CN110013887B - In-situ regeneration method for catalyst deactivation - Google Patents
In-situ regeneration method for catalyst deactivation Download PDFInfo
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- CN110013887B CN110013887B CN201810019659.XA CN201810019659A CN110013887B CN 110013887 B CN110013887 B CN 110013887B CN 201810019659 A CN201810019659 A CN 201810019659A CN 110013887 B CN110013887 B CN 110013887B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000011069 regeneration method Methods 0.000 title claims abstract description 60
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 55
- 230000009849 deactivation Effects 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 230000008929 regeneration Effects 0.000 claims abstract description 44
- 238000009826 distribution Methods 0.000 claims abstract description 40
- 238000004458 analytical method Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 111
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 239000000571 coke Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 8
- 238000005485 electric heating Methods 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 29
- 239000001301 oxygen Substances 0.000 description 29
- 229910052760 oxygen Inorganic materials 0.000 description 29
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 16
- 230000008859 change Effects 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000036284 oxygen consumption Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an in-situ regeneration method for catalyst deactivation, which mainly solves the problem that in the prior art, external coking regeneration is required. The invention adopts an in-situ regeneration method for catalyst deactivation to carry out in-situ regeneration on the deactivated catalyst on a catalyst in-situ regeneration device, wherein the device comprises a gas distribution system, an in-situ regenerator, a heating furnace, a cooler, a gas-liquid separator, an analysis system and a control system, the inlet of the gas distribution system is connected with a gas inlet pipeline, the outlet of the gas distribution system is connected with the in-situ regenerator, the heating furnace is arranged outside the in-situ regenerator, a thermocouple is inserted inside the in-situ regenerator, the outlet of the in-situ regenerator is sequentially connected with the cooler and the gas-liquid separator, and the gas phase outlet of the gas-liquid separator is connected with the analysis system.
Description
Technical Field
The invention relates to an in-situ regeneration method for catalyst deactivation.
Background
The tail gas in the process of producing the propylene oxide by the HPPO method contains various gases such as propylene, propane, oxygen, hydrogen, carbon dioxide and the like, and the propylene has high recovery value, and when the oxygen content in the tail gas is high, the whole device has explosion danger, so the oxygen in the gas needs to be deoxidized.
In the prior deoxidation technology, catalytic combustion is the most effective way for solving the problems of organic pollutant emission and recovery of certain organic matters at present due to low combustion and ignition temperature, no pollutant emission such as NOx and the like, low requirement on fuel gas concentration and other excellent combustion performances. When the propylene tail gas is subjected to a catalytic reaction, due to the condensation reaction, a part of coke is generated besides carbon dioxide and water and is deposited on the catalyst, so that the surface area of the catalyst is reduced, the activity is reduced, and the catalyst is deactivated. The deactivated catalyst caused by carbon deposit may be regenerated through high temperature oxidation to eliminate carbon deposit, and the activity may be recovered partially or completely for further use in industrial production.
The catalyst regeneration is divided into in-device regeneration and out-device regeneration, for the deoxidation catalytic reaction, after the catalyst is deactivated, the shutdown and the unloading are needed, and the deactivated catalyst is transported to a regeneration furnace for in-device coke burning regeneration, so that the workload of loading and unloading the catalyst is greatly increased, the cost is increased, and the problems of abrasion and the like in the catalyst loading process are easy to occur.
Currently, catalyst deactivation regeneration involves fewer in-situ regeneration issues. The invention designs an in-situ coking regeneration method aiming at carbon deposition inactivation of a deoxidation catalyst, and avoids a series of problems of external coking regeneration.
Disclosure of Invention
The technical problem to be solved by the invention is that in the prior art, external coking regeneration is required, and a novel in-situ regeneration method for catalyst deactivation is provided, and has the advantage of in-situ regeneration.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a catalyst inactivated in-situ regeneration method is characterized in that an inactivated catalyst is subjected to in-situ regeneration on a catalyst in-situ regeneration device, the device comprises a gas distribution system, an in-situ regenerator, a heating furnace, a cooler, a gas-liquid separator, an analysis system and a control system, wherein a gas inlet pipeline is connected to an inlet of the gas distribution system, an outlet of the gas distribution system is connected with the in-situ regenerator, the heating furnace is arranged outside the in-situ regenerator, a thermocouple is inserted into the heating furnace, an outlet of the in-situ regenerator is sequentially connected with the cooler and the gas-liquid separator, a gas phase outlet of the gas-liquid separator is connected with the analysis system, and the control system is controlled by a Programmable Logic Controller (PLC); the method comprises the following steps of preparing oxygen-nitrogen mixed gas with a certain oxygen content by a coking medium through a gas distribution system, introducing the oxygen-nitrogen mixed gas from the upper part of an in-situ regenerator, carrying out in-situ regeneration on a catalyst, controlling a heating furnace to carry out temperature programming on a reactor, and recording the temperature of a catalyst bed layer and the composition of reaction tail gas in real time.
In the above technical solution, preferably, the in-situ regenerator is a fixed bed reactor.
In the above technical solution, preferably, a back pressure valve, a pressure gauge and a pressure sensor are arranged on a pipeline connecting the gas distribution system and the in-situ regenerator.
In the above technical solution, preferably, the lower part of the gas-liquid separator is provided with a liquid discharge pipeline, and a pipeline connecting the gas phase outlet and the analysis system is provided with a back pressure valve.
In the above technical solution, preferably, a pressure reducing valve is provided on the gas inlet line.
In the above technical solution, preferably, the control system is connected to the gas distribution system, the temperature control system, the pressure sensor, the level gauge on the gas-liquid separator, the back pressure valve, and the analysis system through signal lines.
In the above technical scheme, preferably, the in-situ regenerator tube core is provided with 5 thermocouples, the regenerator is placed at the center of a cylindrical heating furnace, the heating furnace adopts an open-type electric heating furnace, the heating furnace is provided with 5 heating sections, wherein the first section is a preheating section, the middle three sections are isothermal sections, the fifth section is a heat preservation section, and the upper part and the lower part of the catalyst bed layer are provided with packing layers.
In the above technical solution, preferably, the device is provided with an over-temperature and over-pressure alarm function.
The invention relates to an illegal in-situ regeneration method, which solves the problems of catalyst abrasion and production cost increase caused by external coke burning regeneration of a deactivated catalyst device; the proportion of a coking medium (mainly oxygen-containing mixed gas) is controlled in real time, so that the problem that local overheating of a catalyst bed layer is easy to occur during coking in the device is solved; the composition of the coke-burning tail gas is monitored in real time, so that the regeneration progress can be conveniently mastered. The device does not need to be shut down and unloaded, avoids catalyst abrasion caused by regeneration outside the device, improves the working efficiency and reduces the production cost. Meanwhile, the device is provided with a gas distribution system, so that the oxygen content of the scorching medium can be regulated in real time, and the temperature runaway of the catalyst bed layer is prevented. In addition, an on-line chromatogram is also arranged at the tail gas emission part of the device, so that the composition of the regenerated tail gas can be detected in real time, the regeneration process is controlled, and the regeneration degree of the catalyst can be mastered at any time. The regeneration method can carry out in-situ coking regeneration on the deactivated catalyst, improve the working efficiency and reduce the production cost. Meanwhile, the oxygen content of the coking medium can be adjusted in real time, and the temperature runaway of a catalyst bed layer is prevented; the composition of the reaction tail gas can be monitored in real time, so that the regeneration progress can be monitored conveniently, the regeneration degree of the catalyst can be mastered at any time, and a better technical effect is achieved.
Drawings
FIG. 1 is a flow diagram of an in situ regeneration apparatus for deactivated catalyst according to the present invention.
In figure 1, oxygen pipeline, nitrogen pipeline, spare gas pipeline, gas distribution system, fixed bed reactor, heating furnace, back pressure valve, pressure gauge, pressure sensor, thermocouple, cooler, air inlet, air outlet and air outlet, air outlet,
A gas-liquid separator,
A liquid level meter,
A drain valve,
A back pressure valve,
An on-line chromatogram,
A pressure reducing valve.
FIG. 2 is a cross-sectional view of a fixed bed reactor.
FIG. 3 is a graph of the core temperature and oxygen consumption rate over time for a catalyst regeneration experiment.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
The invention provides a method for in-situ coke burning regeneration without disassembling a deactivated catalyst, which is mainly carried out by the following devices.
As shown in fig. 1, the apparatus is mainly composed of a gas-phase feed metering unit, a reaction unit, and a product separation unit. The control system adopts a PLC control system, and parameters such as temperature, pressure, flow and the like can be automatically acquired, controlled, recorded and printed. The system automatically generates parameter curves and reports and is provided with various safety protection functions.
(1) Gas feed metering unit
This device uses three routes gas: the first path is oxygen, the second path is nitrogen, the oxygen and the nitrogen pass through a gas distribution system and are mixed according to a certain proportion to be used as a scorching medium, and the third path is reserved for standby; in addition, nitrogen can be used for plant purging and replacement and plant gas tightness.
The gas distribution system mainly comprises: computer system, controller, distribution box.
The computer system comprises a computer, automatic gas distribution software and a control card;
the control box comprises a control box main body, a control panel and a power supply;
the gas distribution box comprises a gas distribution box body, a mass flow controller, a stop valve and a matched pipeline so as to ensure accurate gas distribution and control pressure.
(2) Reaction unit
The main body of the reaction unit is a fixed bed reactor, a pressure gauge, a pressure sensor and a spring type safety valve are installed at the inlet of the reactor, the reaction pressure can be uploaded to a computer and can be read on site, and the safety valve ensures the operation safety of the reactor.
The reactor tube core is provided with 5 thermocouples, the reactor is placed at the central position of a cylindrical heating furnace, the heating furnace adopts an open type electric heating furnace, and the heating furnace is provided with 5 heating sections, wherein the first section is a preheating section, the middle three sections are isothermal sections, and the fifth section is a heat preservation section.
In order to reduce the labor intensity of operators, the heating furnace is also provided with a temperature programming, and the temperature raising and lowering process of the reactor can be adopted in the starting and stopping stages of the device.
Each heating section of the heating furnace is provided with a temperature safety switch, and when the temperature of the heating furnace in the section is detected to reach a set high limit value, the power supply of the heating furnace can be automatically cut off, so that the function of protecting the reactor is achieved.
The reactor pressure protection mechanism is mainly a spring type pressure safety valve, when the system pressure is ultrahigh to a set limit value, the spring type safety valve jumps to relieve the pressure of the reaction system, and the effect of protecting the safety of container equipment is achieved.
(3) Product separation unit
The reaction effluent is first cooled in a cooler, and the temperature of the product may be lowered to about 50 deg.c. And the cooled reaction product enters a gas-liquid separator for gas-liquid separation. And the gas separated by the gas-liquid separator enters an online chromatograph for gas composition analysis after being subjected to backpressure control by a backpressure valve, and then is discharged.
The gas-liquid separator is provided with a differential pressure transmitter for detecting the liquid level, when the liquid level in the separator reaches the set height, the liquid level is given for alarming, and an operator can directly discharge the liquid through the liquid discharge double valve group at the bottom of the gas-liquid separator.
In order to prevent the organic gas from liquefying in the gas-liquid separator, the bottom of the gas-liquid separator is subjected to heat preservation and heat tracing, and the temperature of the gas-liquid separator is controlled to be higher than the liquefying temperature of the organic gas. Prevent the liquefaction of organic gas, influence experimental accuracy and gas-liquid separation effect.
The using method of the device comprises the following steps:
opening a bolt at the top of the reactor, arranging a thermowell at a specified position in the reactor, fixing the thermowell, and sequentially filling a filler, a deactivated catalyst and the filler to the specified position; the bolt is screwed down, and then the thermocouple is inserted into the sleeve and fixed.
The burning medium is mixed with oxygen-nitrogen mixed gas with certain oxygen content through a gas distribution system and is introduced from the upper part of the reactor; controlling the heating furnace to perform temperature programming on the reactor, and recording the temperature of the catalyst bed and the composition of reaction tail gas in real time.
The device is used for carrying out a burning regeneration test of the deoxygenation catalyst in the tail gas generated in the production of propylene oxide by the HPPO method.
The experimental steps are as follows:
(1) inert Al with the diameter of 6mm2O3The ceramic balls were loaded into the reactor wick at a distance of 71cm from the orifice, the deactivated catalyst was loaded at a distance of 68cm from the orifice, and then Al was charged2O3The ceramic ball is positioned 48cm away from the pipe orifice;
(2) five thermocouples TE-1114, TE-1115, TE-1116, TE-1117 and TE-1118 in the tube core sleeve of the reactor are respectively arranged at positions 48cm, 68cm, 69.5cm, 71cm and 76cm away from the tube opening, and the temperature change conditions of the coke-burning medium when the coke-burning medium does not enter the catalyst, enters the catalyst bed and leaves the catalyst are respectively considered; the TE-1115 thermocouples, the TE-1116 thermocouples and the TE-1117 thermocouples correspond to the upper edge, the center and the lower edge of the catalyst bed respectively, namely the height of the catalyst bed is 3cm, and the volume is about 20ml, which is shown in figure 2 in detail.
(3) The experiment is started after the reactor is installed and the nitrogen is introduced to detect the air tightness of the system; oxygen-nitrogen mixed gas with 3 percent of oxygen content is configured by a gas distribution system and is used as a coking medium to be introduced into the reactor; setting a heating furnace temperature-rising program, and heating the reactor by the program; in the temperature rise process, the temperature change of a catalyst bed layer and the composition change of tail gas of the device are closely observed so as to observe the coking progress in time, and the temperature of the tube wall and the tube core of the reactor and the oxygen content of oxygen-nitrogen mixed gas entering and exiting the reactor are timely recorded in the experiment process so as to observe the coking progress;
(4) when the temperature of the catalyst bed layer is not obviously increased and the oxygen content in the oxygen-nitrogen mixed gas entering and exiting the reactor is not changed, the completion of coke burning is indicated; introducing nitrogen for purging and cooling;
(5) the experimental data are derived, and the experimental results are analyzed, the tube core temperature and the oxygen consumption rate of the reactor in the catalyst regeneration experiment are shown in the graph of fig. 3 along with the time change under the constant temperature condition of 400 ℃ of the reactor for the oxygen-nitrogen mixed gas with the oxygen content of 3 percent.
[ example 2 ]
The invention provides a method for in-situ coke burning regeneration without disassembling a deactivated catalyst, which is mainly carried out by the following devices.
As shown in fig. 1, the apparatus is mainly composed of a gas-phase feed metering unit, a reaction unit, and a product separation unit. The control system adopts a PLC control system, and parameters such as temperature, pressure, flow and the like can be automatically acquired, controlled, recorded and printed. The system automatically generates parameter curves and reports and is provided with various safety protection functions.
(1) Gas feed metering unit
This device uses three routes gas: the first path is oxygen, the second path is nitrogen, the oxygen and the nitrogen pass through a gas distribution system and are mixed according to a certain proportion to be used as a scorching medium, and the third path is reserved for standby; in addition, nitrogen can be used for plant purging and replacement and plant gas tightness.
The gas distribution system mainly comprises: computer system, controller, distribution box.
The computer system comprises a computer, automatic gas distribution software and a control card;
the control box comprises a control box main body, a control panel and a power supply;
the gas distribution box comprises a gas distribution box body, a mass flow controller, a stop valve and a matched pipeline so as to ensure accurate gas distribution and control pressure.
(2) Reaction unit
The main body of the reaction unit is a fixed bed reactor, a pressure gauge, a pressure sensor and a spring type safety valve are installed at the inlet of the reactor, the reaction pressure can be uploaded to a computer and can be read on site, and the safety valve ensures the operation safety of the reactor.
The reactor tube core is provided with 4 thermocouples, the reactor is placed at the central position of a cylindrical heating furnace, the heating furnace adopts an open type electric heating furnace, and the heating furnace is provided with 4 heating sections, wherein the first section is a preheating section, the middle 2 sections are isothermal sections, and the fourth section is a heat preservation section.
In order to reduce the labor intensity of operators, the heating furnace is also provided with a temperature programming, and the temperature raising and lowering process of the reactor can be adopted in the starting and stopping stages of the device.
Each heating section of the heating furnace is provided with a temperature safety switch, and when the temperature of the heating furnace in the section is detected to reach a set high limit value, the power supply of the heating furnace can be automatically cut off, so that the function of protecting the reactor is achieved.
The reactor pressure protection mechanism is mainly a spring type pressure safety valve, when the system pressure is ultrahigh to a set limit value, the spring type safety valve jumps to relieve the pressure of the reaction system, and the effect of protecting the safety of container equipment is achieved.
(3) Product separation unit
The reaction effluent is first cooled in a cooler, and the temperature of the product may be lowered to about 50 deg.c. And the cooled reaction product enters a gas-liquid separator for gas-liquid separation. And the gas separated by the gas-liquid separator enters an online chromatograph for gas composition analysis after being subjected to backpressure control by a backpressure valve, and then is discharged.
The gas-liquid separator is provided with a differential pressure transmitter for detecting the liquid level, when the liquid level in the separator reaches the set height, the liquid level is given for alarming, and an operator can directly discharge the liquid through the liquid discharge double valve group at the bottom of the gas-liquid separator.
In order to prevent the organic gas from liquefying in the gas-liquid separator, the bottom of the gas-liquid separator is subjected to heat preservation and heat tracing, and the temperature of the gas-liquid separator is controlled to be higher than the liquefying temperature of the organic gas. Prevent the liquefaction of organic gas, influence experimental accuracy and gas-liquid separation effect.
The using method of the device comprises the following steps:
opening a bolt at the top of the reactor, arranging a thermowell at a specified position in the reactor, fixing the thermowell, and sequentially filling a filler, a deactivated catalyst and the filler to the specified position; the bolt is screwed down, and then the thermocouple is inserted into the sleeve and fixed.
The burning medium is mixed with oxygen-nitrogen mixed gas with certain oxygen content through a gas distribution system and is introduced from the upper part of the reactor; controlling the heating furnace to perform temperature programming on the reactor, and recording the temperature of the catalyst bed and the composition of reaction tail gas in real time.
The device is used for carrying out a burning regeneration test of the deoxygenation catalyst in the tail gas generated in the production of propylene oxide by the HPPO method.
The experimental steps are as follows:
(1) inert Al with the diameter of 6mm2O3The ceramic balls were loaded into the reactor core at a distance of 69cm from the nozzle, the deactivated catalyst was loaded at a distance of 65cm from the nozzle, and then Al was charged2O3The ceramic ball reaches the position 45cm away from the pipe orifice;
(2) 4 thermocouples in the shell tube of the reactor tube core were placed at positions 48cm, 68cm, 71cm and 76cm from the tube opening, respectively, and the temperature change of the coke-burning medium when it did not enter the catalyst, entered the catalyst bed and exited the catalyst was examined.
(3) The experiment is started after the reactor is installed and the nitrogen is introduced to detect the air tightness of the system; oxygen-nitrogen mixed gas with 3 percent of oxygen content is configured by a gas distribution system and is used as a coking medium to be introduced into the reactor; setting a heating furnace temperature-rising program, and heating the reactor by the program; in the temperature rise process, the temperature change of a catalyst bed layer and the composition change of tail gas of the device are closely observed so as to observe the coking progress in time, and the temperature of the tube wall and the tube core of the reactor and the oxygen content of oxygen-nitrogen mixed gas entering and exiting the reactor are timely recorded in the experiment process so as to observe the coking progress;
(4) when the temperature of the catalyst bed layer is not obviously increased and the oxygen content in the oxygen-nitrogen mixed gas entering and exiting the reactor is not changed, the completion of coke burning is indicated; introducing nitrogen for purging and cooling;
(5) and (3) deriving experimental data, and analyzing experimental results to obtain a time-dependent change chart of the temperature of a tube core of the reactor and the oxygen consumption rate of the reactor in the catalyst regeneration experiment under the constant temperature condition of 400 ℃ of the reactor.
[ example 3 ]
The invention provides a method for in-situ coke burning regeneration without disassembling a deactivated catalyst, which is mainly carried out by the following devices.
As shown in fig. 1, the apparatus is mainly composed of a gas-phase feed metering unit, a reaction unit, and a product separation unit. The control system adopts a PLC control system, and parameters such as temperature, pressure, flow and the like can be automatically acquired, controlled, recorded and printed. The system automatically generates parameter curves and reports and is provided with various safety protection functions.
(1) Gas feed metering unit
This device uses three routes gas: the first path is oxygen, the second path is nitrogen, the oxygen and the nitrogen pass through a gas distribution system and are mixed according to a certain proportion to be used as a scorching medium, and the third path is reserved for standby; in addition, nitrogen can be used for plant purging and replacement and plant gas tightness.
The gas distribution system mainly comprises: computer system, controller, distribution box.
The computer system comprises a computer, automatic gas distribution software and a control card;
the control box comprises a control box main body, a control panel and a power supply;
the gas distribution box comprises a gas distribution box body, a mass flow controller, a stop valve and a matched pipeline so as to ensure accurate gas distribution and control pressure.
(2) Reaction unit
The main body of the reaction unit is a fixed bed reactor, a pressure gauge, a pressure sensor and a spring type safety valve are installed at the inlet of the reactor, the reaction pressure can be uploaded to a computer and can be read on site, and the safety valve ensures the operation safety of the reactor.
The reactor tube core is provided with 5 thermocouples, the reactor is placed at the central position of a cylindrical heating furnace, the heating furnace adopts an open type electric heating furnace, and the heating furnace is provided with 5 heating sections, wherein the first section is a preheating section, the middle three sections are isothermal sections, and the fifth section is a heat preservation section.
In order to reduce the labor intensity of operators, the heating furnace is also provided with a temperature programming, and the temperature raising and lowering process of the reactor can be adopted in the starting and stopping stages of the device.
Each heating section of the heating furnace is provided with a temperature safety switch, and when the temperature of the heating furnace in the section is detected to reach a set high limit value, the power supply of the heating furnace can be automatically cut off, so that the function of protecting the reactor is achieved.
The reactor pressure protection mechanism is mainly a spring type pressure safety valve, when the system pressure is ultrahigh to a set limit value, the spring type safety valve jumps to relieve the pressure of the reaction system, and the effect of protecting the safety of container equipment is achieved.
(3) Product separation unit
The reaction effluent is first cooled in a cooler, and the temperature of the product may be lowered to about 50 deg.c. And the cooled reaction product enters a gas-liquid separator for gas-liquid separation. And the gas separated by the gas-liquid separator enters an online chromatograph for gas composition analysis after being subjected to backpressure control by a backpressure valve, and then is discharged.
The gas-liquid separator is provided with a differential pressure transmitter for detecting the liquid level, when the liquid level in the separator reaches the set height, the liquid level is given for alarming, and an operator can directly discharge the liquid through the liquid discharge double valve group at the bottom of the gas-liquid separator.
In order to prevent the organic gas from liquefying in the gas-liquid separator, the bottom of the gas-liquid separator is subjected to heat preservation and heat tracing, and the temperature of the gas-liquid separator is controlled to be higher than the liquefying temperature of the organic gas. Prevent the liquefaction of organic gas, influence experimental accuracy and gas-liquid separation effect.
The using method of the device comprises the following steps:
opening a bolt at the top of the reactor, arranging a thermowell at a specified position in the reactor, fixing the thermowell, and sequentially filling a filler, a deactivated catalyst and the filler to the specified position; the bolt is screwed down, and then the thermocouple is inserted into the sleeve and fixed.
The burning medium is mixed with oxygen-nitrogen mixed gas with certain oxygen content through a gas distribution system and is introduced from the upper part of the reactor; controlling the heating furnace to perform temperature programming on the reactor, and recording the temperature of the catalyst bed and the composition of reaction tail gas in real time.
The device is used for carrying out a burning regeneration test of the deoxygenation catalyst in the tail gas generated in the production of propylene oxide by the HPPO method.
The experimental steps are as follows:
(1) inert Al with the diameter of 4mm2O3The ceramic balls were loaded into the reactor wick at a distance of 71cm from the orifice, the deactivated catalyst was loaded at a distance of 68cm from the orifice, and then Al was charged2O3The ceramic ball is positioned 48cm away from the pipe orifice;
(2) placing five thermocouples TE-1114, TE-1115, TE-1116, TE-1117 and TE-1118 in the tube core sleeve of the reactor at positions 48cm, 68cm, 69cm, 71cm and 76cm away from the tube opening respectively, and respectively inspecting the temperature change condition of a coke-burning medium when the coke-burning medium does not enter the catalyst, enters a catalyst bed layer and leaves the catalyst; wherein, the three thermocouples TE-1115, TE-1116 and TE-1117 respectively correspond to the upper edge, the center and the lower edge of the catalyst bed, namely the height of the catalyst bed is 4cm, and the volume is about 26ml, which is shown in figure 2 in detail.
(3) The experiment is started after the reactor is installed and the nitrogen is introduced to detect the air tightness of the system; oxygen-nitrogen mixed gas with 3 percent of oxygen content is configured by a gas distribution system and is used as a coking medium to be introduced into the reactor; setting a heating furnace temperature-rising program, and heating the reactor by the program; in the temperature rise process, the temperature change of a catalyst bed layer and the composition change of tail gas of the device are closely observed so as to observe the coking progress in time, and the temperature of the tube wall and the tube core of the reactor and the oxygen content of oxygen-nitrogen mixed gas entering and exiting the reactor are timely recorded in the experiment process so as to observe the coking progress;
(4) when the temperature of the catalyst bed layer is not obviously increased and the oxygen content in the oxygen-nitrogen mixed gas entering and exiting the reactor is not changed, the completion of coke burning is indicated; introducing nitrogen for purging and cooling;
(5) the experimental data are derived, and the experimental results are analyzed, the tube core temperature and the oxygen consumption rate of the reactor in the catalyst regeneration experiment are shown in the graph of fig. 3 along with the time change under the constant temperature condition of 400 ℃ of the reactor for the oxygen-nitrogen mixed gas with the oxygen content of 3 percent.
The regeneration method can carry out in-situ coking regeneration on the deactivated catalyst, improve the working efficiency and reduce the production cost. Meanwhile, the oxygen content of the coking medium can be adjusted in real time, and the temperature runaway of a catalyst bed layer is prevented; the composition of the reaction tail gas can be monitored in real time, so that the regeneration progress can be monitored conveniently, the regeneration degree of the catalyst can be mastered at any time, and a better technical effect is achieved.
Claims (8)
1. A catalyst deactivation in-situ regeneration method is characterized in that a catalyst deactivation in-situ regeneration device carries out in-situ regeneration on a deactivated catalyst, the device comprises a gas distribution system, an in-situ regenerator, a heating furnace, a cooler, a gas-liquid separator, an analysis system and a control system, wherein the inlet of the gas distribution system is connected with a gas inlet pipeline, the outlet of the gas distribution system is connected with the in-situ regenerator, the heating furnace is arranged outside the in-situ regenerator, a thermocouple is inserted inside the in-situ regenerator, the outlet of the in-situ regenerator is sequentially connected with the cooler and the gas-liquid separator, the gas phase outlet of the gas-liquid separator is connected with the analysis system, and the control system is controlled by a PLC; the coke burning medium is mixed with aerobic nitrogen mixture gas through a gas distribution system, the aerobic nitrogen mixture gas is introduced from the upper part of the in-situ regenerator to carry out in-situ regeneration on the catalyst, the heating furnace is controlled to carry out temperature programming on the reactor, and the temperature of the catalyst bed layer and the reaction tail gas are recorded in real time.
2. The in-situ regeneration process of catalyst deactivation according to claim 1, characterized in that the in-situ regenerator is a fixed bed reactor.
3. The in-situ regeneration method of deactivated catalyst as set forth in claim 1, wherein the pipeline connecting the gas distributing system and the in-situ regenerator is provided with back pressure valve, pressure gauge and pressure sensor.
4. The in-situ regeneration method of catalyst deactivation according to claim 1, wherein a drain line is provided at a lower portion of the gas-liquid separator, and a back pressure valve is provided on a line connecting the gas phase outlet to the analysis system.
5. A process for the in situ regeneration of a deactivated catalyst according to claim 1 wherein the gas inlet line is provided with a pressure relief valve.
6. The in-situ regeneration method of catalyst deactivation according to claim 1, wherein the control system is connected with the gas distribution system, the temperature control system, the pressure sensor, the liquid level meter on the gas-liquid separator, the back pressure valve and the analysis system through signal lines.
7. The in-situ regeneration method of deactivated catalyst according to claim 1, wherein the in-situ regenerator tube core is provided with 5 thermocouples, the regenerator is placed at the center of a cylindrical heating furnace, the heating furnace is an open-type electric heating furnace, the heating furnace is provided with 5 heating sections, wherein the first section is a preheating section, the middle three sections are isothermal sections, the fifth section is a heat preservation section, and the upper part and the lower part of the catalyst bed layer are provided with packing layers.
8. Method for the in situ regeneration of deactivated catalyst according to claim 1, characterized in that said device is provided with an over-temperature, over-pressure alarm function.
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