the gap along the radial direction of the shell to the radius of the shell is 0.2-0.3:1; The catalyst bed is provided with an upper plate surface and a lower plate surface, both of which are plate surfaces through which gas cannot pass, and the lower plate surface extends along the radial direction of the shell to be connected with the inner wall of the shell.

2. The method according to claim 1, wherein: The catalyst bed is provided with an inner side surface and an outer side surface, both of which are mesh surfaces through which gas can pass.

3. The method according to claim 2, wherein: The upper plate surface and the lower plate surface are each independently provided with at least one catalyst feed pipe and at least one catalyst discharge pipe.

4. The method according to claim 3, wherein: The catalyst feed pipe and the catalyst discharge pipe are respectively arranged on the upper plate surface and the lower plate surface.

5. The method according to claim 4, wherein: The ratio of the radius of the catalyst feed pipe and the catalyst discharge pipe to the radial thickness of the catalyst bed is independently 0.05-0.3:

1.

6. The method according to claim 5, wherein: The ratios of the radii of the catalyst feed pipe and the catalyst discharge pipe to the radial thickness of the catalyst bed are independently 0.1-0.2:

1.

7. The method according to any one of claims 1 to 6, wherein: The catalyst bed is used to contact the burnt regenerated catalyst with oxychlorination gas and react to obtain oxychlorination regenerated catalyst and gas product.

8. The method according to claim 1, wherein: The method comprises: introducing oxychlorination gas into a gas feed zone in the reactor, and the oxychlorination gas flows downward and radially through a catalyst bed in the reactor, contacts and reacts with a charred regenerated catalyst loaded in the catalyst bed, and obtains an oxychlorination regenerated catalyst and a gas product; wherein the gas product is collected in a gas discharge zone in the reactor and discharged through a gas discharge pipe; The charred regenerated catalyst is obtained by charring the spent catalyst of continuous reforming.

9. The method according to claim 1, wherein: The temperature of the oxychlorination gas is 500-510°C; The chlorine content of the oxychlorination gas is 0.2-0.8% by weight; the oxygen content is 20-25% by weight.

10. The method according to claim 1, wherein: The carbon deposit amount of the spent catalyst for continuous reforming is 2-7% by weight; the chlorine content is 0.8-1.2% by weight; and the active component content is 0.2-0.4% by weight.

11. The method according to claim 10, wherein: The carbon deposit amount of the spent catalyst for continuous reforming is 3-5% by weight; the chlorine content is 0.9-1.1% by weight; and the active component content is 0.25-0.35% by weight.

12. The method according to claim 1, wherein: The reaction conditions include: temperature of 500-510° C.; gas-to-agent ratio of 800-1000:1; and reaction time of 3-5 hours.

13. The method according to claim 7, wherein: The chlorine content of the oxychlorination regeneration catalyst is 0.9-1.3% by weight; the dispersion of the active component is 0.8-1%; the specific surface area is 180-220 m 2 / g.

14. The method according to claim 13, wherein: The chlorine content of the oxychlorination regeneration catalyst is 1-1.2% by weight; the dispersion of the active component is 0.9-1%; and the specific surface area is 190-210 m 2 / g.

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