CN112206721A - Fixed bed reactor and hydrogenation catalyst regeneration method - Google Patents

Fixed bed reactor and hydrogenation catalyst regeneration method Download PDF

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Publication number
CN112206721A
CN112206721A CN201910627802.8A CN201910627802A CN112206721A CN 112206721 A CN112206721 A CN 112206721A CN 201910627802 A CN201910627802 A CN 201910627802A CN 112206721 A CN112206721 A CN 112206721A
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reactor
temperature
oxygen
catalyst
gas
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CN112206721B (en
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纪玉国
杜周
季静
熊凯
张富春
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J38/02—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

The invention provides a fixed bed reactor and a method for regenerating a hydrogenation catalyst by using the same, wherein the fixed bed reactor comprises a catalyst bed layer; cooling pipelines distributed in the catalyst bed layer; the first temperature measuring device is used for measuring the temperature of one or more positions of the cooling pipeline; and the second temperature measuring device is used for measuring the temperature of one or more positions of the catalyst bed layer. Through install cooling line and a plurality of temperature measuring device additional in the reactor, effectual improvement current fixed bed hydrogenation reactor bed contains the oxygen air current uneven distribution when regenerating the catalyst, and the local hot spot appears, detects lagged scheduling problem, has effectively guaranteed the quality behind the catalyst regeneration.

Description

Fixed bed reactor and hydrogenation catalyst regeneration method
Technical Field
The invention relates to the field of petrochemical industry, in particular to a fixed bed reactor and a method for carrying out hydrogenation catalyst regeneration in the fixed bed reactor.
Background
After the hydrogenation catalyst reacts for a period of time, the surface of the catalyst is covered with a layer of colloid, which affects the activity of the catalyst, and oxygen-containing gas is required to be introduced to oxidize and remove the colloid so as to regenerate the catalytic performance of the catalyst. When the catalyst is regenerated, because the catalyst bed layer has channeling or uneven colloid distribution due to long-term use, when high-temperature oxygen-containing gas is introduced, local temperature rise of the catalyst bed layer is too fast, so that hot spots are formed, and if the local temperature rise of the bed layer cannot be detected in time, the catalyst and a reactor are damaged. To effectively control the reaction temperature, the oxygen-containing gas flow is turned off and the nitrogen flow is increased, which requires a large amount of nitrogen to be injected to meet the demand and the distribution is uneven. These increase the investment and energy consumption of the plant and do not guarantee the quality of the regeneration of the catalyst.
Chinese patent CN200410074514.8 discloses a process for controlling the temperature of catalyst beds by adding product diesel oil between catalyst beds to lower the temperature of catalyst beds. The main technical characteristic is that the hydrogenation product diesel oil is used as cold oil to replace cold hydrogen. The process mainly utilizes the sensible heat of cold oil to reduce the temperature of a catalyst bed layer. In addition, the change of raw materials of the device and the temperature rise of the catalyst bed layer are different under different operation periods, so the quantity of the cold oil required to be injected is greatly changed. And cold oil distributor is fixed knot structure, and the change of cold oil volume has direct influence to cold oil distributor effect, leads to effectively controlling reaction temperature.
In summary, the conventional cold air flow control method can effectively control the reaction temperature, but the injected cold air flow is large, and the investment and energy consumption of the device are increased; by adopting the cold oil control method, although partial investment of the device can be reduced, the radial temperature difference of the bed layer of the hydrogenation reactor is large due to the change of the injection amount of the cold oil, and the reaction temperature cannot be effectively controlled. Both of these methods have problems.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a fixed bed reactor in a first aspect, wherein a cooling pipeline and a plurality of temperature measuring devices are additionally arranged in the reactor, so that the problems of uneven distribution of oxygen-containing airflow, local hot spots, detection delay and the like of the bed layer of the existing fixed bed hydrogenation reactor during catalyst regeneration are effectively solved. The second aspect of the invention provides a method for regenerating a hydrogenation catalyst in the fixed bed reactor provided by the invention, and the third aspect of the invention provides the fixed bed reactor or the application of the method in the regeneration of the hydrogenation catalyst.
In a first aspect, the present invention provides a fixed bed reactor comprising a catalyst bed; cooling pipelines distributed in the catalyst bed layer; the first temperature measuring device is used for measuring the temperature of one or more positions of the cooling pipeline; and the second temperature measuring device is used for measuring the temperature of one or more positions of the catalyst bed layer.
According to some embodiments of the invention, the cooling lines are distributed axially inside the reactor, the first temperature measuring device being arranged radially inside the reactor and the second temperature measuring device being arranged axially inside the reactor.
In some preferred embodiments of the present invention, small holes are added to the side of the cooling line.
According to some embodiments of the invention, the first temperature measuring device is configured to detect the temperature of the cooling line, and the second temperature measuring device is configured to measure and detect the temperature at different positions in the catalyst bed.
According to some embodiments of the present invention, each of the first temperature measuring device and the second temperature measuring device includes one or more thermocouples and a sleeve, and the specific number is determined according to actual needs.
In a second aspect of the present invention, there is provided a process for regenerating a hydrogenation catalyst, which comprises carrying out the regeneration of the hydrogenation catalyst in the above-mentioned reactor.
According to some embodiments of the invention, the method for hydrogenating the catalyst comprises the steps of:
s1: heating the catalyst bed layer to the ignition temperature of the colloid on the surface of the catalyst;
s2: the reactor is fed with a cooling medium through a cooling line and the oxygen comprising gas is fed from the top of the reactor, said cooling medium and said oxygen comprising gas being mixed, preferably in a turbulent manner.
According to some embodiments of the invention, said step S2 comprises that said oxygen comprising gas is introduced in a pulsed manner and/or directly into said reactor, preferably with a pulse interval of 2-20 seconds, more preferably with a pulse interval of 5-10 seconds.
According to some embodiments of the invention, the step S2 further comprises controlling the catalyst bed temperature to be less than 420 ℃, preferably less than 400 ℃.
According to some embodiments of the invention, the catalyst bed temperature is controlled to be below 420 ℃, preferably below 400 ℃ by stopping the introduction of oxygen-containing gas and/or increasing the flow of cooling medium. The flow of the cooling medium is controlled by the flow regulating valve according to the temperature of the catalyst bed layer and the oxygen concentration at the inlet of the reactor, and the requirements of the device under different working conditions can be met.
According to some embodiments of the present invention, the oxygen comprising gas is introduced into the reactor in step S2 a plurality of times, preferably twice.
According to some embodiments of the invention, the oxygen comprising gas is pulsed into the reactor in step S2 for the first time until the catalyst bed temperature is no longer changing and there is no temperature increase. The invention firstly adopts the pulse mode to introduce the oxygen-containing gas, which can prevent the temperature of a certain point in the reactor from being overhigh and causing violent combustion after encountering oxygen to cause temperature runaway so as to reduce the performance of the catalyst or completely inactivate the catalyst.
According to some embodiments of the invention, the oxygen comprising gas is oxygen comprising air, preferably the concentration of oxygen in the oxygen comprising gas is between 0.1 and 10 wt.%, more preferably between 0.1 and 1 wt.%.
According to some embodiments of the invention, the cooling medium is a light hydrocarbon or nitrogen, preferably nitrogen. In the invention, the light hydrocarbon is C1-C4Is used as the gaseous hydrocarbon of (1).
According to some embodiments of the invention, further comprising step S3: the catalyst regeneration is continued according to step S2, the oxygen concentration in the oxygen comprising gas being higher than in step S2, preferably the oxygen concentration in the oxygen comprising gas is 5-10 wt%, such as 5 wt%, 10 wt%.
In the regeneration process of the catalyst, the cooling medium with a certain flow enters the catalyst bed layer in the reactor from the cooling pipeline while the oxygen-containing gas enters from the upper part of the reactor, so that the oxygen-containing gas entering from the top of the reactor forms turbulent flow, and the distribution of the oxygen in the reactor is more uniform. When the thermocouples inside and outside the reactor bed are used for detecting the hot spots in the catalyst bed of the reactor, the pipeline containing oxygen can be closed, and the flow of the cooling medium in the cooling pipeline is increased, so that the temperature in the catalyst bed is effectively reduced, and the regeneration quality of the regenerated catalyst is ensured.
The method of the invention has the advantages of uniform distribution of oxygen-containing airflow in the reactor during catalyst regeneration, timely temperature detection, effective control of the temperature of the catalyst bed layer, low influence on the catalyst regeneration performance and the like.
A third aspect of the invention provides the use of a fixed bed reactor as described above or a process as described above for the regeneration of a catalyst, in particular a hydrogenation catalyst.
Drawings
FIG. 1 is a structural view of a fixed bed reactor.
FIG. 2 is a schematic view of a cooling circuit and a cooling circuit thermowell.
In fig. 1: 1-reactor feed inlet; 2-a manhole; 3-ceramic ball bed layer; 4-a cooling line; 5-a separator; 6-material outlet; 7-catalyst discharge hole; 8-cooling line inlet; 9-catalyst bed layer; 10-a scaffold; 11-cooling the line thermowell; 12-reactor thermowell.
In fig. 2: 14-cooling the gas stream; 4-a cooling line; 11-cooling the line thermowell.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings, which are only drawn for illustrating the basic contents of the present invention and do not limit the scope of the present invention.
As shown in FIG. 1, the ceramic balls and the catalyst are loaded from the manhole 2 of the reactor, and after the reaction period is finished, the ceramic balls and the catalyst are discharged from the discharge hole 7. The nitrogen and air are mixed (to form airflow with specific oxygen proportion), and then the mixture enters the reactor from an inlet 1 at the upper part of the hydrogenation reactor for regeneration, and the regenerated gas flows out from an outlet 6 at the lower part of the reactor and enters a heat exchange and separation downstream unit. According to the requirement of cooling the reactor, nitrogen as a cooling medium enters from a cooling pipeline inlet 8 at the lower part of the reactor, flows out from small holes on the side surface of the cooling pipeline, is mixed with oxygen-containing gas flow to form turbulence, promotes the dispersion of oxygen in a bed layer, and can prevent local overheating of the bed layer. The temperature of the catalyst bed 9 is measured by thermocouples in the reactor thermowell 12 and the cooling line thermowell 11, and one or more sets of cooling line thermowells 11 and reactor thermowells 12 may be provided according to actual needs.
As shown in FIG. 2, the thermowells of the cooling pipeline are distributed in a circular shape on the same horizontal plane, and the temperature of the cooling pipeline, which is also the temperature of the catalyst bed layer at the contact position with the cooling pipeline, can be measured at the same time. The method of the present invention is suitable for the regeneration process of hydrogenation catalysts, and technicians can optimize the operation conditions according to the difference of the operation conditions of the device, which is a means commonly adopted in the field.
Example 1
(1) Before regeneration, the system should be thoroughly purged with nitrogen to a hydrocarbon content of <1.0 (v)%, and hydrogen-free (hydrogen content below 200 ppm).
(2) The blind separates the lines and equipment for supplying oxygen-containing gas to the catalyst regeneration from the lines and equipment for supplying gas, feed and product outputs to the reactor and purges the oil and water in the various vessels, lines.
(3) Before regeneration, the device is in a shutdown state, the materials are emptied, and the reactor and the catalyst are both in a cold state.
(4) Checking that each temperature measuring point, an on-line detecting instrument and the like of the catalyst bed layer are in good condition.
(5) Heating the reactor and the catalyst to 110-120 ℃ with nitrogen at a temperature rise rate of 20-30 ℃/h. And when the low-pressure oil separation tank does not discharge any more oil, N2The cycle was continued for one hour.
(6) The reactor and catalyst temperature was raised to 350 c, the light-off temperature of the gum in the catalyst bed, at a ramp rate of 30 c/hour.
(7) Air is added from the inlet of the reactor in a pulse mode, the pulse interval is 5-10 seconds, the concentration of oxygen in the gas at the inlet is not more than 1 (wt)%, a cooling pipeline is opened, the oxygen is fully distributed in the reactor, thermoelectric even data arranged longitudinally and transversely in the reactor are observed, the temperature change of a reactor bed layer is noticed, the highest temperature of a catalyst bed layer is not more than 400-420 ℃, if the highest temperature exceeds the temperature, the pulse addition of the air is stopped immediately, the flow of the nitrogen in the cooling pipeline is increased, and after the temperature is reduced, the air is introduced, so that the flow of the nitrogen in the cooling pipeline is reduced.
(8) When the temperature of the catalyst bed layer is not changed and the temperature does not rise, the air is directly introduced from pulse instead, the concentration of oxygen is kept unchanged, the temperature change of the reactor bed layer is observed, the temperature of the bed layer is strictly controlled below 420 ℃, if the temperature is exceeded, the air is immediately stopped to increase the flow of the nitrogen in the cooling pipeline, and after the temperature is reduced, the air is introduced to reduce the flow of the nitrogen in the cooling pipeline.
(9) When the temperature of the catalyst bed layer is not changed and the temperature does not rise, the air is introduced in a pulse mode instead of directly introduced air, the pulse interval is 5-10 seconds, the concentration of oxygen in the gas at the inlet is increased to 5 (wt)%, the temperature of the bed layer is strictly controlled below 420 ℃, if the temperature exceeds, the air is stopped to be added immediately, the flow of nitrogen in the cooling pipeline is increased, and after the temperature is reduced, the air is introduced to reduce the flow of the nitrogen in the cooling pipeline.
(10) When the temperature of the catalyst bed layer is not changed and the temperature does not rise, the air is directly introduced from pulse instead, the oxygen concentration is kept unchanged, the temperature change of the reactor bed layer is observed, the temperature of the bed layer is strictly controlled below 420 ℃, if the temperature is exceeded, the air is immediately stopped to increase the flow of the nitrogen in the cooling pipeline, and after the temperature is reduced, the air is introduced to reduce the flow of the nitrogen in the cooling pipeline.
(11) After the combustion reaction is finished, the concentration of oxygen in the gas at the inlet is increased to 10 wt%, final coking is carried out, the bed layer is strictly controlled below 420 ℃, the addition of air is immediately stopped, the flow of nitrogen in the cooling pipeline is increased, and after the temperature is reduced, air is introduced to reduce the flow of nitrogen in the cooling pipeline.
(12) When the oxygen concentration at the inlet and the outlet of the reactor is the same, no oxygen is consumed; analysis of tail gas CO2A concentration of less than 0.3 (wt)%; regeneration is considered complete when there is essentially no temperature rise in the reactor. After the regeneration was completed, the catalyst was taken out and analyzed for its specific surface area to be 125m2/g。
Comparative example 1
(1) Before regeneration, the system should be thoroughly purged with nitrogen to a hydrocarbon content of <1.0 (v)%, and hydrogen-free (hydrogen content below 200 ppm).
(2) The blind separates the lines and equipment for supplying oxygen-containing gas to the catalyst regeneration from the lines and equipment for supplying gas, feed and product outputs to the reactor and purges the oil and water in the various vessels, lines.
(3) Before regeneration, the device is in a shutdown state, the materials are emptied, and the reactor and the catalyst are both in a cold state. Checking that each temperature measuring point, an on-line detecting instrument and the like of the catalyst bed layer are in good condition.
(4) Heating the reactor and the catalyst to 110-120 ℃ with nitrogen at a temperature rise rate of 20-30 ℃/h. And no oil is discharged in the low branch tankWhen N is present2The cycle was continued for one hour.
(5) The reactor and catalyst temperatures were increased to 350 ℃ at a ramp rate of 30 ℃/hr.
(6) Adding air from the inlet of the reactor, wherein the oxygen concentration at the inlet is not more than 1 (wt)%, observing the thermoelectric even data in the reactor, paying attention to the temperature change of the bed layer of the reactor, ensuring that the highest temperature of the catalyst bed layer is not more than 400-420 ℃, if the highest temperature exceeds, immediately stopping adding the air, and introducing the air after the temperature is reduced. Because the thermocouple arrangement in the reactor is too little, the temperature of each area of the catalyst bed layer can not be monitored, so that the temperature of the catalyst bed layer is in a temperature runaway state, and the temperature is reduced to below 400 ℃ after the nitrogen purging is carried out for ten hours.
(7) When the temperature of the catalyst bed layer is not changed any more and the temperature is not increased, air is introduced, the oxygen concentration air amount at an inlet is increased to 5 wt%, and the temperature of the bed layer is strictly controlled below 420 ℃.
(8) After the combustion reaction is finished, the air quantity is increased to 10 wt%, and finally the coke is burnt, and the bed layer is strictly controlled below 420 ℃.
(9) When the oxygen concentration at the inlet and the outlet of the reactor is the same, no oxygen is consumed; analysis of tail gas CO2A concentration of less than 0.3 (wt)%; regeneration is considered complete when there is essentially no temperature rise in the reactor.
After the regeneration was completed, the catalyst was taken out and analyzed for its specific surface area, which was 65m2The specific surface data of the catalyst is greatly reduced.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A fixed bed reactor, comprising:
a catalyst bed layer;
cooling pipelines distributed in the catalyst bed layer; the first temperature measuring device is used for measuring the temperature of one or more positions of the cooling pipeline;
and the second temperature measuring device is used for measuring the temperature of one or more positions of the catalyst bed layer.
2. The reactor of claim 1, wherein the cooling lines are axially distributed within the reactor, the first temperature measuring device is radially disposed within the reactor, and the second temperature measuring device is axially disposed within the reactor.
3. The reactor of claim 1 or 2, wherein the first and second temperature measuring devices each comprise one or more thermocouples and a sleeve.
4. A method of regenerating a hydrogenation catalyst comprising being carried out in a reactor according to any one of claims 1-3, preferably comprising the steps of:
s1: heating the catalyst bed layer to the ignition temperature of the colloid on the surface of the catalyst;
s2: the reactor is fed with a cooling medium through a cooling line and the oxygen comprising gas is fed from the top of the reactor, said cooling medium and said oxygen comprising gas being mixed, preferably in a turbulent manner.
5. The method according to claim 4, wherein the step S2 includes: the oxygen comprising gas is introduced and/or introduced directly into the reactor in pulses, preferably with a pulse interval of 2-20 seconds, more preferably with a pulse interval of 5-10 seconds.
6. The method of claim 4 or 5, wherein the step S2 further comprises controlling the catalyst bed temperature to be lower than 420 ℃, preferably lower than 400 ℃; preferably, the catalyst bed temperature is controlled below 420 ℃, preferably below 400 ℃ by stopping the introduction of oxygen-containing gas and/or increasing the flow of cooling medium.
7. Method according to any of claims 4-6, wherein the oxygen comprising gas is introduced into the reactor in step S2 a plurality of times, preferably twice, more preferably a first time in a pulsed manner and a second time directly into the reactor.
8. Method according to any of claims 4-7, wherein the oxygen comprising gas is oxygen comprising air, preferably the concentration of oxygen in the oxygen comprising gas is 0.1-10 wt%, more preferably 0.1-1 wt%, and/or the cooling medium is a light hydrocarbon or nitrogen, preferably nitrogen.
9. The method according to any one of claims 4 to 8, further comprising step S3: the catalyst regeneration is continued according to step S2, wherein the oxygen concentration in the oxygen comprising gas is higher than in step S2, preferably the oxygen concentration in the oxygen comprising gas is 5-10 wt%.
10. Use of the reactor according to any one of claims 1-3 or the process according to any one of claims 4-9 for catalyst regeneration, in particular for hydrogenation catalyst regeneration.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB776022A (en) * 1954-02-03 1957-05-29 Gulf Research Development Co Method for regenerating stationary beds of catalyst
DE2119127A1 (en) * 1970-04-20 1971-11-04 Chemical Construction Corp., New York, N.Y. (V.St.A.) Reactor for exothermic catalytic reaction
CN1298925A (en) * 2000-06-12 2001-06-13 中国石油化工集团公司 External regeneration process of hydrogenating catalyst
CN101932671A (en) * 2008-01-30 2010-12-29 埃克森美孚化学专利公司 The method of recycling catalyst between catalyst regenerator and external catalyst water cooler
CN102814150A (en) * 2012-09-04 2012-12-12 山东齐鲁石化工程有限公司 Radial fixed bed oxidative dehydrogenation reactor for regenerating catalyst by sections
CN103769246A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Regeneration method for catalyst used for methylation of toluene
CN107970867A (en) * 2017-12-08 2018-05-01 河南心连心化肥有限公司 A kind of radial reactor and preparation method for preparing 2- methylfurans
CN108786664A (en) * 2018-05-21 2018-11-13 合肥嘉科工贸有限公司 A kind of multistage thermostatic type cold shocking type methanol synthesis reactor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB776022A (en) * 1954-02-03 1957-05-29 Gulf Research Development Co Method for regenerating stationary beds of catalyst
DE2119127A1 (en) * 1970-04-20 1971-11-04 Chemical Construction Corp., New York, N.Y. (V.St.A.) Reactor for exothermic catalytic reaction
CN1298925A (en) * 2000-06-12 2001-06-13 中国石油化工集团公司 External regeneration process of hydrogenating catalyst
CN101932671A (en) * 2008-01-30 2010-12-29 埃克森美孚化学专利公司 The method of recycling catalyst between catalyst regenerator and external catalyst water cooler
CN102814150A (en) * 2012-09-04 2012-12-12 山东齐鲁石化工程有限公司 Radial fixed bed oxidative dehydrogenation reactor for regenerating catalyst by sections
CN103769246A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Regeneration method for catalyst used for methylation of toluene
CN107970867A (en) * 2017-12-08 2018-05-01 河南心连心化肥有限公司 A kind of radial reactor and preparation method for preparing 2- methylfurans
CN108786664A (en) * 2018-05-21 2018-11-13 合肥嘉科工贸有限公司 A kind of multistage thermostatic type cold shocking type methanol synthesis reactor

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