CN110639598A - Catalyst oxychlorination and drying method for catalyst regeneration process and catalyst regeneration process - Google Patents
Catalyst oxychlorination and drying method for catalyst regeneration process and catalyst regeneration process Download PDFInfo
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- CN110639598A CN110639598A CN201810682408.XA CN201810682408A CN110639598A CN 110639598 A CN110639598 A CN 110639598A CN 201810682408 A CN201810682408 A CN 201810682408A CN 110639598 A CN110639598 A CN 110639598A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
- B01J38/44—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material and adding simultaneously or subsequently free oxygen; using oxyhalogen compound
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/32—Regeneration or reactivation of catalysts comprising compounds of halogens
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
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Abstract
The present disclosure relates to a method for oxychlorination and drying of a catalyst for a catalyst regeneration process and a catalyst regeneration process. The method comprises the following steps: s1, enabling the coked catalyst to sequentially enter an oxychlorination area, a drying area and a cooling area of a regenerator; s2, taking air as inlet air and dividing the air into first inlet air and second inlet air, enabling the first inlet air to sequentially pass through a cooling area and a drying area and enter an oxychlorination area, enabling the second inlet air and a chlorine injection agent to be mixed and enter the oxychlorination area, and enabling a catalyst in the oxychlorination area to be in contact with the exhaust air of the drying area, the second inlet air and the chlorine injection agent to perform oxychlorination reaction; s3, dechlorinating the gas discharged from the oxychlorination area, and returning to the step S2 as the inlet gas with or without additional air. In the method, all gases come from air and chlorine injection agents and are not mixed with the gases in the scorching zone, the gases are independently circulated and are convenient to control, the oxygen concentration in the oxychlorination zone is improved, and the dispersion of the noble metals on the catalyst is facilitated.
Description
Technical Field
The disclosure relates to the field of catalyst regeneration methods, and in particular relates to a catalyst oxychlorination and drying method for a catalyst regeneration process and a catalyst regeneration process.
Background
The catalyst generally comprises a support, at least one noble metal, at least one halogen or other additive element. For example, platinum-containing metals are deposited on a chlorinated alumina support. Such catalysts are used to reform aromatics or produce aromatics by dehydrocyclization and/or dehydrogenation, such as continuous reforming catalysts. Taking the continuous reforming catalyst as an example, during the reaction process of the catalyst, platinum metal aggregation can occur, which affects the catalyst effect, and during the regeneration of the catalyst, after the coke burning treatment, the chlorine element on the carrier can be lost, so that an oxychlorination step needs to be performed to adjust the chlorine content on the catalyst, and the metal on the catalyst is fully oxidized and dispersed, so that the catalyst activity is recovered.
CN1136056C discloses a method and apparatus for regenerating an aromatic compound preparation or reforming catalyst for improved oxychlorination. Comprising the steps of combustion, oxychlorination and calcination, in which regeneration at least one chlorinating agent, at least one oxygen-containing gas and water are fed to the oxychlorination step in such a way that the molar ratio of water to chlorine is between 3 and 50, the oxychlorination step being carried out in the presence of a gas containing less than 21% oxygen and at least 50ppm chlorine (based on HCl) and at a temperature of between 350 and 600 ℃ and operating at a pressure of between 0.3 and 0.8 MPa. The oxygen-containing gas is a regeneration gas which is partially from a burning zone, subjected to washing dechlorination, drying dehydration and oxygen supplementation, and is partially from a lower roasting zone.
CN1100852C discloses a regeneration method and equipment for a hydrocarbon conversion catalyst, the catalyst to be regenerated passes through a scorching zone, an oxychlorination zone, a predrying zone and a roasting zone of a regenerator from top to bottom in sequence, the added predrying zone can use the regenerated recycle gas after dechlorination and drying for predrying the catalyst after oxychlorination, so that the consumption of the dry gas in the roasting zone is reduced, the amount of the oxygen-containing gas in the roasting zone is determined by the oxygen consumption required by scorching, the gas entering the roasting zone can completely enter the oxychlorination zone and then enter a regenerated gas circulation loop for supplying oxygen for scorching, no redundant oxygen-containing gas in the roasting zone of the regenerator can be emptied, and the purification measure of the emptied gas in the roasting zone is cancelled.
CN101835877A discloses a regeneration method and a container for reforming catalyst, in which a carbon-containing catalyst sequentially passes through a first-stage coking zone, a second-stage coking zone, an oxychlorination zone and a calcination zone in a regenerator. A portion of the gaseous effluent from the oxychlorination zone is recycled to the inlets of the two coking zones via at least one scrubbing zone. Recycling a part of unwashed gas effluent with higher oxygen content from the oxychlorination zone to a secondary coking zone, and reducing the aggregation degree of metal platinum in the secondary coking zone by improving the oxygen content in the secondary coking zone, wherein the effluent gas of the secondary coking zone is mixed with the effluent gas of the oxychlorination zone, washed and dried and then recycled to the oxychlorination zone.
CN101835878A discloses a regeneration method of reforming catalyst, i.e. the carbon-containing catalyst passes through a first-stage coking zone, a second-stage coking zone, an oxychlorination zone and a calcination zone in sequence in a regenerator. A portion of the gaseous effluent from the oxychlorination zone is recycled to the inlets of the two coking zones via at least one scrubbing zone. A portion of the unwashed, higher oxygen content gaseous effluent from the oxychlorination zone is recycled to the secondary coking zone, reducing the level of accumulation of metallic platinum in the secondary coking zone by increasing the oxygen content in the secondary coking zone.
CN104226379B discloses a regeneration method of a continuous reforming catalyst, which comprises introducing a spent catalyst after reaction into a regenerator, passing through a coking zone, an oxychlorination zone and a roasting zone in sequence, directly injecting a part of the regenerated gas discharged from the outlet of the coking zone without any treatment into the oxychlorination zone, and introducing the oxychlorination outlet gas into a regenerated gas system to return to the coking zone or discharge. The method utilizes hot regeneration gas to adjust the atmosphere of the oxychlorination zone, and can reduce the chlorine injection amount to the oxychlorination zone.
In the existing catalyst regeneration process, part of gas discharged from a coking zone is usually introduced into an oxychlorination zone, part of the gas discharged from the oxychlorination zone is also recycled to the coking zone, the gas flow in the oxychlorination zone cannot be independently controlled, and the oxygen content of the gas in the oxychlorination zone is low.
Disclosure of Invention
It is an object of the present disclosure to provide a process for the oxychlorination and drying of a catalyst in which the oxychlorination zone oxygen partial pressure is high and the oxychlorination process gas stream can be controlled separately in a loop.
The inventor of the present disclosure finds that the increase of the oxygen partial pressure content in the gas flow during the oxychlorination process is beneficial to promoting the dispersion of the noble metal on the catalyst and avoiding the metal aggregation, thereby improving the regeneration efficiency of the catalyst and the catalytic capability of the regenerated catalyst.
In order to achieve the above object, a first aspect of the present disclosure provides a method for oxychlorination and drying of a catalyst used in a catalyst regeneration process, the method comprising the steps of: s1, enabling the coked catalyst to sequentially enter an oxychlorination area, a drying area and a cooling area of a regenerator; s2, taking air as inlet air and dividing the air into first inlet air and second inlet air, enabling the first inlet air to sequentially pass through the cooling zone and the drying zone to enter the oxychlorination zone, enabling the second inlet air and a chlorine injection agent to be mixed and enter the oxychlorination zone, and enabling the catalyst in the oxychlorination zone to be in contact with the exhaust air of the drying zone, the second inlet air and the chlorine injection agent to perform oxychlorination reaction; (ii) a S3, dechlorinating the gas discharged from the oxychlorination area, and returning to the step S2 as the inlet gas with or without additional air.
Optionally, the inlet gas to the oxychlorination zone consists of the exhaust gas from the drying zone, the second inlet gas and the chlorine injection agent; the inlet gas to the cooling zone is composed of the first inlet gas.
Optionally, the oxychlorination zone, the drying zone, and the cooling zone gases are not mixed with the char zone gases.
Optionally, the air is dedusted and dried and then subjected to step S2 as the intake air.
Optionally, the method comprises: the gas exiting the oxychlorination zone is subjected to heat exchange, dechlorination and cooling with or without make-up air and returned as the recycle gas to step S2.
Optionally, the method comprises: and enabling the second inlet gas and the gas discharged from the oxychlorination area to enter the oxychlorination area after heat exchange.
Optionally, the method comprises: and heating the second inlet air, mixing the second inlet air with the chlorine injection agent, and then feeding the second inlet air into the oxychlorination zone, wherein the inlet temperature of the oxychlorination zone is 420-560 ℃.
Optionally, the method comprises: drying and boosting the inlet air, and then dividing the inlet air into two parts in step S2, wherein the pressure of the inlet air after boosting is 0.15-1.5 MPaG; the pressure of the oxychlorination zone, the drying zone and the cooling zone is 0.15-1.0 MPaG respectively and independently; the pressure of the cooling area is 2-35 kPa higher than that of the drying area; the pressure of the drying area is 2-35 kPa higher than that of the oxychlorination area.
Optionally, the method comprises: and enabling the first inlet gas to enter the cooling area to exchange heat with the catalyst and then to be discharged, heating the exhaust gas of the cooling area and then entering the drying area to dry the catalyst, and enabling the exhaust gas of the drying area to enter the oxychlorination area to carry out the oxychlorination reaction.
In a second aspect of the present disclosure, there is provided a process for regenerating a catalyst comprising the method of oxychlorination and drying of the catalyst according to the first aspect of the present disclosure.
The beneficial effects of this disclosure include:
(1) air is directly used as an oxychlorination gas, so that the oxygen partial pressure of an oxychlorination area is improved, the catalyst noble metal dispersion and oxychlorination efficiency are facilitated, and the catalyst noble metal is cheap and easy to obtain;
(2) the gas is all from air and chlorine injection agent, the air is recycled after drying and oxychlorination processes, becomes a relatively independent circulation system, is not mixed with the gas in the burning area, and is convenient to operate;
(3) the gas in the oxychlorination area, the drying area and the cooling area is recycled, so that resources are saved, and gas emission is reduced.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a process flow diagram of one embodiment of the disclosed method for catalyst oxychlorination and drying for a catalyst regeneration process.
Description of the reference numerals
1 pressure boosting device 2 drying area inlet heating device
3 oxychlorination zone inlet heating equipment 4 heat exchange equipment
5 dechlorination equipment 6 cooling equipment
7 drying equipment A oxychlorination zone
Drying zone B and cooling zone C
10 intake 11 first intake
12 second inlet 13 cooling zone exhaust
21 inlet gas 31 of drying zone, second inlet gas and chlorine injection agent mixed material
32 oxychlorination zone vent gas 33 chlorine injection agent
34 the dried oxychlorination zone effluent gas.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
In the present disclosure, the use of directional words such as "up" and "down" generally means up and down in the normal use state of the device, unless stated to the contrary. The "inner and outer" are with respect to the outline of the device itself.
As shown in fig. 1, a first aspect of the present disclosure provides a method for catalyst oxychlorination and drying for a catalyst regeneration process, the method comprising the steps of: s1, enabling the coked catalyst to sequentially enter an oxychlorination area, a drying area and a cooling area of a regenerator; s2, taking air as inlet air and dividing the air into first inlet air and second inlet air, enabling the first inlet air to sequentially pass through a cooling area and a drying area to enter an oxychlorination area, enabling the second inlet air and a chlorine injection agent to be mixed and enter the oxychlorination area, and enabling a catalyst in the oxychlorination area to be in contact with the second inlet air and the chlorine injection agent to perform oxychlorination reaction; s3, dechlorinating the gas discharged from the oxychlorination area, and returning to the step S2 as the inlet gas with or without additional air.
According to the catalyst oxychlorination and drying method, air is used as inlet air, the oxygen content of the gas in the oxychlorination area, the drying area and the cooling area is high, the gas discharged from the oxychlorination area is recycled after dechlorination, an independent gas circulation system is formed, operation and control are convenient, the oxygen concentration of the oxychlorination area is effectively improved, the volume fraction of oxygen in the oxychlorination area can reach more than 20% and can reach 20-23%, the noble metal dispersion on the catalyst is facilitated, the oxychlorination efficiency is improved, and the gas does not need to be discharged outside the system.
According to the present disclosure, in order to ensure that the oxygen content in the gas in the oxychlorination zone, the drying zone and the cooling zone is in a higher range and to facilitate the control operation, preferably, in the method of the present disclosure, the gas in the oxychlorination zone, the drying zone and the cooling zone is not mixed with the gas in the coking zone, i.e. the recycle gas in the coking zone does not enter the oxychlorination zone, the drying zone and the cooling zone, the gas discharged from the oxychlorination zone, the drying zone and the cooling zone does not return to the coking zone, and the three zones of the oxychlorination zone, the drying zone and the cooling zone and the coking zone respectively form two independent circulation systems for the control operation.
The meaning of the oxychlorination zone, drying zone and cooling zone is well known to those skilled in the art in light of this disclosure, i.e., the area of the apparatus within the regenerator where the coked catalyst is oxychlorinated, dried and cooled in the catalyst regeneration process. The configuration and operating conditions within the oxychlorination zone, drying zone and cooling zone may be conventional in the art, for example as shown in figure 1, preferably the oxychlorination zone, drying zone and cooling zone are arranged in sequence from top to bottom so that the coked catalyst flows by gravity through the oxychlorination zone, drying zone and cooling zone in sequence; preferably, the pressure of the oxychlorination zone, the drying zone and the cooling zone can be respectively and independently 0.15-1.0 MPaG, so that the oxychlorination treatment effect of the catalyst is improved, and the proper gas circulation pressure in the system is kept; further, the pressure of the cooling area is preferably 2-35 kPa higher than that of the drying area; the pressure of the drying zone is preferably 2-35 kPa higher than that of the oxychlorination zone so as to maintain the gas circulation of the oxychlorination zone, the drying zone and the cooling zone; specifically, for example, in one embodiment of the present disclosure, the pressure in the oxychlorination zone may be 0.35 to 0.44MPaG, the pressure in the drying zone may be 0.35 to 0.455MPaG, and the pressure in the cooling zone may be 0.375 to 0.49 MPaG; in another embodiment of the present disclosure, the pressure of the oxychlorination zone may be 0.785-0.885 MPaG, the pressure of the drying zone may be 0.79-0.9 MPaG, the pressure of the cooling zone may be 0.815-0.935 MPaG, and the temperature of the regenerated catalyst at the outlet of the cooling zone is preferably 100-300 ℃; the dechlorination process and apparatus may be conventional in the art, for example, dechlorination may be carried out by adsorption with a solid dechlorinating agent, the mass content of chlorine in the gas exiting the oxychlorination zone after dechlorination meets the environmental emission requirements, and may preferably be < 10ppm, and the formation of chlorine in the gas exiting the oxychlorination zone to form hydrogen chloride which can be prevented from corroding downstream equipment. To promote adequate contact and action in each zone, it is preferred that the first feed gas is contacted countercurrently with the catalyst in the oxychlorination zone, the drying zone and the cooling zone, respectively.
In order to further independently control the gas flow circulation in the oxychlorination and drying processes according to the present disclosure, in a preferred embodiment of the present disclosure, the inlet gas to the oxychlorination zone may consist of the exhaust gas from the drying zone, the second inlet gas and the chlorine injection agent; the inlet gas to the cooling zone may consist of the first inlet gas. In this embodiment, the system air for the entire oxychlorination, drying and cooling zones is all from the air inlet and optional chlorine injection agent, and does not involve the regeneration air for the coking zone, and the gases for the oxychlorination, drying and cooling zones are independently circulated and controlled separately.
According to the present disclosure, the oxygen content in the air is higher than that of the gas discharged from a general coking zone, the air is low in cost and easy to obtain, the gas in the coking zone circulates independently without entering an oxychlorination zone, a drying zone and a cooling zone, and the gas in the oxychlorination zone, the drying zone and the cooling zone circulates independently and is independent from the coking zone, that is, the system gas in the oxychlorination zone, the drying zone and the cooling zone is all from the air and is not mixed with the gas in the coking zone, and independent gas circulation is formed, so that the control is convenient.
According to the present disclosure, in order to maintain the oxygen content and the amount of the recycle gas, the gas discharged from the oxychlorination zone is preferably dechlorinated and supplemented with air, and then returned to step S2 as the inlet gas, and further, the supplemented air is preferably dedusted and dried to avoid moisture or other impurities carried by the air from affecting the oxychlorination process.
In accordance with the present disclosure, to facilitate recycling of the gas exiting the oxychlorination zone, in one embodiment, the process may comprise: the gas discharged from the oxychlorination zone is subjected to heat exchange, dechlorination and cooling, and then mixed with the intake air as a circulating gas, and the process continues to step S2. Wherein, the gas discharged from the oxychlorination area can exchange heat with the second inlet gas and also can exchange heat with other cold fluid; in the case that the heat exchange process cannot make the gas discharged from the oxychlorination zone reach the desired temperature, further, cooling can be performed, and the cooling medium and method can be conventional in the art, for example, air, cooling water or other cooling medium can be used to cool the gas discharged from the oxychlorination zone to achieve the cooling effect; the methods and apparatus for performing dechlorination may be conventional in the art and will not be described in detail herein. Wherein the temperature of the gas discharged from the heat exchange and/or cooling oxychlorination zone is less than 60 ℃, and preferably normal temperature to 40 ℃;
in accordance with the present disclosure, to facilitate circulation of gas within the system, the method may include: the feed gas is dried and/or boosted and then divided into a first feed gas and a second feed gas, preferably the feed gas is dried and boosted sequentially, and the gas discharged from the oxychlorination zone may be mixed with the feed gas as a recycle gas and then divided into two parts after being boosted and dried together. The methods and apparatus for drying and boosting can be conventional in the art, for example, drying can be carried out using a solid desiccant, and gas boosting can be carried out using a compressor.
Further, the pressure of the boosted intake air can be changed in a large range, preferably, the pressure of the boosted intake air can be 0.15-1.5 MPaG, and more preferably 0.5-0.95 MPaG, so as to maintain the proper gas pressure and flow rate in the system and the proper oxygen partial pressure in the oxychlorination zone, thereby ensuring the effect of the oxychlorination treatment.
In accordance with the present disclosure, in order to uniformly disperse the injected chlorine in the oxychlorination zone and to ensure the oxychlorination zone temperature, the method may include: and heating the second inlet gas and then feeding the second inlet gas into an oxychlorination zone, wherein the inlet temperature of the oxychlorination zone can be 420-560 ℃, and is preferably 490-540 ℃.
According to the present disclosure, to fully utilize energy within a system, the method may comprise: the second inlet gas and the gas exhausted from the oxychlorination area exchange heat, then are mixed with a chlorine injection agent and enter the oxychlorination area, so that the temperature of the second part of gas is raised by the gas exhausted from the oxychlorination area; further, under the condition that the heat exchange step can not enable the second part of gas to reach the temperature required by the inlet of the oxychlorination zone, the second part of gas after heat exchange can be subjected to heating treatment and then enters the oxychlorination zone. The heating and heat exchange methods and apparatus may be conventional in the art, for example heat exchange may be carried out using a heat exchanger, and heating may be carried out using an electric heater.
In accordance with the present disclosure, chlorine injection agents may be used in the oxychlorination reaction to provide supplemental chlorine to the catalyst, and the type of chlorine injection agent may be conventional in the art, such as perchloroethylene or carbon tetrachloride; the mode of addition of the chlorine injection agent is not particularly limited, and for example, the chlorine injection agent may be introduced into the oxychlorination zone alone or in combination with the second feed gas, and in one embodiment of the present disclosure, the method may include: the second inlet gas is heated and mixed with the chlorine injection agent and then enters the oxychlorination area. In the embodiment of the present disclosure in which the second inlet air exchanges heat with the gas discharged from the oxychlorination region, the second part of the gas can exchange heat with the gas discharged from the oxychlorination region, and then the second part of the gas is heated by the heating device, the second inlet air at the outlet of the heating device is injected with the chlorine injection agent, and the mixture flow reaches the inlet temperature of the oxychlorination region and enters the oxychlorination region.
According to the present disclosure, in order to make full use of the energy within the system, the method may comprise: the first inlet gas enters a cooling area to exchange heat with the catalyst and then is discharged, so that the catalyst is cooled by the first part of gas, and the heat carried in the catalyst is fully utilized to heat the first part of gas; the exhaust from the cooling zone (i.e. the warmed first gas) may be heated and passed to a drying zone to achieve the heat required to dry the catalyst and to a drying zone to dry the catalyst from the oxychlorination zone, and the exhaust from the drying zone may then be passed to the oxychlorination zone for the oxychlorination reaction.
According to the present disclosure, the boosted charge (including the gas exiting the dechlorinated oxychlorination zone as recycle gas) is divided into two portions, the flow ratio of the first charge to the second charge may vary over a wide range, the present disclosure does not specifically require, and preferably, the ratio of the mass flow rates of the first charge to the second charge may be 1: (0.5 to 1.2), preferably 1: (0.7-1) so that the catalyst reaches a proper temperature at the outlet of the cooling zone and chlorine injection in the oxychlorination zone can be more fully dispersed.
A second aspect of the present disclosure provides a catalyst regeneration process comprising the method of catalyst oxychlorination and drying of the first aspect of the present disclosure. Specifically, the process may include firstly burning the catalyst to be regenerated, then sequentially feeding the burned catalyst into an oxychlorination zone, a drying zone and a cooling zone, performing oxychlorination and drying treatment on the catalyst by using the method of the first aspect of the present disclosure, and obtaining the regenerated catalyst from an outlet of the cooling zone.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
Examples
As shown in fig. 1, this example is used to illustrate the catalyst oxychlorination and drying and cooling method of the present disclosure, which comprises: the coked catalyst sequentially enters an oxychlorination area A, a drying area B and a cooling area C, air is used as inlet air 10, the pressure is increased by a pressure increasing device 1 and is divided into two parts, the first inlet air 11 enters the cooling area, the second inlet air 12 enters the oxychlorination area, exhaust gas 13 of the cooling area enters the drying area (inlet gas 21 of the drying area) after passing through a heating device 2 at an inlet of the drying area and enters the oxychlorination area A in a regenerator; the second inlet gas 12 exchanges heat with the gas 32 discharged from the oxychlorination area, is heated by the oxychlorination area inlet heating device 3, is mixed with a chlorine injection agent 33, enters the oxychlorination area A, is in contact with a catalyst for oxychlorination, the volume concentration of oxygen in the oxychlorination area is about 21%, the gas 32 discharged from the oxychlorination area exchanges heat with the second inlet gas 12 by the heat exchange device 4, is dechlorinated by the dechlorination device 5, is cooled by the cooling device 6, and finally returns to the inlet of the pressure boosting device 1 for recycling after being dried by the drying device 7.
The present invention will be described in detail with reference to specific examples. In the following examples, the catalyst circulation amount is 1000kg/h, taking continuous reforming catalyst regeneration as an example. And (3) cooling the regenerated catalyst to below 250 ℃ after the inlet gas (first inlet gas) of the cooling zone exchanges heat with the catalyst through the cooling zone. The outlet gas of the cooling zone is heated to 500 ℃ by a heater and enters a drying zone, the second inlet gas in the pressure boosting device exchanges heat with the outlet gas of the oxychlorination zone, the temperature of the heating device is raised, the second inlet gas is mixed with the injected carbon tetrachloride, and the second inlet gas enters the oxychlorination zone at the temperature of 500 ℃. The mass flow rates of the first intake air and the second intake air are 1: 0.87. After the catalyst oxychlorination process is completed, HCl in the gas is removed from the outlet gas through heat exchange and temperature reduction and dechlorination equipment with the inlet gas of the oxychlorination area, the gas is cooled to 40 ℃ through cooling equipment, water is removed through drying equipment, and the gas enters pressure boosting equipment for recycling. The catalyst regenerated in this way, comparable in performance to the new catalyst, allows the reforming reaction products to be of a quality and to remain stable over the life of the catalyst. The method is adopted to regenerate the catalyst, and the non-regenerated new catalyst has C5 when the reforming reaction temperature is 530 ℃ and the hydrogen-oil ratio is 2.4+Product octane number 104, C5+The yield is more than or equal to 90 percent, and the hydrogen yield is more than or equal to 3.8 percent; the catalyst is recycled after being regenerated, and the product can keep C5 in the life cycle of the catalyst under the condition that the reaction conditions are not changed+Product octane number 104, C5+The yield is more than or equal to 90 percent, and the hydrogen yield is more than or equal to 3.8 percent. In the regeneration process, the gases in the oxychlorination area, the drying area and the cooling area are independently circulated, the balance of the gases in the oxychlorination area, the drying area and the cooling area is ensured, the gases do not need to be balanced with the coking area, and the operation and the control are convenient.
Comparative example
This comparative example serves to illustrate a different oxychlorination and drying process than the present disclosure. The prior oxychlorination and drying method is adopted, and the method is different from the method in the embodiment in that: the oxychlorination outlet gas and the regenerated coke-burning circulating gas are mixed and then return to the coke-burning zone, one part of air is used in the drying zone and the oxychlorination zone, the other part of the air is used in the coke-burning circulating gas, the volume concentration of oxygen in the oxychlorination zone is about 21% in the embodiment, the volume concentration of oxygen in the oxychlorination zone is about 4-7% in the comparative example, the volume concentration is far less than the oxygen concentration in the oxychlorination zone in the embodiment, and the oxychlorination updating of the catalyst is not facilitated. In order to maintain the oxygen balance of the regeneration system, the amount of air supplied to the oxychlorination zone and the drying zone is limited, and the operation process of the method is complicated.
As can be seen from the comparison of the examples and comparative examples, the method for oxychlorination and drying of the catalyst of the present disclosure directly uses air as an oxychlorination gas, increases the oxygen partial pressure in the oxychlorination zone, and facilitates the dispersion of the catalyst noble metal. The gas in the oxychlorination area, the drying area and the cooling area is recycled, so that resources are saved, and gas emission is reduced. The oxychlorination gas is not mixed with the coking gas, and becomes a relatively independent system with the coking area, thereby being convenient for operation.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method for oxychlorination and drying of a catalyst used in a catalyst regeneration process, the method comprising the steps of:
s1, enabling the coked catalyst to sequentially enter an oxychlorination area, a drying area and a cooling area of a regenerator;
s2, taking air as inlet air and dividing the air into first inlet air and second inlet air, enabling the first inlet air to sequentially pass through the cooling zone and the drying zone to enter the oxychlorination zone, enabling the second inlet air and a chlorine injection agent to be mixed and enter the oxychlorination zone, and enabling the catalyst in the oxychlorination zone to be in contact with the exhaust air of the drying zone, the second inlet air and the chlorine injection agent to perform oxychlorination reaction;
s3, dechlorinating the gas discharged from the oxychlorination area, and returning to the step S2 as the inlet gas with or without additional air.
2. The process of claim 1 wherein the oxychlorination zone, the drying zone, and the cooling zone gases are not mixed with a char zone.
3. The process of claim 1 wherein the oxychlorination zone inlet gas consists of the drying zone effluent gas, the second inlet gas and the chlorine injection agent; the inlet gas to the cooling zone is composed of the first inlet gas.
4. The method of claim 1, wherein the air is dedusted and dried and then subjected to step S2 as the intake air.
5. The method of claim 1, wherein the method comprises: the gas exiting the oxychlorination zone is subjected to heat exchange, dechlorination and cooling with or without make-up air and returned as the recycle gas to step S2.
6. The method of claim 1, wherein the method comprises: and enabling the second inlet gas and the gas discharged from the oxychlorination area to enter the oxychlorination area after heat exchange.
7. The method according to claim 1 or 6, wherein the method comprises: and heating the second inlet air, mixing the second inlet air with the chlorine injection agent, and then feeding the second inlet air into the oxychlorination zone, wherein the inlet temperature of the oxychlorination zone is 420-560 ℃.
8. The method of claim 1, wherein the method comprises: drying and boosting the inlet air, and then dividing the inlet air into two parts in step S2, wherein the pressure of the inlet air after boosting is 0.15-1.5 MPaG; the pressure of the oxychlorination zone, the drying zone and the cooling zone is 0.15-1.0 MPaG respectively and independently; the pressure of the cooling area is 2-35 kPa higher than that of the drying area; the pressure of the drying area is 2-35 kPa higher than that of the oxychlorination area.
9. The method of claim 1, wherein the method comprises: and enabling the first inlet gas to enter the cooling area to exchange heat with the catalyst and then to be discharged, heating the exhaust gas of the cooling area and then entering the drying area to dry the catalyst, and enabling the exhaust gas of the drying area to enter the oxychlorination area to carry out the oxychlorination reaction.
10. A process for regenerating a catalyst, comprising oxychlorination and drying of a catalyst according to any one of claims 1 to 9.
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