CN109126641A - Fischer-tropsch synthetic catalyst fluid bed reduction device and on-line period method - Google Patents
Fischer-tropsch synthetic catalyst fluid bed reduction device and on-line period method Download PDFInfo
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- CN109126641A CN109126641A CN201710451396.5A CN201710451396A CN109126641A CN 109126641 A CN109126641 A CN 109126641A CN 201710451396 A CN201710451396 A CN 201710451396A CN 109126641 A CN109126641 A CN 109126641A
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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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/18—Reducing with gases containing free hydrogen
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
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Abstract
The present invention relates to fischer-tropsch synthetic catalyst fluid bed reduction fields, disclose fischer-tropsch synthetic catalyst fluid bed reduction device and on-line period method.The device includes: fluid bed reduction reactor (1), catalyst sampling collector (2) and sampling line (5)；Catalyst sampling collector (2) is connected by the sampling line (5) with sample cock (50) with fluid bed reduction reactor (1), for taking out the fischer-tropsch synthetic catalyst in fluid bed reduction reactor (1)；Wherein, fluid bed reduction reactor (1) includes that the reducing gas pipeline (3) with air intake valve (30) and the fischer-tropsch synthetic catalyst with material inlet valve (40) add agent pipeline (4)；Catalyst sampling collector (2) includes collecting tank (21), pressure gauge (22) and the exhaust emissions pipeline (23) with drain tap (24).It is reliable that online flexibly sampling, sampling sample quality in fischer-tropsch synthetic catalyst fluidizing reduction process may be implemented in the present invention.
Description
Technical field
The present invention relates to fischer-tropsch synthetic catalyst fluid bed reduction fields, and in particular to fischer-tropsch synthetic catalyst fluidized bed is also
Original device and on-line period method.
Background technique
F- T synthesis technology is the key technology of ICL for Indirect Coal Liquefaction technology, mainly includes activation, the Fischer-Tropsch conjunction of catalyst
At the processes such as reaction, the cooling of Fischer-Tropsch synthetic and separation and Fischer-Tropsch synthesis oil/cerotin refining upgrading, the wherein activation of catalyst
It has a decisive role.At present the fischer-tropsch synthetic catalyst reducing process of mainstream be divided into gas-liquid-solid three-phase slurry bed system reduction and
Gas-particle two-phase fluidizes bed and restores two kinds.
Compared to slurry bed system reducing process, gas-solid fluidized bed reducing process is will catalysis in the presence of gas-particle two-phase
Agent is restored, and reducibility gas (the generally gaseous mixture of hydrogen and carbon monoxide) serves as pair that reducing agent and catalyst are stired and make muddy
Weight function has the advantages such as reduction pressure is low, the recovery time is short.
In the mistake that fischer-tropsch synthetic catalyst carries out also original production or research reducing process parameter influences catalyst performance
Cheng Zhong is sampled analysis to the catalyst in reduction reactor, is beneficial to grasp the degree that catalyst is reduced, facilitates tune
Whole technology controlling and process.But it compared to there is no atoleine guard catalyst in slurry bed system reducing process, is easy ingress of air and produces
Secondary oxidation reaction is given birth to, so that reduction-state catalyst member or whole lose catalytic activity.Therefore fluid bed reduction technique is applied
When, sampling and discharging to reduction rear catalyst are one of the key technologies of the technique successful operation.
CN103551207A discloses a kind of fixed fluidized bed or gas-solid bubbling bed fischer-tropsch catalysts reduction activation system, packet
Include: at least one fixed fluidized-bed reactor or gas-solid bubbling bed reactor, fischer-tropsch catalysts are reduced activation wherein；Extremely
A few cyclone separator, the tail that fine particle underproof in fischer-tropsch catalysts and/or dust and reduction activation are generated
Gas is mutually separated with the fischer-tropsch catalysts after reduction activation.Preferably, the system also includes the meterings of: at least one fischer-tropsch catalysts
Scale, the quality of the catalyst for controlling the reduction activation entered in Fischer-Tropsch synthesis device；With at least one gas mixer,
Composition for reducing gas or reducing atmosphere needed for adjusting fischer-tropsch catalysts reduction activation.The invention provides F- T synthesis and urges
The gas-particle two-phase fluidisation bed of agent goes back original system, but without reference to how on-line analysis or the method that monitors reduction process, or
The method of line sampling.
CN201778047U discloses a kind of high-temperature fluidized bed device of process sampling, including, high-temperature fluidized bed device
And air inlet pipe and feeder thereon；Wherein, high-temperature fluidized bed device lower part sets a process sampling rifle, the sampling of process sampling rifle
Port is between high-temperature fluidized bed device air inlet pipe and feeder.What the device can be reacted in fluidized-bed reactor
It realizes simultaneously to reaction mass on-line period.But since sampling gun capacity is smaller, it is impossible to be used in sample is largely drawn off.This
Outside, the not set suitable atmosphere protection of this sampling system and hazardous gas tapping equipment, sample will not be sent out after being unable to ensure reduction
Raw secondary oxidation is reacted and is reoxidized；It is easy to send out by the reducibility gas being discharged in reactor with sample in sampling process
Life explodes and generates safety accident.
Apply at present for fischer-tropsch synthetic catalyst reduction fluidized-bed reactor, usually used discharge method be
Discharge pipe is arranged in reactor bottom, and plug valve is arranged on discharge pipe, realizes discharging by the switch of plug valve.Because of reactor
The requirement of heating design is generally shown in Fig. 1 there are the pipeline of certain length between discharging plug valve and reactor.Work as reduction reaction
In the process or after carrying out on-line period, in the pipeline can remaining sample, since temperature is low and without reducibility gas, this portion in pipeline
Reduction reaction or reduction will not occur for divided catalyst not exclusively, influence the sample or final catalyst of subsequent samples, reduce
The using effect and reactivity worth of catalyst progress F- T synthesis.In addition, being inevitably present portion using above-mentioned sampler
Divided catalyst fine powder remains on plug valve, so that plug valve can not completely close, generates gas leakage phenomenon, it is difficult to guarantee device
Air-tightness.In addition, catalyst sampling needs to carry out after temperature of reactor decline when using above-mentioned sampler, cannot achieve
On-line period.
Summary of the invention
The purpose of the invention is to realize the fischer-tropsch synthetic catalyst of progress reduction reaction in fluid bedreactors
On-line period provides fischer-tropsch synthetic catalyst fluid bed reduction device and on-line period method, which, which has, takes
The advantage that the sample time is flexible, sample quality is reliable, it can be ensured that the accuracy of reduction-state evaluating catalyst data.
To achieve the goals above, the first aspect of the present invention provides a kind of fischer-tropsch synthetic catalyst fluid bed reduction dress
It sets, which includes: fluid bed reduction reactor 1, catalyst sampling collector 2 and sampling line 5；Catalyst sampling collector
2 are connected by the sampling line 5 with sample cock 50 with fluid bed reduction reactor 1, anti-for taking out fluid bed reduction
Answer the fischer-tropsch synthetic catalyst in device 1；
Wherein, fluid bed reduction reactor 1 includes having the reducing gas pipeline 3 of air intake valve 30 and with material inlet valve
40 fischer-tropsch synthetic catalyst adds agent pipeline 4；Reducing gas pipeline 3 is for conveying reproducibility into fluid bed reduction reactor 1
Gas makes the fischer-tropsch synthetic catalyst in fluid bed reduction reactor 1 be fluidized and be occurred reduction reaction；Catalyst sampling is received
Storage 2 includes collecting tank 21, pressure gauge 22 and the exhaust emissions pipeline 23 with drain tap 24；Band is set on sampling line 5
There are the back-blowing pipeline 6 of back-blowing valve 60 and the nitrogen pipeline 7 with nitrogen valve 70.
The second aspect of the present invention provides fischer-tropsch synthetic catalyst fluid bed reduction device of the invention and carries out on-line period
Method make the fluid bed reduction reactor this method comprises: (A) is passed through reducibility gas to fluid bed reduction reactor
Interior fischer-tropsch synthetic catalyst is fluidized, and carries out reduction reaction under the reducing conditions；(B) to catalyst sampling collector and
After sampling line is filled with nitrogen, the fluid bed reduction reactor is connected to by the sampling line and catalyst sampling is received
Storage, make to be fluidized and carried out in the fluid bed reduction reactor part fischer-tropsch synthetic catalyst of reduction reaction into
Enter the catalyst sampling collector, while the catalyst sampling collector carries out exhaust emissions；(C) use back-blowing by institute
It states after sampling line purged, the fluid bed reduction reactor and the catalyst sampling collector is disconnected；(D) by institute
The atmosphere stated in catalyst sampling collector is replaced into nitrogen；And adjust the flow of the reducibility gas, make gas agent ratio with into
Gas agent when row step (A) is than identical.
Preferably, in step (A), the reducibility gas is to contain H2With the gaseous mixture of CO, and H2With the molar ratio of CO
For (5~40): 1, the empty tower gas velocity of the reducibility gas is 0.05~0.4m/s, and the gas agent ratio is 1.6~12.4m3/
(kgCat·h)。
Preferably, in step (A), reduction reaction temperature is 240~280 DEG C；Reducibility gas pressure be 0.1~
0.6MPa, preferably 0.15~0.5MPa.
Preferably, in step (B), the nitrogen that nitrogen reaches is filled with to the catalyst sampling collector and sampling line
Pressure is less than the reducibility gas pressure；It is preferred that pressure difference between nitrogen pressure and reducibility gas pressure be 0.05~
0.1MPa。
Preferably, this method further comprises: during carrying out the reduction reaction, it is more to repeat step (B)-(D)
It is secondary, for taking out the fischer-tropsch synthetic catalyst of the experience different reduction reaction times.
Through the above technical solutions, may be implemented to carry out reduction reaction in fluidized-bed reactor when fischer-tropsch synthetic catalyst
When, under without exposure to oxygen or air conditions, the on-line period of catalyst is completed using pressure difference, and blowback can be passed through
Step avoids sample carryover in pipeline.Realize that sample time is flexible in fluid bed reduction technical process, sampling process is without oxygen again
Change risk, sample quality is reliable, ensure that the reliability of sampling analysis result.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of prior art fluid bed reduction reactor, has discharge duct；
Fig. 2 is fischer-tropsch synthetic catalyst fluid bed reduction schematic device provided by the invention.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, in the case where without particularly describing, term " top " or " bottom " respectively describe vertical side
To " top " or " lower part " of upper container." middle part " is on structure of container in the part between " top " and " bottom ".
The first aspect of the present invention provides a kind of fischer-tropsch synthetic catalyst fluid bed reduction device, as shown in Fig. 2, the dress
It sets and includes:
Fluid bed reduction reactor 1, catalyst sampling collector 2 and sampling line 5；Catalyst sampling collector 2 passes through
Sampling line 5 with sample cock 50 is connected with fluid bed reduction reactor 1, for taking out fluid bed reduction reactor 1
Interior fischer-tropsch synthetic catalyst；
Wherein, fluid bed reduction reactor 1 includes having the reducing gas pipeline 3 of air intake valve 30 and with material inlet valve
40 fischer-tropsch synthetic catalyst adds agent pipeline 4；Reducing gas pipeline 3 is for conveying reproducibility into fluid bed reduction reactor 1
Gas makes the fischer-tropsch synthetic catalyst in fluid bed reduction reactor 1 be fluidized and be occurred reduction reaction；Catalyst sampling is received
Storage 2 includes collecting tank 21, pressure gauge 22 and the exhaust emissions pipeline 23 with drain tap 24；Band is set on sampling line 5
There are the back-blowing pipeline 6 of back-blowing valve 60 and the nitrogen pipeline 7 with nitrogen valve 70.
In the present invention, fluid bed reduction reactor 1 can be fluidized-bed reactor commonly used in the art, can be realized
Fischer-tropsch synthetic catalyst forms catalyst fluidization bed under the drive of certain reducibility gas.Fluid bed reduction reaction
Device 1 can be pressure high-temp resistant container.
Catalyst sampling collector 2 is small-sized pressure vessel, and collecting tank 21 therein is used to contain the catalyst of sampling amount,
Pressure gauge 22 can indicate the pressure in collecting tank 21.When exhaust emissions pipeline 23 is used to that on-line period will to be carried out, from fluidized bed
The reducibility gas being discharged in reduction reactor 1 is discharged into exhaust collection processing unit.Catalyst sampling collector 2 can be
Demountable device can separate after completing on-line period with fluid bed reduction reactor 1.
In the present invention, under preferable case, reducing gas pipeline 3 is passed through fluidized bed from the bottom of fluid bed reduction reactor 1
The inside of reduction reactor 1.
In the present invention, under preferable case, reducing gas pipeline 3 protrudes into the part of fluid bed reduction reactor 1 with gas
Distributor 31；The gas outlet 32 of multiple bottoms towards fluid bed reduction reactor 1 is set on gas distributor 31.Gas outlet 32
Direction when can be conducive to be passed through reducibility gas, the fischer-tropsch synthetic catalyst of 1 bottom of fluid bed reduction reactor is abundant
Fluidisation, there is no the dead zones of catalyst residence.
In the present invention, under preferable case, fischer-tropsch synthetic catalyst adds agent pipeline 4 from the middle part of fluid bed reduction reactor 1
It is passed through, and leads to the bottom of fluidized-bed reactor 1.
In the present invention, under preferable case, sampling line 5 is connected to bottom and the collecting tank 21 of fluid bed reduction reactor 1
Top；Sampling line 5 enters collecting tank 21 and leads to the bottom of collecting tank 21.
In the present invention, under preferable case, the bottom of fluid bed reduction reactor 1 is arranged or is not provided with catalyst discharge port.
It is preferred that being not provided with catalyst discharge port, on-line period is carried out by catalyst sampling collector 2.
Reduction reaction process may be implemented using fischer-tropsch synthetic catalyst fluid bed reduction device provided by the invention not stop
On-line period in the case where only.And when using the reduction reactor of the prior art as shown in Figure 1, each reaction time reaches
When sample time, such as to sample to require atmosphere in reactor is first converted to nitrogen and stop reduction reaction and by the temperature of reactor
Degree is cooled to room temperature.When carrying out the sampling of multiple times, need to restart again to carry out reduction reaction.Such as it is reacted
6h, 15h and for 24 hours when sampling, needing respectively to carry out the reaction time respectively is 6h, 15h and reaction independent three times for 24 hours,
In need heating and temperature-fall period three times, the total operating time for completing three sub-samplings very long (including will heat up every time and cool down
Time, and the time reacted).In addition, requiring the gas in metathesis reactor in each heating and temperature-fall period
Atmosphere (nitrogen displaced air, reducibility gas displacement nitrogen), thus need to consume more nitrogen, hydrogen and carbon monoxide.Again
Have, completes sampling by the way that the catalyst discharge port of reactor bottom is arranged in using when reduction reactor shown in FIG. 1, not only deposit
The risk of sample quality is influenced by secondary oxidation in sample ingress of air, and the sealing of discharge port is because of catalyst fine particle
Influence and require very high.Therefore, compared under, fischer-tropsch synthetic catalyst fluid bed reduction device provided by the invention can be with
Time saving, reduction material consumption may be implemented in primary heating before only starting reaction and the primary cooling after gross sample, and
Sampling carries out under nitrogen protection, and the result of catalyst performance test is more acurrate.
Second aspect of the present invention provides fischer-tropsch synthetic catalyst fluid bed reduction device of the invention and carries out on-line period
Method, this method comprises:
(A) it is passed through reducibility gas to fluid bed reduction reactor, closes the Fischer-Tropsch in the fluid bed reduction reactor
It is fluidized at catalyst, and carries out reduction reaction under the reducing conditions；
(B) after being filled with nitrogen to catalyst sampling collector and sampling line, the stream is connected to by the sampling line
Change bed reduction reactor and the catalyst sampling collector, make to carry out in the fluid bed reduction reactor fluidisation and into
The part fischer-tropsch synthetic catalyst of row reduction reaction enters the catalyst sampling collector, while catalyst sampling is collected
Device carries out exhaust emissions；
(C) it after being purged the sampling line using back-blowing, by the fluid bed reduction reactor and described urges
Agent sampling collector disconnects；
(D) atmosphere in the catalyst sampling collector is replaced into nitrogen；And adjust the stream of the reducibility gas
Amount makes gas agent ratio with gas agent when carrying out step (A) than identical.
Method provided by the invention is used for the catalyst sampling collector for being replaced into nitrogen atmosphere to be subjected to reduction reaction
Fischer-tropsch synthetic catalyst sampling, it is ensured that the catalyst of taking-up avoids contact with air, and secondary oxidation does not occur, to protect
Demonstrate,prove the reliability of analytical sampling results of property.
In method provided by the invention, volume (m of the gas agent than referring to reducibility gas3) reacted with fluid bed reduction
Ratio between the quality (kg) for the fischer-tropsch synthetic catalyst that the unit time feeds in device.On-line period makes fluid bed reduction reactor
The Mass lost of interior fischer-tropsch synthetic catalyst needs accordingly adjustment to continue for the consistency for keeping reduction reaction conditions
The flow of reducibility gas when reduction reaction is constant with the condition for meeting gas agent ratio.
In the present invention, under preferable case, in step (A), the reducibility gas is to contain H2With the gaseous mixture of CO, and
H2Molar ratio with CO is (5~40): 1, the empty tower gas velocity of the reducibility gas is 0.05~0.4m/s, and the gas agent ratio is
1.6~12.4m3/(kgCat·h)。
In the present invention, under preferable case, in step (A), reduction reaction temperature is 240~280 DEG C；Reducibility gas pressure
Power is 0.1~0.6MPa, preferably 0.15~0.5MPa.
In the present invention, under preferable case, in step (B), it is filled with to the catalyst sampling collector and sampling line
The nitrogen pressure that nitrogen reaches is less than the reducibility gas pressure；It is preferred that between nitrogen pressure and reducibility gas pressure
Pressure difference is 0.05~0.1MPa.
In the present invention, this method further comprises: during carrying out the reduction reaction, repeating step (B)-(D)
Repeatedly, for taking out the fischer-tropsch synthetic catalyst of the experience different reduction reaction times.
In the present invention, back-blowing used in step (C) is the reducibility gas.
Using on-line period method provided by the invention, can be taken in the non-stop situation of reduction reaction process
Sample, can it is time saving, reduce material consumption, and sampling carry out under nitrogen protection, catalyst performance test result it is more acurrate.
On-line period method provided by the invention is illustrated in combination with fig. 2 in fischer-tropsch synthetic catalyst fluid bed reduction of the invention
Application process on device.
(1) open material inlet valve 40 adds agent pipeline 4 to be added into fluid bed reduction reactor 1 by fischer-tropsch synthetic catalyst
A certain amount of fischer-tropsch synthetic catalyst is then shut off material inlet valve 40；
It opens air intake valve 30 to replace the atmosphere in fluid bed reduction reactor 1 by reducing gas pipeline 3, first
It is replaced into nitrogen and is replaced as H again2, reducibility gas is then replaced into (containing H2With the gaseous mixture of CO), and stablize H2With mole of CO
Than, reducibility gas pressure, gentle dose of empty tower gas velocity ratio, fischer-tropsch synthetic catalyst is in fluidized state；Pass through gas chromatographic detection
Gas composition meets reduction reaction requirement in fluid bed reduction reactor 1, starts to carry out heating behaviour to fluidized bed reduction reactor 1
Make.
(2) maintain the flow of reducibility gas constant, according to the heating curve of setting by the temperature of fluid bed reduction reactor 1
Degree is increased to reduction temperature, starts to carry out reduction reaction to catalyst.Set reduction reaction starting point, be set in reduction reaction into
Row 6h, 15h and for 24 hours when on-line period fluid bed reduction reactor 1 in catalyst carry out performance evaluation.
(3) when the reduction reaction time reaching 6h, start the sampling operation for carrying out catalyst: by catalyst sampling collector
2 connection sampling lines 5；Nitrogen valve 70 and drain tap 24 are opened, by nitrogen pipeline 7 by 2 He of catalyst sampling collector
Atmosphere in sampling line 5 is replaced into nitrogen completely, and nitrogen pressure in collecting tank 21 is maintained to be less than fluid bed reduction reactor 1
Middle reducibility gas pressure；
Nitrogen valve 70 and drain tap 24 are closed, sample cock 50 is opened, the Fischer-Tropsch in fluid bed reduction reactor 1 closes
At catalyst in the pressure difference in nitrogen pressure in collecting tank 21 and fluid bed reduction reactor 1 between reducibility gas pressure
Under effect, into nitrogen protection under collecting tank 21；Meanwhile opening drain tap 24 makes the reduction for following catalyst to be discharged together
Property gas is discharged into utility line via exhaust emissions pipeline 23 and is focused on；
When weighing the sample size that catalyst quality obtained in collecting tank 21 is needed, opens back-blowing valve 60 and pass through
Back-blowing pipeline 6 purges catalyst sampling collector 2 and sampling line 5 with reducibility gas, can purge twice；It is then shut off
Sample cock 50 turns off back-blowing valve 60 and opens simultaneously nitrogen valve 70, will be replaced into nitrogen in catalyst sampling collector 2
Gas closes drain tap 24；It is the fischer-tropsch synthetic catalyst sample of the taking-up under nitrogen protection in collecting tank 21.By the sample of taking-up
Product carry out performance evaluation.
(4) according to the quality of the fischer-tropsch synthetic catalyst of taking-up, the air inflow of reducibility gas is adjusted, so that fluidized bed is also
Gas agent ratio in former reactor 1 and the gas agent in step (1) continue reduction reaction than identical (i.e. with before sampling consistent).
(5) when the reduction reaction time reach 15h and for 24 hours when, repeat the above steps (3) and (4) respectively, and taking-up experienced
The fischer-tropsch synthetic catalyst sample of 15h and for 24 hours reduction reaction is used for performance evaluation.
The present invention will be described in detail by way of examples below.
Embodiment 1
Reduction reaction sampling is carried out using reduction reaction device of the invention shown in Fig. 2.
(1) fluid bed reduction reactor is added in 1kg fischer-tropsch synthetic catalyst to be restored；It will be in fluid bed reduction reactor
Atmosphere is successively replaced as nitrogen, H2, then it is replaced as reducibility gas (H2Molar ratio with CO is 5:1), set reducibility gas
Pressure is 0.1MPa, and the empty tower gas velocity of reducibility gas is 0.1m/s, and gas agent ratio is 1.6m3/(kgCat·h).Utilize gas phase color
Detection gas composition is composed, H is worked as2/ CO=(5 ± 0.1): start to carry out warming temperature to fluidized bed reduction reactor when 1.
(2) maintain the flow of reducibility gas constant, according to the heating curve of setting by the temperature of fluid bed reduction reactor
Degree is increased to 240 DEG C, starts to carry out reduction reaction to catalyst.Setting reduction reaction temperature is stablized 15min after reaching 240 DEG C and is made
For the starting point of reduction reaction, reduction reaction proceed to 6h, 15h and for 24 hours when carry out on-line period respectively.
(3) when the recovery time reaching 6h, start the sampling operation for carrying out catalyst: catalyst sampling collector 2 is connected
Connect sampling line 5；Nitrogen valve 70 and drain tap 24 are opened, by catalyst sampling collector 2 and is sampled by nitrogen pipeline
Atmosphere in pipeline 5 is replaced into nitrogen completely, and maintaining nitrogen pressure in collecting tank is 0.05MPa；
Nitrogen valve 70 and drain tap 24 are closed, sample cock 50 is opened, the Fischer-Tropsch in fluid bed reduction reactor 1 closes
At catalyst in the pressure difference in nitrogen pressure in collecting tank 21 and fluid bed reduction reactor 1 between reducibility gas pressure
Under effect, into nitrogen protection under collecting tank 21；Meanwhile opening drain tap 24 makes the reduction for following catalyst to be discharged together
Property gas is discharged into utility line via exhaust emissions pipeline 23 and is focused on；
When catalyst quality obtained in weighing collecting tank 21 reaches 20g, opens back-blowing valve 60 and pass through reverse-blow pipe
Line 6 purges catalyst sampling collector 2 and sampling line 5, can purge twice；It is then shut off sample cock 50, is turned off anti-
Blowing valve 60 opens simultaneously nitrogen valve 70, and nitrogen will be replaced into catalyst sampling collector 2, closes drain tap 24；
It is the fischer-tropsch synthetic catalyst sample of the taking-up under nitrogen protection in collecting tank 21.
(4) according to the quality of the fischer-tropsch synthetic catalyst of taking-up, adjusting the air inflow of reducibility gas is original 98%,
So that the gas agent ratio in fluid bed reduction reactor is 1.6m3/ (kgCath), continues reduction reaction.
(5) when the recovery time reach 15h and for 24 hours when, repeat the above steps (3) and (4) respectively, taking-up experienced 15h and
The fischer-tropsch synthetic catalyst sample of reduction reaction for 24 hours.
Comparative example 1
Reduction reaction sampling is carried out using reduction reaction device shown in FIG. 1.
(1) reactor shown in FIG. 1 is added in 1kg fischer-tropsch synthetic catalyst to be restored；Atmosphere in reactor is successively set
Change nitrogen, H into2, then it is replaced as reducibility gas (H2Be 5:1 with the molar ratio of CO), set reducibility gas pressure as
0.1MPa, the empty tower gas velocity of reducibility gas are 0.1m/s, and gas agent ratio is 1.6m3/(kgCat·h).Utilize gas chromatographic detection
Gas composition works as H2/ CO=(5 ± 0.1): start to carry out warming temperature to reactor when 1.
(2) it maintains the flow of reducibility gas constant, the temperature of reactor is increased to 240 according to the heating curve of setting
DEG C, start to carry out reduction reaction to catalyst.Setting reduction reaction temperature stablizes 15min as reduction reaction after reaching 240 DEG C
Starting point, be sampled when reduction reaction proceeds to 6h.
(3) when the recovery time reaching 6h, atmosphere is that nitrogen stops reduction reaction and drops reactor in metathesis reactor
After warming to room temperature, the plunger valve for opening reactor bottom takes out 20g catalyst, turns off plunger valve.
(4) repeat the above steps (1)-(3), and reduction reaction carries out 15h and for 24 hours respectively, carries out catalyst sampling respectively.
Embodiment 2
Reduction reaction sampling is carried out using reduction reaction device of the invention shown in Fig. 2.
(1) fluid bed reduction reactor is added in 1kg fischer-tropsch synthetic catalyst to be restored；It will be in fluid bed reduction reactor
Atmosphere is successively replaced as nitrogen, H2, then it is replaced as reducibility gas (H2Molar ratio with CO is 40:1), set reproducibility gas
Body pressure is 0.6MPa, and the empty tower gas velocity of reducibility gas is 0.4m/s, and gas agent ratio is 12.4m3/(kgCat·h).Utilize gas
Phase chromatography detection gas composition, works as H2/ CO=(40 ± 0.2): start to carry out warming temperature to fluidized bed reduction reactor when 1.
(2) maintain the flow of reducibility gas constant, according to the heating curve of setting by the temperature of fluid bed reduction reactor
Degree is increased to 280 DEG C, starts to carry out reduction reaction to catalyst.Setting reduction reaction temperature is stablized 15min after reaching 280 DEG C and is made
For the starting point of reduction reaction, reduction reaction carry out 6h, 15h and for 24 hours when carry out on-line period respectively.
(3) when the recovery time reaching 6h, start the sampling operation for carrying out catalyst: catalyst sampling collector 2 is connected
Connect sampling line 5；Nitrogen valve 70 and drain tap 24 are opened, by catalyst sampling collector 2 and is sampled by nitrogen pipeline 7
Atmosphere in pipeline 5 is replaced into nitrogen completely, and maintaining nitrogen pressure in collecting tank 21 is 0.5MPa；
Nitrogen valve 70 and drain tap 24 are closed, sample cock 50 is opened, the Fischer-Tropsch in fluid bed reduction reactor 1 closes
At catalyst in the pressure difference in nitrogen pressure in collecting tank 21 and fluid bed reduction reactor 1 between reducibility gas pressure
Under effect, into nitrogen protection under collecting tank 21；Meanwhile opening drain tap 24 makes the reduction for following catalyst to be discharged together
Property gas is discharged into utility line via exhaust emissions pipeline 23 and is focused on；
When catalyst quality obtained in weighing collecting tank 21 reaches 20g, opens back-blowing valve 60 and pass through reverse-blow pipe
Line 6 purges catalyst sampling collector 2 and sampling line 5, can purge twice；It is then shut off sample cock 50, is turned off anti-
Blowing valve 60 opens simultaneously nitrogen valve 70, and nitrogen will be replaced into catalyst sampling collector 2, closes drain tap 24；
It is the fischer-tropsch synthetic catalyst sample of the taking-up under nitrogen protection in collecting tank 21.
(4) according to the quality of the fischer-tropsch synthetic catalyst of taking-up, adjusting the air inflow of reducibility gas is original 98%,
So that the gas agent ratio in fluid bed reduction reactor is 12.4m3/ (kgCath), continues reduction reaction.
(5) when the recovery time reach 15h and for 24 hours when, repeat the above steps (3) and (4) respectively, taking-up experienced 15h and
The fischer-tropsch synthetic catalyst sample of reduction reaction for 24 hours.
Comparative example 2
Reduction reaction sampling is carried out using reduction reaction device shown in FIG. 1.
(1) reactor shown in FIG. 1 is added in 1kg fischer-tropsch synthetic catalyst to be restored；Atmosphere in reactor is successively set
Change nitrogen, H into2, then it is replaced as reducibility gas (H2Be 40:1 with the molar ratio of CO), set reducibility gas pressure as
0.6MPa, the empty tower gas velocity of reducibility gas are 0.4m/s, and gas agent ratio is 12.4m3/(kgCat·h).It is examined using gas-chromatography
Gas composition is surveyed, H is worked as2/ CO=(40 ± 0.2): start to carry out warming temperature to reactor when 1.
(2) it maintains the flow of reducibility gas constant, the temperature of reactor is increased to 280 according to the heating curve of setting
DEG C, start to carry out reduction reaction to catalyst.Setting reduction reaction temperature stablizes 15min as reduction reaction after reaching 280 DEG C
Starting point, reduction reaction carry out 6h when be sampled.
(3) when the recovery time reaching 6h, atmosphere is that nitrogen stops reduction reaction and drops reactor in metathesis reactor
After warming to room temperature, the plunger valve for opening reactor bottom takes out 20g catalyst, turns off plunger valve.
(4) repeat the above steps (1)-(3), and reduction reaction carries out 15h and for 24 hours respectively, carries out catalyst sampling respectively.
Embodiment 3
Reduction reaction sampling is carried out using reduction reaction device of the invention shown in Fig. 2.
(1) fluid bed reduction reactor is added in 1kg fischer-tropsch synthetic catalyst to be restored；It will be in fluid bed reduction reactor
Atmosphere is successively replaced as nitrogen, H2, then it is replaced as reducibility gas (H2Molar ratio with CO is 20:1), set reproducibility gas
Body pressure is 0.3MPa, and the empty tower gas velocity of reducibility gas is 0.25m/s, and gas agent ratio is 7.0m3/(kgCat·h).Utilize gas
Phase chromatography detection gas composition, works as H2/ CO=(20 ± 0.2): start to carry out warming temperature to fluidized bed reduction reactor when 1
(2) maintain the flow of reducibility gas constant, according to the heating curve of setting by the temperature of fluid bed reduction reactor
Degree is increased to 260 DEG C, starts to carry out reduction reaction to catalyst.Setting reduction reaction temperature is stablized 15min after reaching 260 DEG C and is made
For the starting point of reduction reaction, reduction reaction carry out 6h, 15h and for 24 hours when carry out on-line period respectively.
(3) when the recovery time reaching 6h, start the sampling operation for carrying out catalyst: catalyst sampling collector 2 is connected
Connect sampling line 5；Nitrogen valve 70 and drain tap 24 are opened, by catalyst sampling collector 2 and is sampled by nitrogen pipeline 7
Atmosphere in pipeline 5 is replaced into nitrogen completely, and maintaining nitrogen pressure in collecting tank 21 is 0.25MPa；
Nitrogen valve 70 and drain tap 24 are closed, sample cock 50 is opened, the Fischer-Tropsch in fluid bed reduction reactor 1 closes
At catalyst in the pressure difference in nitrogen pressure in collecting tank 21 and fluid bed reduction reactor 1 between reducibility gas pressure
Under effect, into nitrogen protection under collecting tank 21；Meanwhile opening drain tap 24 makes the reduction for following catalyst to be discharged together
Property gas is discharged into utility line via exhaust emissions pipeline 23 and is focused on；
When catalyst quality obtained in weighing collecting tank 21 reaches 20g, opens back-blowing valve 60 and pass through reverse-blow pipe
Line 6 purges catalyst sampling collector 2 and sampling line 5, can purge twice；It is then shut off sample cock 50, is turned off anti-
Blowing valve 60 opens simultaneously nitrogen valve 70, and nitrogen will be replaced into catalyst sampling collector 2, closes drain tap 24；
It is the fischer-tropsch synthetic catalyst sample of the taking-up under nitrogen protection in collecting tank 21.
(4) according to the quality of the fischer-tropsch synthetic catalyst of taking-up, adjusting the air inflow of reducibility gas is original 98%,
So that the gas agent ratio in fluid bed reduction reactor is 7.0m3/ (kgCath), continues reduction reaction.
(5) when the recovery time reach 15h and for 24 hours when, repeat the above steps (3) and (4) respectively, taking-up experienced 15h and
The fischer-tropsch synthetic catalyst sample of reduction reaction for 24 hours.
Comparative example 3
Reduction reaction sampling is carried out using reduction reaction device shown in FIG. 1.
(1) reactor shown in FIG. 1 is added in 1kg fischer-tropsch synthetic catalyst to be restored；Atmosphere in reactor is successively set
Change nitrogen, H into2, then it is replaced as reducibility gas (H2Be 20:1 with the molar ratio of CO), set reducibility gas pressure as
0.3MPa, the empty tower gas velocity of reducibility gas are 0.25m/s, and gas agent ratio is 7.0m3/(kgCat·h).It is examined using gas-chromatography
Gas composition is surveyed, H is worked as2/ CO=(20 ± 0.2): start to carry out warming temperature to reactor when 1.
(2) it maintains the flow of reducibility gas constant, the temperature of reactor is increased to 260 according to the heating curve of setting
DEG C, start to carry out reduction reaction to catalyst.Setting reduction reaction temperature stablizes 15min as reduction reaction after reaching 260 DEG C
Starting point, reduction reaction carry out 6h when be sampled.
(3) when the recovery time reaching 6h, atmosphere is that nitrogen stops reduction reaction and drops reactor in metathesis reactor
After warming to room temperature, the plunger valve for opening reactor bottom takes out 20g catalyst, turns off plunger valve.
(4) repeat the above steps (1)-(3), and reduction reaction carries out 15h and for 24 hours respectively, carries out catalyst sampling respectively.
Catalyst is carried out when by reduction reaction time that embodiment 1-3 and comparative example 1-3 are respectively completed in 6h, 15h and for 24 hours
The result of time consumed by sampling and gas flow is listed in table 1.
Table 1
From the operation of embodiment and comparative example as can be seen that the method for on-line period provided by the invention is multiple and different
Sample time can not stop reduction reaction when being sampled.In table 1 embodiment complete 6h, 15h and for 24 hours when sampling when,
Total time is considerably less than comparative example.
And method provided by the invention do not need it is repeated multiple times heated up and cooled down, reduce in test of many times because rise
Warm rate difference is impacted with rate of temperature fall difference to catalyst performance and the error that generates.In table 1 data show compared to
Comparative example, embodiment can save gas usage in large quantities.
Device and method provided by the invention can save sample time significantly and reduce gas usage, reduce material consumption,
Nitrogen protection sampling increases the accuracy of test data.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of fischer-tropsch synthetic catalyst fluid bed reduction device, the device include:
Fluid bed reduction reactor (1), catalyst sampling collector (2) and sampling line (5)；
Catalyst sampling collector (2) by with sample cock (50) sampling line (5) and fluid bed reduction reactor (1)
It is connected, for taking out the fischer-tropsch synthetic catalyst in fluid bed reduction reactor (1)；
Wherein, fluid bed reduction reactor (1) includes having the reducing gas pipeline (3) of air intake valve (30) and with inlet valve
The fischer-tropsch synthetic catalyst of door (40) adds agent pipeline (4)；Reducing gas pipeline (3) is used for into fluid bed reduction reactor (1)
Conveying reducibility gas makes the fischer-tropsch synthetic catalyst in fluid bed reduction reactor (1) be fluidized and be occurred reduction reaction；
Catalyst sampling collector (2) includes collecting tank (21), pressure gauge (22) and the exhaust emissions with drain tap (24)
Pipeline (23)；
It is provided with the back-blowing pipeline (6) of back-blowing valve (60) on sampling line (5) and has the nitrogen of nitrogen valve (70)
Gas pipeline (7).
2. reduction apparatus according to claim 1, wherein reducing gas pipeline (3) is from fluid bed reduction reactor (1)
Bottom is passed through the inside of fluid bed reduction reactor (1)；
Reducing gas pipeline (3) protrudes into the part of fluid bed reduction reactor (1) with gas distributor (31)；Gas distributor
(31) gas outlet (32) of multiple bottoms towards fluid bed reduction reactor (1) is set on.
3. reduction apparatus according to claim 1 or 2, wherein fischer-tropsch synthetic catalyst add agent pipeline (4) from fluidized bed also
It is passed through in the middle part of former reactor (1), and leads to the bottom of fluidized-bed reactor (1).
4. reduction apparatus according to claim 1, wherein sampling line (5) is connected to the bottom of fluid bed reduction reactor (1)
The top in portion and collecting tank (21)；Sampling line (5) enters collecting tank (21) and leads to the bottom of collecting tank (21).
5. reduction apparatus described in any one of -4 according to claim 1, wherein the bottom of fluid bed reduction reactor (1)
It is arranged or is not provided with catalyst discharge port.
6. the side of the progress on-line period of fischer-tropsch synthetic catalyst fluid bed reduction device described in any one of claim 1-5
Method, this method comprises:
(A) it is passed through reducibility gas to fluid bed reduction reactor, urges the F- T synthesis in the fluid bed reduction reactor
Agent is fluidized, and carries out reduction reaction under the reducing conditions；
(B) after being filled with nitrogen to catalyst sampling collector and sampling line, the fluidized bed is connected to by the sampling line
Reduction reactor and the catalyst sampling collector make fluidized and gone back in the fluid bed reduction reactor
Original reaction part fischer-tropsch synthetic catalyst enter the catalyst sampling collector, while the catalyst sampling collector into
Row exhaust emissions；
(C) after being purged the sampling line using back-blowing, by the fluid bed reduction reactor and the catalyst
Sampling collector disconnects；
(D) atmosphere in the catalyst sampling collector is replaced into nitrogen；And the flow of the reducibility gas is adjusted, make
Gas agent ratio is with gas agent when carrying out step (A) than identical.
7. according to the method described in claim 6, wherein, in step (A), the reducibility gas is to contain H2With mixing for CO
Close gas, and H2Molar ratio with CO is (5~40): 1, the empty tower gas velocity of the reducibility gas is 0.05~0.4m/s, described
Gas agent ratio is 1.6~12.4m3/(kgCat·h)。
8. according to the method described in claim 7, wherein, in step (A), reduction reaction temperature is 240~280 DEG C；Reduction
Property gas pressure be 0.1~0.6MPa, preferably 0.15~0.5MPa.
9. according to the method described in claim 8, wherein, in step (B), to the catalyst sampling collector and probe tube
Line charge enters the nitrogen pressure that nitrogen reaches and is less than the reducibility gas pressure；It is preferred that nitrogen pressure and the reducibility gas
Pressure difference between pressure is 0.05~0.1MPa.
10. the method according to any one of claim 6-9, wherein this method further comprises: carrying out described go back
During original reaction, step (B)-(D) is repeated repeatedly, for taking out the F- T synthesis of the experience different reduction reaction times
Catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111795840A (en) * | 2019-04-09 | 2020-10-20 | 国家能源投资集团有限责任公司 | Device and method for on-line sampling and separating total components of Fischer-Tropsch synthesis reactor |
| CN114269466A (en) * | 2019-06-26 | 2022-04-01 | 埃克斯能量有限责任公司 | Fluidized bed reactor system allowing particle sampling during ongoing reactions |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2622293A1 (en) * | 1987-10-21 | 1989-04-28 | Total France | SYSTEM FOR THE COLLECTION OF A SOLID PARTICLE ENCLOSURE IN A FLUIDIZED BED |
| EP1099473A1 (en) * | 1999-11-11 | 2001-05-16 | Union Carbide Chemicals & Plastics Technology Corporation | Sampling sysem for fluidized bed gas phase polymerization reaction systems |
| US20050047965A1 (en) * | 2003-08-29 | 2005-03-03 | Coute Nicolas P. | Catalyst sampling system |
| CN200996898Y (en) * | 2006-12-30 | 2007-12-26 | 中国石油大学(北京) | Solid particle sampler of multi-point axial parallel negative-pressure for fluidized bed |
| CN201867312U (en) * | 2010-11-18 | 2011-06-15 | 安徽淮化股份有限公司 | Gas-liquid-solid three-phase simultaneously sampling device of fluidized bed reactor |
| CN202083568U (en) * | 2011-04-27 | 2011-12-21 | 上海梅山钢铁股份有限公司 | Pulverized coal sampling device |
| CN202177522U (en) * | 2011-07-19 | 2012-03-28 | 宝山钢铁股份有限公司 | Solid sampling device in high-temperature fluid-bed process |
| CN102507259A (en) * | 2011-09-28 | 2012-06-20 | 神华集团有限责任公司 | Method for sampling solid particles in gas-liquid two phases |
| CN202387441U (en) * | 2011-12-08 | 2012-08-22 | 神华集团有限责任公司 | Sampling device for reactor |
| CN103657538A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for loading and unloading catalysts for fixed fluidized bed reactor |
| CN104198223A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Online particle sampling unit of minitype fluidized bed and application thereof |
| CN204085939U (en) * | 2014-08-29 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | A kind of sampler being applied to the online particle sampling of miniature fluidized bed |
| CN104697295A (en) * | 2013-12-04 | 2015-06-10 | 铜陵市永生机电制造有限责任公司 | Fluidized bed |
| CN204855079U (en) * | 2015-05-27 | 2015-12-09 | 广东大唐国际潮州发电有限责任公司 | Pressure, automatic device that sweeps of differential pressure measurement |
| CN105709858A (en) * | 2014-12-01 | 2016-06-29 | 神华集团有限责任公司 | Catalyst continuous reducing apparatus and method |
| WO2016141403A1 (en) * | 2015-03-06 | 2016-09-15 | Alcoa Of Australia Limited | Online sampling device |
| CN106552632A (en) * | 2015-09-30 | 2017-04-05 | 神华集团有限责任公司 | A kind of method of reducing of Fischer-Tropsch synthetic iron-based catalyst |
-
2017
- 2017-06-15 CN CN201710451396.5A patent/CN109126641B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2622293A1 (en) * | 1987-10-21 | 1989-04-28 | Total France | SYSTEM FOR THE COLLECTION OF A SOLID PARTICLE ENCLOSURE IN A FLUIDIZED BED |
| EP1099473A1 (en) * | 1999-11-11 | 2001-05-16 | Union Carbide Chemicals & Plastics Technology Corporation | Sampling sysem for fluidized bed gas phase polymerization reaction systems |
| US20050047965A1 (en) * | 2003-08-29 | 2005-03-03 | Coute Nicolas P. | Catalyst sampling system |
| CN200996898Y (en) * | 2006-12-30 | 2007-12-26 | 中国石油大学(北京) | Solid particle sampler of multi-point axial parallel negative-pressure for fluidized bed |
| CN201867312U (en) * | 2010-11-18 | 2011-06-15 | 安徽淮化股份有限公司 | Gas-liquid-solid three-phase simultaneously sampling device of fluidized bed reactor |
| CN202083568U (en) * | 2011-04-27 | 2011-12-21 | 上海梅山钢铁股份有限公司 | Pulverized coal sampling device |
| CN202177522U (en) * | 2011-07-19 | 2012-03-28 | 宝山钢铁股份有限公司 | Solid sampling device in high-temperature fluid-bed process |
| CN102507259A (en) * | 2011-09-28 | 2012-06-20 | 神华集团有限责任公司 | Method for sampling solid particles in gas-liquid two phases |
| CN202387441U (en) * | 2011-12-08 | 2012-08-22 | 神华集团有限责任公司 | Sampling device for reactor |
| CN103657538A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for loading and unloading catalysts for fixed fluidized bed reactor |
| CN104697295A (en) * | 2013-12-04 | 2015-06-10 | 铜陵市永生机电制造有限责任公司 | Fluidized bed |
| CN104198223A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Online particle sampling unit of minitype fluidized bed and application thereof |
| CN204085939U (en) * | 2014-08-29 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | A kind of sampler being applied to the online particle sampling of miniature fluidized bed |
| CN105709858A (en) * | 2014-12-01 | 2016-06-29 | 神华集团有限责任公司 | Catalyst continuous reducing apparatus and method |
| WO2016141403A1 (en) * | 2015-03-06 | 2016-09-15 | Alcoa Of Australia Limited | Online sampling device |
| CN204855079U (en) * | 2015-05-27 | 2015-12-09 | 广东大唐国际潮州发电有限责任公司 | Pressure, automatic device that sweeps of differential pressure measurement |
| CN106552632A (en) * | 2015-09-30 | 2017-04-05 | 神华集团有限责任公司 | A kind of method of reducing of Fischer-Tropsch synthetic iron-based catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111795840A (en) * | 2019-04-09 | 2020-10-20 | 国家能源投资集团有限责任公司 | Device and method for on-line sampling and separating total components of Fischer-Tropsch synthesis reactor |
| CN111795840B (en) * | 2019-04-09 | 2023-08-22 | 国家能源投资集团有限责任公司 | Full-component online sampling and separating device and method for Fischer-Tropsch synthesis reactor |
| CN114269466A (en) * | 2019-06-26 | 2022-04-01 | 埃克斯能量有限责任公司 | Fluidized bed reactor system allowing particle sampling during ongoing reactions |
| CN114269466B (en) * | 2019-06-26 | 2023-08-18 | 埃克斯能量有限责任公司 | Fluidized bed reactor system allowing particle sampling during ongoing reactions |
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