CN115430364A - Method and system for online replacement of catalyst of slurry bed synthesis reactor - Google Patents
Method and system for online replacement of catalyst of slurry bed synthesis reactor Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 188
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 110
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000004913 activation Effects 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 229940057995 liquid paraffin Drugs 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 3
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- 239000002994 raw material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 1
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- 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
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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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
- B01J8/001—Controlling catalytic processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
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Abstract
The invention provides a method and a system for replacing a catalyst of a slurry bed synthesis reactor on line; the method comprises the following steps: (1) Calculating the discharge amount of catalyst slurry in the slurry bed synthesis reactor and the make-up amount of fresh catalyst when the relative deviation between the actual value of the CO conversion rate and the set lower limit value is X; (2) Preparing catalyst slurry according to the calculated fresh catalyst replenishing amount; (3) Conveying the prepared catalyst slurry to an activation reactor for activation; (4) When the relative deviation value reaches X, discharging the catalyst according to the calculated discharge amount of the catalyst slurry; (5) And after the discharging is finished, conveying the activated fresh catalyst to the slurry bed synthesis reactor. The invention can replace the catalyst on line, can remove part of crushed and inactivated fine catalyst in time, reduces the problems of blockage, scaling and the like of a rear pipeline, avoids the problems of shutdown replacement and maintenance to delay production, and improves the production efficiency.
Description
Technical Field
The invention relates to the technical field of catalyst replacement, in particular to a method and a system for online replacement of a catalyst of a slurry bed synthesis reactor.
Background
With the continuous development of biomass utilization technology, the biomass oil-making technology becomes the focus of people's attention, and the technology for making synthetic oil by indirect liquefaction of biomass is the focus of continuous research of experts and scholars. The biomass indirect liquefaction is to convert biomass raw materials such as crop straws, forestry wastes, diatom and the like into the biomass containing H by advanced and reliable gasification technology 2 And raw synthesis gas mainly containing CO is converted into synthesis gas raw materials suitable for synthesis reaction through the procedures of purification, compression and the like of the raw synthesis gas, and then liquid products are obtained through condensation and separation under the catalytic action of a selected catalyst system (palladium system, cobalt system, iron system and the like). Compared with a fixed bed reactor, the slurry bed synthesis reactor has the advantages of good heat transfer effect, high heat efficiency, uniform temperature distribution, relatively easy temperature control, low catalyst consumption, capability of supplementing a catalyst on line in an operating state, no centralized agent loading and unloading process, high operation flexibility, low operation and maintenance cost, low price and the like, and is more and more widely applied to the biomass oil production technology.
However, the slurry bed synthesis reactor needs a catalyst with very fine particles, the particle size of the catalyst is only dozens of microns, the using amount of the catalyst is large, the hydrodynamic behavior in the reactor and the complex reaction process in the reactor are interwoven, the reaction is a strong exothermic reaction, and temperature runaway is easily caused once the reaction is out of control. In continuous operation, the activity of the catalyst is reduced with the time, meanwhile, the quality of the product is also affected, the catalyst is easy to break due to the fine catalyst particles themselves, and the catalyst is easy to be used continuously for a long time, and the fine particle catalyst or broken catalyst is carried out of the reactor along with the reaction product, so that the problem of blockage and scaling of the following pipeline is easily caused.
Disclosure of Invention
In order to solve the above problems, in one aspect, the present invention provides an online catalyst replacement method for a slurry bed synthesis reactor, comprising the following steps:
(1) Calculating the discharge amount of catalyst slurry in the slurry bed synthesis reactor and the make-up amount of fresh catalyst when the relative deviation between the actual value of the CO conversion rate and the set lower limit value is X;
(2) Preparing catalyst slurry according to the supplement amount of the fresh catalyst determined in the step 1;
(3) Conveying the catalyst slurry obtained in the step 2 to an activation reactor for activation to obtain a fresh catalyst with catalytic activity;
(4) When the relative deviation between the actual value of the CO conversion rate and the set lower limit value reaches X, conveying the catalyst slurry in the slurry bed synthesis reactor to a catalyst unloading tank according to the unloading amount of the catalyst slurry determined in the step 1;
(5) And (4) after the discharging is finished, conveying the activated fresh catalyst in the step (3) to the slurry bed synthesis reactor.
Further, in the step 1, the deviation X of the actual value of the CO conversion rate from the set lower limit value is not higher than 32%.
Further, in the step 5, after the activated fresh catalyst is conveyed to the slurry bed synthesis reactor, the actual value of the CO conversion rate does not deviate from the set upper limit value by more than 12%.
Further, in the step 2, the catalyst and the heavy diesel oil or the liquid paraffin are mixed according to the mass percentage of 1: 2.8-1: 3.2 stirring to prepare catalyst slurry.
Further, in the step 3, the step of conveying the catalyst slurry to an activation reactor for activation specifically includes:
the activation time of the catalyst slurry in the activation reactor is 12-28 hours, the activation temperature is 240-270 ℃, and the activation pressure is 3.0-3.2 MPa.
Further, in the step 4, the transferring the catalyst slurry in the slurry bed synthesis reactor to the catalyst discharge tank specifically includes:
and conveying the catalyst slurry through a pressure difference between the slurry bed synthesis reactor and a catalyst discharge tank, wherein the temperature in the catalyst discharge tank is not lower than 160 ℃.
On the other hand, the invention also provides an online catalyst replacement system for the slurry bed synthesis reactor, which comprises an activation reactor, the slurry bed synthesis reactor and a catalyst discharge tank, wherein the activation reactor is connected with the catalyst inlet end of the slurry bed synthesis reactor, the catalyst discharge tank is connected with the catalyst outlet end of the slurry bed synthesis reactor, and the activation reactor is also connected with a catalyst slurry preparation tank for preparing catalyst slurry; the device comprises a slurry bed synthesis reactor, and is characterized by also comprising a first detector for detecting the content of CO in feed gas of the slurry bed synthesis reactor and a second detector for detecting the content of CO in product gas, wherein the first detector and the second detector are connected with a calculator for calculating the CO conversion rate, and an actuator connected with the calculator is arranged on a pipeline between the activation reactor and the slurry bed synthesis reactor.
Furthermore, a first delivery pump is arranged on a pipeline between the catalyst slurry preparation tank and the activation reactor, and a second delivery pump is arranged on a pipeline between the activation reactor and the slurry bed synthesis reactor.
Furthermore, the feed end of the catalyst slurry preparation tank is connected with a catalyst pipeline and an auxiliary material pipeline, and the auxiliary material in the auxiliary material pipeline is heavy diesel oil or liquid paraffin.
Furthermore, a first feeding valve is further arranged on a pipeline between the catalyst slurry preparation tank and the activation reactor, a second feeding valve is arranged on a pipeline between the activation reactor and the slurry bed synthesis reactor, and a discharge valve is arranged on a pipeline between the slurry bed synthesis reactor and the catalyst discharge tank.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1) According to the online replacing method and system for the catalyst of the slurry bed synthesis reactor, the catalyst can be replaced online in the operation process of the slurry bed synthesis reactor, part of crushed and inactivated fine catalyst can be removed in time, the problems of blockage, scaling and the like of a subsequent pipeline are reduced, the shutdown replacement and maintenance caused by the problems are avoided, the production is delayed, and the production efficiency is improved;
2) According to the online replacement method and system for the catalyst in the slurry bed synthesis reactor, the first detector and the second detector are arranged, the performance condition of the catalyst in the slurry bed synthesis reactor can be monitored in real time, when the catalytic performance of the catalyst is reduced to exceed a limit value, the system can start a corresponding catalyst replacement program, and on the premise of not influencing the slurry bed synthesis reactor, part of deactivated catalyst is replaced, so that the replacement time is saved, and the production efficiency is improved;
3) According to the online replacement method and the online replacement system for the catalyst in the slurry bed synthesis reactor, provided by the invention, the discharge amount of slurry containing part of deactivated catalyst and the supplement amount of fresh catalyst can be accurately calculated through online monitoring and corresponding functional relation calculation, so that the operation of the slurry bed synthesis reactor is more stable and the product quality is more stable on the premise of smooth and safe online replacement of the catalyst;
4) According to the method and the system for replacing the catalyst of the slurry bed synthesis reactor on line, the flow rate of the supplemented catalyst is controlled through the actuator, so that the reaction is ensured to be in a controllable range, and the method and the system are safe and reliable.
Drawings
FIG. 1 is a schematic structural diagram of an online catalyst replacement system for a slurry bed synthesis reactor according to the present invention.
1-catalyst slurry preparation tank; 2-activating the reactor; 3-slurry bed synthesis reactor; 4-catalyst discharge tank; 5-a first delivery pump; 6-a second delivery pump; 7-a first detector; 8-a second detector; 9-a calculator; 10-an actuator; 11-a first feed valve; 12-a second feed valve; 13-a discharge valve; 14-catalyst line; 15-auxiliary line; 16-feed gas line; 17-product gas line.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention. In the drawings, the size and relative sizes of certain features may be exaggerated for clarity.
In the description of the present invention, unless expressly stated or limited otherwise, the terms "connected" and "coupled" are to be construed broadly, e.g., as meaning a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; the term "connecting" may refer to a direct connection, an indirect connection through an intermediate, a connection between two elements or an interaction relationship between two elements, and a person skilled in the art can understand the specific meaning of the above terms in the present invention in a specific case.
In the description of the present invention, the terms "upper", "lower", "left", "right", "front", "rear", and the like are used in the orientations and positional relationships shown in the drawings only for convenience of description and simplicity of operation, and do not indicate or imply that the designated device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In addition, in the description of the present invention, the terms "first" and "second" are used only for distinguishing in description.
In one aspect, the invention provides an online replacement method for a catalyst of a slurry bed synthesis reactor, which comprises the following steps:
(1) Calculating the discharge amount of catalyst slurry in the slurry bed synthesis reactor and the make-up amount of fresh catalyst when the relative deviation between the actual value of the CO conversion rate and the set lower limit value is X;
specifically, the actual value of the CO conversion rate in the slurry bed synthesis reactor can be obtained by detecting the CO content in the feed gas and the product gas, the catalyst is damaged and deactivated as the reaction time in the slurry bed synthesis reactor is prolonged, the CO conversion rate is reduced, the measured actual value of the CO conversion rate gradually approaches the set lower limit value of the CO conversion rate, the actual value of the CO conversion rate is compared with the set value of the CO conversion rate, when the relative deviation between the actual value of the CO conversion rate and the set lower limit value is X, the catalyst can be replaced, and the discharge amount of the catalyst slurry containing the deactivated catalyst to be discharged and the replenishment amount of the fresh catalyst are calculated by adopting the set functional relationship. The deviation between the actual value of the CO conversion rate and the set lower limit value is not higher than 32%, in this embodiment, the value of X is preferably 25%, and of course, an appropriate relative deviation value may be selected according to actual use requirements, which is not limited herein.
Further, the relative deviation, the discharge amount, and the replenishment amount are calculated as follows:
in the formula (1), W slurry The amount of catalyst slurry discharged is expressed in kg; sigma W oil The yield of the synthetic oil from the last catalyst replacement to the current catalyst replacement is unit t; x is the number of cat Is the weight percentage of the initial catalyst in the catalyst slurry in the slurry bed reactor.
W cat ＝3∑W oil (2)
In the formula (2), W cat The catalyst make-up is in kg; sigma W oil For replacing the catalyst from the last time to the present timeProduction of synthetic oil in t.
In formula (3), X is the relative deviation of the CO conversion rate; x is a radical of a fluorine atom Set lower limit value A set lower limit value for the CO conversion; x is the number of CO Actual values for CO conversion.
Specifically, the CO conversion is calculated by the following formula:
wherein, in the formula (4), x CO Actual value of CO conversion; f 0 The unit is kmol/h, and the molar flow of raw material gas of a slurry bed synthesis reactor is shown in the specification; f 1 The unit is kmol/h of the synthesis gas molar flow of a slurry bed synthesis reactor; y is 0CO The mole fraction of CO in the raw material gas; y is 1CO Is the mole fraction of CO in the syngas.
(2) Preparing catalyst slurry according to the supplement amount of the fresh catalyst determined in the step 1;
specifically, the catalyst slurry is prepared by uniformly stirring a catalyst and an auxiliary material, wherein the auxiliary material can be heavy diesel oil or liquid paraffin, the catalyst and the auxiliary material are uniformly stirred and prepared in a catalyst slurry preparation tank according to the mass percent of 1:3, the temperature in the catalyst slurry preparation tank is 60 ℃, and the pressure in the catalyst slurry preparation tank is 1.0MPa.
(3) Conveying the catalyst slurry obtained in the step 2 to an activation reactor for activation to obtain a fresh catalyst with catalytic activity;
specifically, after catalyst slurry preparation is completed, the activation reactor is determined to be qualified through nitrogen replacement, the temperature of the activation reactor is not lower than 160 ℃, then the catalyst slurry is conveyed into the activation reactor for activation, the activation time of the catalyst slurry in the activation reactor is 12-28 hours, the activation temperature is 240-270 ℃, the activation pressure is 3.0-3.2 MPa, and a fresh catalyst with stable catalytic activity performance can be obtained.
(4) When the relative deviation between the actual value of the CO conversion rate and the set lower limit value reaches X, conveying the catalyst slurry in the slurry bed synthesis reactor to a catalyst unloading tank according to the unloading amount of the catalyst slurry determined in the step 1;
specifically, by monitoring the actual value of the CO conversion rate of the slurry bed synthesis reactor in real time, when the relative deviation value reaches X, determining that the catalyst discharge tank is qualified after nitrogen replacement, the pressure is about 2.5MPa, the temperature in the catalyst discharge tank is not lower than 160 ℃, conveying the catalyst slurry containing part of deactivated catalyst in the slurry bed synthesis reactor into the catalyst discharge tank, and introducing the catalyst slurry into the catalyst discharge tank under the action of the pressure difference between the slurry bed synthesis reactor and the catalyst discharge tank.
(5) After the unloading is finished, conveying the activated fresh catalyst in the step 3 to the slurry bed synthesis reactor;
after the discharging is finished, determining that the reaction state in the slurry bed synthesis reactor is stable, the temperature gradient is distributed stably in the radial direction, and after the pressure is relatively stable, supplementing fresh activated catalyst slurry into the slurry bed synthesis reactor through the activation reactor, in the process of supplementing the fresh catalyst, closely paying attention to the relative deviation between the actual value of the CO conversion rate and the set lower limit value and the temperature and pressure change condition of the slurry bed synthesis reactor, the reaction in the slurry bed synthesis reactor is strengthened, the heat release is increased, the temperature and the pressure of the reactor fluctuate, the actual value of the CO conversion rate rises along with the increase, the actual value is slowly close to the set upper limit value of the CO conversion rate, in the supplementing process, the flow rate of the supplemented catalyst can be adjusted, the phenomenon that the reaction in the slurry bed synthesis reactor is out of control to cause temperature runaway is avoided, when the relative deviation between the actual value of the CO conversion rate and the set upper limit value is detected to be higher than 12%, the catalyst supplementing is stopped, otherwise, and the condition that the catalyst slurry in the activation reactor is completely conveyed into the slurry bed synthesis reactor is determined; in the actual operation process, in order to ensure the safety of the slurry bed synthesis reactor, the catalyst is preferably stopped to be supplemented when the actual value of the CO conversion rate deviates 5 percent from the set upper limit value.
The step 1-5 is a catalyst replacing process, and the operation flow of the step 1-5 is repeated according to a certain catalyst replacing time period and the relative deviation value of the set actual value of the CO conversion rate and the set lower limit value, so as to carry out the next catalyst replacing operation. The relative deviation values may be the same or different for each replacement.
On the other hand, as shown in the attached figure 1 of the specification, the invention also provides an online catalyst replacement system for a slurry bed synthesis reactor, which comprises an activation reactor 2, a slurry bed synthesis reactor 3 and a catalyst discharge tank 4, wherein the activation reactor 2 is connected with a catalyst inlet end of the slurry bed synthesis reactor 3, the catalyst discharge tank 4 is connected with a catalyst outlet end of the slurry bed synthesis reactor 3, and the activation reactor 2 is further connected with a catalyst slurry preparation tank 1 for preparing catalyst slurry; the system also comprises a first detector 7 for detecting the content of CO in raw material gas of the slurry bed synthesis reactor 3 and a second detector 8 for detecting the content of CO in product gas, wherein the first detector 7 and the second detector 8 are connected with a calculator 9 for calculating CO conversion rate, specifically, the first detector 7 is arranged on a raw material gas pipeline 16, the second detector is arranged on a product gas pipeline 17, the first detector 7 transmits the detected CO molar flow rate in the raw material gas of the slurry bed synthesis reactor 3 to the calculator 9, the second detector 8 transmits the detected CO molar flow rate in the product gas of the slurry bed synthesis reactor 3 to the calculator 9, the calculator 9 calculates data transmitted by the first detector 7 and the second detector 8, an actual value of the CO conversion rate is calculated by a formula (4), an actuator 10 connected with the calculator 9 is arranged on a pipeline between the activation reactor 2 and the slurry bed synthesis reactor 3, the actuator 10 can be used for adjusting the flow rate of catalyst slurry on the pipeline, preferably, a pressure detector and a pressure detector for monitoring the temperature of the slurry bed synthesis reactor 3 are also arranged on the pipeline, a supplementary reaction pressure detector is connected with the reactor 10, and a flow rate signal for controlling the slurry bed is sent to the reactor.
In an optimized implementation mode, a first delivery pump 5 is arranged on a pipeline between the catalyst slurry mixing tank 1 and the activation reactor 2, a second delivery pump 6 is arranged on a pipeline between the activation reactor 2 and the slurry bed synthesis reactor 3, the delivery of corresponding catalyst slurry is completed through the delivery pumps, a first feed valve 11 is further arranged on a pipeline between the catalyst slurry mixing tank 1 and the activation reactor 2, a second feed valve 12 is arranged on a pipeline between the activation reactor 2 and the slurry bed synthesis reactor 3, a discharge valve 13 is arranged on a pipeline between the slurry bed synthesis reactor 3 and the catalyst discharge tank 4, the flow rate of the corresponding pipeline can be adjusted through each valve, and the second feed valve 12 is in signal linkage with an actuator 10 and used for adjusting and controlling the flow rate of the supplementary catalyst.
In an optimized implementation mode, the feed end of the catalyst slurry mixing tank 1 is connected with a catalyst pipeline 14 and an auxiliary material pipeline 15, and the auxiliary material in the auxiliary material pipeline 15 is heavy diesel oil or liquid paraffin.
The method for replacing the catalyst on-line in the present invention will be described with reference to specific examples.
Example 1
(1) The operating temperature of the slurry bed synthesis reactor 3 is 220 ℃, the operating pressure is 3.1MPa, the flow rate of raw material gas at the inlet of the slurry bed synthesis reactor 3 is 103kmol/h, the molar content of CO is 18.2%, the molar content of CO in product gas at the outlet of the slurry bed synthesis reactor 3 is 9.3%, the CO conversion rate is 60%, the CO conversion rate range set by the system is 45% -70%, the activity of the catalyst is reduced after the slurry bed synthesis reactor 3 is continuously operated for 1 week, and the calculator 9 displays that the CO conversion rate is gradually reduced. It was calculated that when the actual value of the CO conversion rate was deviated from the set lower limit value by 25% (at this time, the CO conversion rate was about 34%), the discharged amount of the catalyst slurry containing the deactivated catalyst to be discharged was 300kg, and the replenished amount of the fresh catalyst was 70kg.
(2) 210kg of heavy diesel oil and 70kg of a catalyst to be activated are added to a catalyst slurry preparation tank 1, the temperature of the catalyst slurry preparation tank 1 is maintained at about 60 ℃, the pressure is maintained at about 1.0MPa, and the mixture is fully stirred for about 0.5 hour to obtain 280kg of catalyst slurry.
(3) And after the activation reactor 2 is qualified through nitrogen replacement, starting the first conveying pump 5, opening the first feeding valve 11, conveying the catalyst slurry in the catalyst slurry preparation tank 1 into the activation reactor 2 for activation, closing the first feeding valve 11 after the catalyst slurry is conveyed, and closing the first conveying pump 5. The catalyst is continuously activated in the activation reactor 2 for 12 to 28 hours, the activation temperature is maintained at 240 to 270 ℃, and the pressure is 3.0 to 3.2MPa, so that the fresh catalyst with stable catalytic activity performance is obtained.
(4) The calculator 9 shows that the actual value of the CO conversion rate is lower than the system set lower limit value, and when the relative deviation is close to 25%, the catalyst discharge tank is qualified by nitrogen replacement, the temperature of the catalyst discharge tank is not lower than 160 ℃, the discharge valve 13 is opened, 300kg of catalyst slurry containing part of deactivated catalyst is discharged into the catalyst discharge tank 4 under the action of the pressure difference between the slurry bed synthesis reactor 3 and the catalyst discharge tank 4, and after the discharge is finished, the discharge valve 13 is closed.
(5) After the reaction state in the slurry bed synthesis reactor 3 is determined to be stable, the temperature gradient is distributed stably in the radial direction, and the pressure is relatively stable, the second delivery pump 6 is started, the second feed valve 12 is opened, 280kg of activated fresh catalyst slurry in the activation reactor 2 is delivered to the slurry bed synthesis reactor 3, during the process of supplementing the fresh catalyst, the flow rate of the supplemented catalyst is controlled through the actuator 10, the relative deviation value between the actual value of the CO conversion rate and the set lower limit value displayed by the calculator 9 and the temperature and pressure change condition of the slurry bed synthesis reactor 3 are closely noticed, the fresh catalyst slurry is completely supplemented, the second feed valve 12 is closed, the second delivery pump 6 is closed, and about 48 hours are consumed for completing one catalyst replacement.
Example 2
(1) The operation temperature of the slurry bed synthesis reactor 3 is 210 ℃, the operation pressure is 3.0MPa, the flow rate of the raw material gas at the inlet of the slurry bed synthesis reactor 3 is 500kmol/h, the molar content of CO is 19.3 percent, the molar content of CO in the product gas at the outlet of the slurry bed synthesis reactor 3 is 9.8 percent, and the conversion rate of CO is 52 percent. The set range of the CO conversion rate of the system is 45-70%, the activity of the catalyst is reduced after the slurry bed synthesis reactor 3 is continuously operated for 1 week, the calculator 9 displays that the CO conversion rate is gradually reduced, and when the relative deviation between the actual value of the CO conversion rate and the set lower limit value reaches 20% (at the moment, the CO conversion rate is about 36%), the discharge amount of the catalyst slurry containing the deactivated catalyst to be discharged is 1500kg, and the make-up amount of the fresh catalyst is 350kg.
(2) 1050kg of heavy diesel oil and 350kg of catalyst to be activated are added into the catalyst slurry preparation tank 1, the temperature of the catalyst slurry preparation tank 1 is maintained at about 60 ℃, the pressure is about 1.0MPa, and the catalyst slurry is fully stirred for about 0.5 hour to obtain 1400kg of catalyst slurry.
(3) And determining that the activation reactor 2 is qualified through nitrogen replacement, starting the first delivery pump 5, opening the first feed valve 11, delivering the catalyst slurry in the catalyst slurry preparation tank 1 into the activation reactor 2 for activation, closing the first feed valve 11 after the catalyst slurry is delivered, and closing the first delivery pump 5. The catalyst is continuously activated in the activation reactor 2 for about 12 to 28 hours, the activation temperature is maintained at 240 to 270 ℃, and the pressure is 3.0 to 3.2MPa, so that the fresh catalyst with stable catalytic activity performance is obtained.
(4) The calculator 9 shows that the actual value of the CO conversion rate is lower than the lower limit of the set target value of the system, the relative deviation is close to 20%, the catalyst discharge tank is qualified by replacing nitrogen, the temperature of the catalyst discharge tank 4 is not lower than 160 ℃, the discharge valve 13 is opened, 1500kg of catalyst slurry containing a part of deactivated catalyst is discharged into the catalyst discharge tank 4 under the action of the pressure difference between the slurry bed synthesis reactor 3 and the catalyst discharge tank 4, and the discharge valve 13 is closed after the discharge is finished.
(5) After the reaction state in the slurry bed synthesis reactor is determined to be stable, the temperature gradient is distributed stably in the radial direction, and the pressure is relatively stable, the second delivery pump 6 is started, the second feed valve 12 is opened, 1400kg of activated fresh catalyst slurry in the activation reactor 2 is delivered to the slurry bed synthesis reactor 3, during the process of supplementing the fresh catalyst, the flow rate on a catalyst supplementing pipeline is controlled through the actuator 10, the relative deviation value of the actual value of the CO conversion rate displayed by the calculator 9 and the set lower limit value and the temperature and pressure change condition of the slurry bed synthesis reactor 3 are closely noticed, the fresh catalyst slurry is completely supplemented, the second feed valve 12 is closed, the second delivery pump 6 is closed, and about 48 hours are consumed for completing one catalyst replacement.
It should be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention. Although an embodiment of the present invention has been described, it is to be understood that the present invention should not be limited to this embodiment, and variations and modifications can be made by those skilled in the art within the spirit and scope of the present invention as defined in the appended claims.
Claims (10)
1. An online replacing method for a catalyst of a slurry bed synthesis reactor is characterized by comprising the following steps:
(1) Calculating the discharge amount of catalyst slurry in the slurry bed synthesis reactor and the make-up amount of fresh catalyst when the relative deviation between the actual value of the CO conversion rate and the set lower limit value is X;
(2) Preparing catalyst slurry according to the supplement amount of the fresh catalyst determined in the step 1;
(3) Conveying the catalyst slurry obtained in the step 2 to an activation reactor for activation to obtain a fresh catalyst with catalytic activity;
(4) When the relative deviation between the actual value of the CO conversion rate and the set lower limit value reaches X, conveying the catalyst slurry in the slurry bed synthesis reactor to a catalyst unloading tank according to the unloading amount of the catalyst slurry determined in the step 1;
(5) And (3) after the discharging is finished, conveying the activated fresh catalyst in the step (3) to the slurry bed synthesis reactor.
2. The method for replacing the catalyst of the slurry bed synthesis reactor in an on-line manner as recited in claim 1, wherein in the step 1, the deviation X of the actual value of the CO conversion rate from the set lower limit value is not higher than 32%.
3. The method for replacing the catalyst of the slurry bed synthesis reactor in-line as claimed in claim 1, wherein in the step 5, after the activated fresh catalyst is delivered to the slurry bed synthesis reactor, the actual value of the CO conversion rate is not deviated from the set upper limit value by more than 12%.
4. The method for replacing the catalyst of the slurry bed synthesis reactor in an online manner according to claim 1, wherein in the step 2, the catalyst and the heavy diesel oil or the liquid paraffin are stirred according to a mass percentage of 1.
5. The method for replacing the catalyst of the slurry bed synthesis reactor on line according to claim 1, wherein the step 3, the step of conveying the catalyst slurry to the activation reactor for activation specifically comprises the following steps:
the activation time of the catalyst slurry in the activation reactor is 12-28 hours, the activation temperature is 240-270 ℃, and the activation pressure is 3.0-3.2 MPa.
6. The method for replacing the catalyst of the slurry bed synthesis reactor on line as claimed in claim 1, wherein the step 4 of transferring the catalyst slurry in the slurry bed synthesis reactor to the catalyst discharge tank specifically comprises:
and conveying the catalyst slurry through the pressure difference between the slurry bed synthesis reactor and a catalyst discharge tank, wherein the temperature in the catalyst discharge tank is not lower than 160 ℃.
7. The system for replacing the catalyst of the slurry bed synthesis reactor on line is characterized by comprising an activation reactor, a slurry bed synthesis reactor and a catalyst discharge tank, wherein the activation reactor is connected with the catalyst inlet end of the slurry bed synthesis reactor; the device comprises a slurry bed synthesis reactor, and is characterized by also comprising a first detector for detecting the content of CO in feed gas of the slurry bed synthesis reactor and a second detector for detecting the content of CO in product gas, wherein the first detector and the second detector are connected with a calculator for calculating the CO conversion rate, and an actuator connected with the calculator is arranged on a pipeline between the activation reactor and the slurry bed synthesis reactor.
8. The on-line catalyst replacement system for the slurry bed synthesis reactor according to claim 7, wherein a first delivery pump is arranged on a pipeline between the catalyst slurry preparation tank and the activation reactor, and a second delivery pump is arranged on a pipeline between the activation reactor and the slurry bed synthesis reactor.
9. The system for replacing the catalyst of the slurry bed synthesis reactor in the on-line manner as claimed in claim 7, wherein the feed end of the catalyst slurry preparation tank is connected with a catalyst pipeline and an auxiliary material pipeline, and the auxiliary material in the auxiliary material pipeline is heavy diesel oil or liquid paraffin.
10. The system for on-line replacement of catalyst in a slurry bed synthesis reactor as claimed in claim 8, wherein a first feeding valve is further disposed on the pipeline between the catalyst slurry preparation tank and the activation reactor, a second feeding valve is disposed on the pipeline between the activation reactor and the slurry bed synthesis reactor, and a discharge valve is disposed on the pipeline between the slurry bed synthesis reactor and the catalyst discharge tank.
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