CN104845661B - A kind of catalytic cracking regenerator experimental simulation method and device - Google Patents
A kind of catalytic cracking regenerator experimental simulation method and device Download PDFInfo
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Abstract
The invention discloses a kind of catalytic cracking regenerator experimental simulation method, comprise the following steps: after gas 1 and gas 2 on-line mixing, enter reactor；Mixed gas makes the catalyst in reaction tube be in fluidized state；Mixed gas is reacted with catalyst；Reacted gas is through gas solid separation；Gas after separating is measured and/or analyzes and implements the device of said method.The present invention utilizes fluidization principle, under the operating condition set, ensure that reclaimable catalyst is in good fluidized state in reaction tube, it is thus possible to effectively simulate the regenerative process of spent catalytic cracking catalyst under industry state, to predicting and instructing actual industrial process significant.
Description
Technical field
The present invention relates to a kind of method and device being simulated experiment, be specifically related to the reality of a kind of catalytic cracking regenerator
Test analogy method and device.
Background technology
Catalytic cracking technology is one of important technical of PETROLEUM PROCESSING, and its process-technology-evolutions is the most ripe,
Also it is one of important crude oil secondary operations means, it is provided that gasoline and the bavin of 30% of domestic market 70%～80%
Oil.
Catalytic cracking flow process mainly includes three parts:
1. the catalytic cracking of raw oil；
2. catalyst regeneration；
3. product separates.
In catalytic cracking use catalyst because of in course of reaction surface can adhere to coke (catalyst now be referred to as tie
Char catalyst or reclaimable catalyst) and activity reduces, so Regeneration Treatment must be carried out.Catalyst after regeneration is again introduced into
The carrying out of catalytic reaction in reactor.Therefore, Cracking catalyst is constantly circulated between reactor and regenerator.Generally
When leaving reactor, on reclaimable catalyst, phosphorus content is about 1wt%, it is necessary in regenerator, burning-off carbon deposit is to recover catalyst
Activity.Molecular sieve catalyst is typically required to phosphorus content is down to below 0.2wt%, and super-stable Y molecular sieves is catalyzed
Agent then requires to be down to below 0.05wt%.
In catalytic cracking unit, the Main Function of regenerator is to utilize air (industrial referred to as main air) burning-off coking catalysis
Coke in agent, to recover the activity of catalyst, also provides for the heat needed for catalytic cracking reaction simultaneously.Therefore, catalyst regeneration
It is highly important link in catalytic cracking process, the regeneration issues of catalyst must be attached great importance to when studying catalytic cracking.
Catalytic cracking regenerator is simulated test, it was predicted that and instruct actual industrial process to be the most just particularly important.
The device and method of experimental simulation catalytic cracking has had much to be reported, such as WO9960396, EP1393062,
US6069012、CN2538415.But the catalytic cracking reaction of raw oil is mainly simulated and studies (i.e. by said method
First part of catalytic cracking flow process), and the response situation in catalytic cracking regenerator can not be simulated well and
Research.
At present, in laboratory conditions, for the regenerative process of catalytic cracking catalyst, the research work carried out mainly wraps
Include: coke content on reclaimable catalyst and the Nomenclature Composition and Structure of Complexes of coke, different catalysts are burnt kinetics and burn
Mechanism etc..These research work all use Static Analysis Method, i.e. coked catalyst to be in static state, in constant temperature or program
Under conditions of intensification, the rule that research coke reacts with the oxygen in carrier gas.Reactor used in these research process
General use quartz glass U-tube or straight tube, a certain amount of catalyst be placed in reaction tube, pipe external resistance wire or
Outsourcing electric furnace heats, and burns in the carrier gas containing oxygen, by measuring containing of carbon dioxide and carbon monoxide in tail gas
Amount and Changing Pattern thereof study the regenerative process of reclaimable catalyst.CN2268256Y such as discloses a kind of fast precise fixed
Carbon instrument, its catalyst sample is laid in injector, is then pushed by injector and is tied with the quartz ampoule of high power electric furnace silk and burns
Device burns, determines the carbon content on coked catalyst by measuring the concentration of carbon dioxide in tail gas.Special according to this
Process described by profit, catalyst remains static in reaction tube, owing to being limited by reaction tube size, it is impossible to make to urge
Agent is in monolayer of particles state, can only be spread out by catalyst as far as possible, it is ensured that catalyst is fully contacted with gas.Patent
CN104280511A discloses a kind of cast iron and determines carbon analyzer it can also be used to the survey of coke content on spent catalytic cracking catalyst
Fixed, utilize non-constant voltage numeratio, eliminate " drop " phenomenon present in constant voltage numeratio, but its method and principle and patent
CN2268256Y is similar to, and is also a kind of Static Analysis Method.
But, in actual industrial process, in catalytic cracking unit in regenerator coked catalyst be not be in static
State.Catalyst is under certain gas flow rate, and bed no longer maintains fixing resting state.Now, catalyst is suspended in gas
In stream, demonstrate the most irregular motion, referred to as fluidized state.Either single hop regeneration, two-stage regeneration, or quickly flow
Changing bed regeneration, coked catalyst, under the effect of Air for burning coke, is in fluidized state.Operating gas velocity general control 0.5～
In the range of 1.5m/s (void tower linear speed), turbulent bed that its fluidized state major part belongs to or fast fluidized bed, small part is bubbling
Bed.This gas-solid fluidized state in regenerator not only (includes that effective oxygen concentration and effective carbon are dense to the valid density of reactant
Degree) have a direct impact, and can to gas (oxygen in gas phase) Gu mass transfer between-(coke on catalyst granules) is biphase
Produce impact with heat transfer, and then affect the burning carbon speed of whole regenerative process.Such as in bubbling fluidized bed regenerator, bubble phase
And the resistance to mass tranfer between Emulsion Phase can produce material impact to coke-burning rate.Therefore, industrial catalyticing cracking device to be studied is again
Raw device burn efficiency, except need to consider the factors such as the phosphorus content of regeneration temperature, partial pressure of oxygen (or oxygen concentration), catalyst it
Outward, the problems such as the flowing in regenerator, mass transfer, heat transfer must also be considered.
Regenerative response speed determines the efficiency of regenerator, its directly activity and selectivity, life of device to catalyst
Production capacity power produces material impact.Regenerative response speed depends on the burn rate of carbon in coke, and affects and burn carbon reaction rate
Principal element has the mass transfer between regeneration temperature, partial pressure of oxygen (or oxygen concentration), the phosphorus content of catalyst, gas-particle two-phase and heat transfer feelings
Condition etc..Above-mentioned Static Analysis Method, although the carbon content etc. on regeneration temperature, oxygen concentration and catalyst can be investigated
The factor impact on coke-burning rate, but the mass transfer between the gas-particle two-phase caused by fluidized state and heat transfer cannot be investigated to instead
Answer the valid density of thing and the impact of coke-burning rate.Therefore, it is essentially different with the regenerative process under industrial condition.
It is known that the exploitation of novel process and/or raw catelyst is subjected to grope to enlarged experiment from lab scale, then arrive
The research process of commercial Application.Therefore, can laboratory research data are the most forward-looking (i.e. correctly reflect the actual feelings of industry
Condition) it is the key of technological development.Therefore, the catalytic cracked regenerated rule that obtained of prior art or regenerator technique mathematics are used
Model is unpredictable and instructs actual industrial process.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of catalytic cracking meeting actual industrial process
Regenerator experimental simulation method.The method utilizes fluidization principle, under the operating condition set, it is ensured that reclaimable catalyst is instead
Good fluidized state should be in managing, so that reclaimable catalyst is fully contacted with fluidizing gas, reaches stable and burn effect
Really, thus effectively simulate the regenerative process of spent catalytic cracking catalyst under industry state, enable researchers at laboratory bar
Under part, it is thus achieved that the coke burning regeneration data more consistent with commercial plant, thus realize coke on spent catalytic cracking catalyst
Content and the Nomenclature Composition and Structure of Complexes of coke, different catalysts is burnt kinetics and burns the research of mechanism.
In order to realize the above-mentioned purpose of the present invention, this catalytic cracking regenerator experimental simulation method comprises the following steps:
Gas 1 is passed through reaction tube, and the flow velocity of regulation gas 1 makes the catalyst in reaction tube be in fluidized state；
Reacting by heating pipe reaches reaction temperature simultaneously, hereafter keeps or temperature programming；
After reaching reaction temperature, gas 2 and gas 1 on-line mixing, mixed gas subsequently enters reactor；
Mixed gas is reacted with catalyst；
Reacted gas is through gas solid separation；
Gas after gas solid separation is measured and/or analyzes.
Conditions different in catalytic cracking can be entered by above-mentioned catalytic cracking regenerator experimental simulation method easily
Row simulation experiment.Such as: located in reaction tube with guarantee catalyst by the loadings and gas flow rate controlling reclaimable catalyst
In different fluidized states；By controlling composition and the flow of gas in gas 1 and gas 2, realize reclaimable catalyst not
With the regenerative process under atmosphere；Realize on spent catalytic cracking catalyst by connecting different analysis and detection devices
Coke content and the Nomenclature Composition and Structure of Complexes of coke, different catalysts is burnt kinetics and burns the research of mechanism.
Change reaction tube fluidized state, regulation gas speed and the method changing reclaimable catalyst loadings can be used.Along with
The raising of gas speed, beds experiences the states such as fixed bed, particulate expansion bed, bubbling bed, turbulent bed, fast bed.Therefore, excellent
Choosing changes the method for gas speed.
Report multiple method at present to determine fluidized state, including visual observation, non-uniform index method, bed expansion
Method, pressure oscillation method, gas tracer time of staying method etc..Wherein pressure oscillation method is easy to measure and quantitative analysis owing to having
Feature, (see Kashkin VN, Lakhmostov VS, Zolotarskii IA, et for method for optimizing
al.Studiesontheonset velocityof turbulent fluidizationfor alpha-
Aluminaparticles [J] .Chemical Engineering Journal, 2003,91,215-218.).
In above-mentioned catalytic cracking regenerator experimental simulation method, gas 1 is the one in nitrogen, helium or argon, and it is excellent
Elect nitrogen as；Gas 2 is air or oxygen, and it is preferably oxygen.
During simulation experiment, can be by the volume of oxygen in gas after the effusion meter regulation mixing in two gas circuits
Content.The volume content of oxygen controls 0%～100%, preferably 0%～21%.So can realize reclaimable catalyst to exist
Coke burning regeneration process under gas with various atmosphere, especially investigates the oxygen concentration impact on burning reaction rate.
In order to ensure that catalyst is in the flow regime of bubbling bed, turbulent bed or fast fluidized bed in reaction tube, simultaneously
Catalyst will not be carried over again reaction tube, and in the lower cylindrical drum of reaction tube, the void tower linear speed of gas is designed as 0.1m/s～3m/s,
It is preferably 0.5m/s～1.5m/s；In upper cylindrical drum, the void tower linear speed of gas is designed as 0.01m/s～3m/s, and it is preferably
0.05m/s～0.8m/s.The present invention can also change the flow regime of catalyst by regulating the flow velocity of gas in reaction tube,
Thus investigate flowing, gas-solid biphase mass transfer and heat transfer and catalyst is burnt the impact of reaction rate.
The reaction tube used in this method is heated by being distributed in the thermocouple feedback control within reaction tube by temperature controller
Temperature and the rate of heat addition, and it is capable of temperature programming control, it is simple in experimentation, investigate different regeneration temperature to burning
The impact of speed, its temperature range controls at 400～1100 DEG C, and it is preferably 600～800 DEG C.
The method of gas dosing has and much can select, such as draining water gathering of gas law.
Analysis method can select one or both in gas chromatogram, mass spectrum, and it is preferably gas chromatogram and mass spectrum connection
With.If using gas chromatogram, can directly determine the content of carbon monoxide, carbon dioxide and remaining oxygen in tail gas,
The burning carbon amounts of whole simulation process can be calculated according to tail gas amount.If employing mass spectral analysis, then can reflect whole
In simulation process, the Changing Pattern of various logistics, is particularly suitable for Temperature Programmed Processes.
Another object of the present invention is to provide a kind of catalytic cracking regenerator experimental simulation meeting real reaction process
Device.As shown in Figure 1: this device, including gas circuit (1), gas circuit (2), the venting valve that is arranged in gas circuit (1) and gas circuit (2)
(4) divide with gas circuit (3), the gas of cross valve (7) with mass flowmenter (5), mixing valve (6), cross valve (7), connection gas circuit (1)
Cloth device (8), reaction tube (9), heating furnace (10), gas-solid separator (11), exsiccator (12), reversal valve (13), exhaust collection and
Quantifier (14) and analyze detecting system (15), described gas circuit (1) and gas circuit (2) be both connected on mixing valve (6), described mixing
Valve (6) is connected on the gas distributor (8) of described reaction tube (9) bottom through cross valve (7), described reaction tube (9) top
Gas-solid separator (11) be connected with exsiccator (12), described exsiccator (12) is by reversal valve (13) and exhaust collection and metering
Device (14) and/or analysis detecting system (15) are connected.
In order to maintain the fluidized state that reaction tube inner catalyst is good before reaching preset temperature, and do not cause regeneration anti-
The carrying out answered.Gas circuit (3) is set and connects the first pressure maintaining valve (4-1) and cross valve (7), make the gas 1 in gas circuit (1) individually enter
Reaction tube (9), maintains reaction tube (9) interior fluidized state.Because gas 2 is not introduced in reaction tube (9), therefore regenerative response is not
Have and carry out.
After gas 1 and gas 2 are respectively through gas circuit (1) and gas circuit (2) on-line mixing, enter through gas distributor (8)
Reaction tube (9), contacts with the reclaimable catalyst in reaction tube (9), makes catalyst be in fluidized state, and concurrent raw burn Jiao reacts,
Gas after burning and catalyst are separated by gas-solid separator (11), tail gas by analyze detecting system carry out metering and
Gas composition analysis, thus the method realizing above-mentioned catalytic cracking regenerator experimental simulation.
Said apparatus can pass through pressure maintaining valve (4) and gas flowmeter (5) controls gas flow rate to ensure that catalyst exists
Reaction tube is in different fluidized states.
The core component of this experimental provision is reaction tube, needs to carry out careful design.In order to fully simulate industry again
The flow regime of raw device inner catalyst, reaction tube uses variable diameter design, the ratio of upper cylindrical drum diameter D2 and lower cylindrical drum diameter D1
Value is 1～6, and it is preferably 1.5～3, and taper seat is 0 °～60 ° with the angle α of vertical line, and it is preferably 27 °～35 °.
Reasonably reaction tube size is that catalyst is at the normal important guarantee of internal fluidisation.Must account for the quiet of catalyst
Only bed height, relation between bed diameter and grain diameter, it is ensured that the constant pressure fall of bed, simultaneously need to control suitable
Gas speed.Can judge whether catalyst is in above-mentioned good fluidisation shape according to the formula that Romero and Johanson revises
State.
FrmfFred number, u2 mf/(gdp)
RemfReynolds number under the conditions of incipient fluidizing
ρpGrain density, kg/m3
ρfFluidizing gas density, kg/m3
HmfUnder the conditions of incipient fluidizing bed height, m
D reaction tube diameter, m
umfUnder the conditions of incipient fluidizing bed superficial gas velocity, m/s
dpParticle diameter, m
μ fluidizing gas viscosity, Pa s
Due to catalytic cracking catalyst regeneration temperature typically more than 600 DEG C, experiment sometimes needs to reach more than 800 DEG C,
Therefore reaction tube material need to select exotic material.Can use the quartz glass tube of traditional experiment device, quartz glass tube is resistance to
High-temperature behavior is excellent, the softening point temperature of quartz glass about 1730 DEG C, can use for a long time at 1100 DEG C, and the short time is the highest to be made
By temperature up to 1450 DEG C, and corrosion-resistant, Heat stability is good.But the mechanical strength of quartz glass tube is general.May be used without
High-temperature alloy Steel material 310S, resistant to elevated temperatures while, can improve mechanical strength.
High-power resistance silk can be used outside reaction tube to heat, it would however also be possible to employ electric furnace heats, by temperature control
Instrument is by being distributed in the thermocouple feedback control heating-up temperature within reaction tube and the rate of heat addition, and is capable of temperature programming
Control, it is simple in experimentation, investigate the different regeneration temperature impact on coke-burning rate.
In order to make the gas of entrance reaction tube have one to be uniformly distributed diametrically, at the bottom design gas of reaction tube
Distributor (8).Gas distributor (8) should ensure gas being uniformly distributed on reaction tube cross section, reduces gas pressure drop again,
Orifice plate or metal sintering plate can be used；The opening diameter of orifice plate is 0.1mm～5mm, and it is preferably 0.5～1mm, and percent opening is
1～100/cm2, it is preferably 9～25/cm2；The aperture of metal sintering plate is 10nm～100 μm, and it is preferably 1～20 μ
m。
Although have employed expanding design on the top of reaction tube, greatly reduce gas flow rate, major part catalyst granules
The bottom of reaction tube can be dropped back into because of the reduction of gas speed, but still suffer from a small amount of fine grained and be distributed in going out of reaction tube
Mouthful, therefore to avoid catalyst granules to be carried over reaction tube, at the offgas outlet at reaction tube top, devise gas solid separation
Device (11).Gas-solid separator should ensure that fine particle is separated, and reduces the pressure drop of gas again, can use pottery
Porous material or metal sintering plate；The aperture of ceramic porous material and metal sintering plate is 10nm～10 μm, and it is preferably 80nm
～1 μm.
Can select one or both in gas chromatogram, mass spectrum for analysis detecting system, it is preferably gas chromatogram
And mass spectrometry.If using gas chromatogram, can directly determine the carbon monoxide in tail gas, carbon dioxide and residue oxygen
The content of gas, can calculate the burning carbon amounts of whole simulation process according to tail gas amount.If employing mass spectral analysis, then can be anti-
The Changing Pattern of various logistics in whole simulation process should be gone out, be particularly suitable for Temperature Programmed Processes.
The present invention utilizes reaction tube and the gas distributor of fluidization principle design reducing, in the operating condition set
Under, it is possible to ensure that reclaimable catalyst is in good fluidized state in reaction tube, make reclaimable catalyst abundant with fluidizing gas
Contact, reaches stable and burns effect such that it is able to the regeneration of spent catalytic cracking catalyst under simulation industry state effectively
Process.It is possible not only to investigate the factor shadows to burning reaction rate such as regeneration temperature, partial pressure of oxygen (oxygen concentration), catalyst phosphorus content
Ring, but also Gas-particle Flows, gas-solid two alternate mass transfers and heat transfer can be studied on the impact burning reaction rate.Therefore, profit
With suitably analyzing detecting system, the present invention can make researcher in laboratory conditions, it is thus achieved that more consistent with commercial plant
Coke burning regeneration data, thus realize coke content in spent catalytic cracking agent and the Nomenclature Composition and Structure of Complexes of coke, different catalysis
Agent is burnt kinetics and burns the research of mechanism.
Accompanying drawing explanation
Fig. 1 is core component and the flow chart of catalytic cracking regenerator experimental simulation device of the present invention.
Fig. 2 is under the experiment condition described in example 4, CO and CO2Mass spectra peak variation with temperature rule.
Fig. 3 is CO and CO under the conditions of the experiment 1 described in example 52Mass spectra peak contrast
Fig. 4 is CO and CO under the conditions of the experiment 2 described in example 52Mass spectra peak contrast
Fig. 5 is CO and CO under the conditions of the experiment 3 described in example 52Mass spectra peak contrast
Fig. 6 is CO and CO under the conditions of the experiment 4 described in example 52Mass spectra peak contrast
Accompanying drawing identifier declaration:
1 gas circuit (1)；
2 gas circuits (2)；
3 gas circuits (3)；
4 pressure maintaining valves, 4-1 the first pressure maintaining valve, 4-2 the second pressure maintaining valve；
5 mass flowmenters, 5-1 the first mass flowmenter, 5-2 the second mass flowmenter, 5-3 the 3rd mass stream
Gauge；
6 mixing valves；
7 cross valves；
8 gas distributors；
9 reaction tubes；
10 heating furnaces；
11 gas-solid separators；
12 exsiccators；
13 reversal valves；
14 exhaust collections and quantifier；
15 analyze detecting system, 15-1 gas chromatogram, 15-2 mass spectrum.
Detailed description of the invention
The invention discloses a kind of catalytic cracking regenerator experimental simulation method and device, those skilled in the art can borrow
Mirror present disclosure, is suitably modified technological parameter and realizes present invention.It is important to note that all similar replacements and changing
Dynamic apparent to those skilled in the art, they are considered as being included in the present invention.Method of the present invention
And device is described by preferred embodiment, related personnel substantially can be without departing from present invention, spirit and model
Enclose and interior method described herein and device be modified or suitably change and combine, realize and apply the technology of the present invention.
Embodiment 1: the mensuration of reclaimable catalyst phosphorus content in bubbling bed fluidized state
As it is shown in figure 1, gas circuit (1) uses helium, gas circuit (2) uses air, by the mass flowmenter in two gas circuits
Controlling the volumn concentration of oxygen in mixed gas is 1%, and total gas flow is 1.5L/min.Reaction tube (9) uses stone
English glass material, its underpart cylindrical drum diameter D1 is 35mm, and ratio of height to diameter is 100, and Upper cylindrical cylinder diameter D2 is 210mm, Gao Jing
Ratio is 10, D2:D1=6；Taper seat is 60 ° with the angle α of vertical line, and now in reaction tube, the empty tower gas velocity of bottom is 0.1m/
S, the empty tower gas velocity on top is 0.01m/s.Gas distributor uses orifice plate, and opening diameter is 0.5mm, and percent opening is 9/cm2；
The metal sintering plate that gas-solid separator uses aperture to be 10nm.The outside of reaction tube (9) uses electric furnace to heat, and passes through
It is distributed in the thermocouple feedback control heating-up temperature within reaction tube and the rate of heat addition, and is capable of multi-segment program liter temperature control
System.
Experimental simulation process is as follows: first precise reclaimable catalyst 5g is placed in reaction tube (9), temperature in reaction tube
Before the regeneration temperature that degree is not up to preset, first catalyst is made to be in good bubbling bed fluidized state with helium.Open first
Venting valve (4-1), regulates the first mass flowmenter (5-1) and makes the flow of helium be 1.5L/min, and rotary four-way valve (7) is to gas circuit
(3) connect reaction tube (9), make the catalyst in reaction tube (9) be in bubbling bed fluidized state.Then heating furnace (10) is opened,
The temperature of reaction tube middle and lower part is made to reach 400 DEG C with the programming rate of 20 DEG C/min, and stable in this temperature.Treat that temperature reaches pre-
If after temperature, open the second venting valve (4-2), regulate the second mass flowmenter (5-2) and the stream of the 3rd mass flowmenter (5-3)
Amount is respectively 1.429L/min and 0.071L/min.Then rotary four-way valve (7) connects reaction tube (9) to gaseous mixture, same in this
Time open reversal valve (13) and start to collect tail gas to exhaust collection and quantifier (14).Response time is 300s, then measures tail
Air volume the composition by chromatograph (15-1) analysis tail gas.Amount and the composition of tail gas according to tail gas can determine and regenerate
Burning carbon amounts in journey, thus calculate the phosphorus content on catalyst.Its analysis result such as table 1:
Table 1
Embodiment 2: the mensuration of reclaimable catalyst phosphorus content in turbulent bed fluidized state
As it is shown in figure 1, gas circuit (1) uses high pure nitrogen, gas circuit (2) uses purity oxygen, by the quality in two gas circuits
It is 10% that effusion meter controls the volumn concentration of oxygen in mixed gas, and total gas flow is 20L/min.Reaction tube (9)
Using 310S stainless steel material, its underpart cylindrical drum diameter D1 is 20mm, and ratio of height to diameter is 15, and Upper cylindrical cylinder diameter D2 is
40mm, ratio of height to diameter is 3, D2:D1=2；Taper seat is 30 ° with the angle α of vertical line, the now empty tower gas velocity of bottom in reaction tube
For 1.06m/s, the empty tower gas velocity on top is 0.26m/s.The metal sintering plate that gas distributor uses aperture to be 10 μm, gas-solid divides
Aperture is used to be the ceramic porous material of 100nm from device.The outside of reaction tube (9) uses electric furnace to heat, by dividing
Cloth is in the thermocouple feedback control heating-up temperature within reaction tube and the rate of heat addition, and is capable of multi-segment program liter temperature control.
Analyze detecting system and use gas chromatogram, can carbon monoxide and the volume content of carbon dioxide in on-line analysis tail gas.
Experimental simulation process is as follows: first precise reclaimable catalyst 50g is placed in reaction tube (9), in reaction tube
Before the regeneration temperature that temperature is not up to preset, first catalyst is made to be in good turbulent bed fluidized state with pure nitrogen gas.Open
First venting valve (4-1), regulates the first mass flowmenter (5-1) and makes the flow of nitrogen be 20L/min, and rotary four-way valve (7) is extremely
Gas circuit (3) connects reaction tube (9), makes the catalyst in reaction tube (9) be in turbulent bed fluidized state.Then heating furnace is opened
(10), the temperature of reaction tube middle and lower part is made to reach 680 DEG C with the programming rate of 20 DEG C/min, and stable in this temperature.Treat temperature
After reaching preset temperature, open venting valve (4-2), regulate the second mass flowmenter (5-2) and the 3rd mass flowmenter (5-3)
Flow is respectively 18L/min and 2L/min.Then rotary four-way valve (7) connects reaction tube (9) to gaseous mixture, simultaneously opens
Reversal valve (13) starts to collect tail gas to exhaust collection and quantifier (14).Response time is 30s, and then metering exhaust gas volumes is also
The composition of tail gas is analyzed by chromatograph (15-1).Amount and the composition of tail gas according to tail gas can determine the burning in regenerative process
Carbon amounts, thus calculate the phosphorus content on catalyst.Its analysis result is as shown in table 2:
Table 2
Embodiment 3: the mensuration of reclaimable catalyst phosphorus content in fast fluidized bed fluidized state
As it is shown in figure 1, gas circuit (1) uses high-purity argon gas, gas circuit (2) uses purity oxygen, by the quality in two gas circuits
It is 90% that effusion meter controls the volumn concentration of oxygen in mixed gas, and total gas flow is 60L/min.Reaction tube (9)
Using 310S stainless steel material, its underpart cylindrical drum diameter D1 is 20mm, and ratio of height to diameter is 1, and Upper cylindrical cylinder diameter D2 is 25mm,
Ratio of height to diameter is 0.5, D2:D1=1.2；Taper seat is 5 ° with the angle α of vertical line, and now in reaction tube, the empty tower gas velocity of bottom is
3m/s, the empty tower gas velocity on top is 2m/s.The metal sintering plate that gas distributor uses aperture to be 20 μm, gas-solid separator uses
Aperture is the ceramic porous material of 10 μm.The outside of reaction tube (9) uses electric furnace to heat, by being distributed in reaction tube
Internal thermocouple feedback control heating-up temperature and the rate of heat addition, and it is capable of multi-segment program liter temperature control.Analyze detection system
System uses gas chromatogram, can carbon monoxide and the volume content of carbon dioxide in on-line analysis tail gas.
Experimental simulation process is as follows: first precise reclaimable catalyst 150g is placed in reaction tube (9), in reaction tube
Before the regeneration temperature that temperature is not up to preset, first catalyst is made to be in good fast fluidized bed fluidized state with pure argon.
Open the first venting valve (4-1), regulate the first mass flowmenter (5-1) and make the flow of argon be 60L/min, rotary four-way valve
(7) connect reaction tube (9) to gas circuit (3), make the catalyst in reaction tube (9) be in fast fluidized bed fluidized state.Then beat
Open heating furnace (10), make the temperature of reaction tube middle and lower part reach 1100 DEG C with the programming rate of 20 DEG C/min, and stable warm at this
Degree.After temperature reaches preset temperature, open the second venting valve (4-2), the second regulation mass flowmenter (5-2) and the 3rd mass
The flow of effusion meter (5-3) is respectively 6L/min and 54L/min.Then rotary four-way valve (7) connects reaction tube to gaseous mixture
(9), simultaneously open reversal valve (13) to start to collect tail gas to exhaust collection and quantifier (14).Response time is 30s, so
Rear metering exhaust gas volumes the composition by chromatograph (15-1) analysis tail gas.Amount and the composition of tail gas according to tail gas can measure
Go out the burning carbon amounts in regenerative process, thus calculate the phosphorus content on catalyst.Its analysis result is as shown in table 3:
Table 3
Embodiment 4: carbon monoxide and the research of carbon dioxide Conduce Disciplinarian in regenerative process
Gas circuit (1) uses high pure nitrogen, and gas circuit (2) uses purity oxygen, is controlled by the mass flowmenter in two gas circuits
In mixed gas, the volumn concentration of oxygen is 10%, and total gas flow is 20L/min.Reaction tube (9) uses 310S not
Rust Steel material, its underpart cylindrical drum diameter D1 is 20mm, and ratio of height to diameter is 15, and Upper cylindrical cylinder diameter D2 is 40mm, and ratio of height to diameter is
3, D2:D1=2；Taper seat is 30 ° with the angle α of vertical line, and now in reaction tube, the empty tower gas velocity of bottom is 1.06m/s, on
The empty tower gas velocity in portion is 0.26m/s.The metal sintering plate that gas distributor uses aperture to be 1 μm, gas-solid separator uses aperture
Ceramic porous material for 90nm.The outside of reaction tube (9) uses electric furnace to heat, by being distributed in inside reaction tube
Thermocouple feedback control heating-up temperature and the rate of heat addition, and be capable of multi-segment program rise temperature control.Analysis detecting system is adopted
Use on-line mass spectroscopy.
Experimental simulation process is as follows: first precise reclaimable catalyst 50g is placed in reaction tube (9), opens first steady
Determine valve (4-1) and the second venting valve (4-2), regulate the second mass flowmenter (5-2) and the flow of the 3rd mass flowmenter (5-3)
It is respectively 18L/min and 2L/min.Then rotary four-way valve (7) connects reaction tube (9) to gaseous mixture, simultaneously opens commutation
Valve (13) is to mass spectrum (15-2) on-line analysis.Finally open heating furnace (10), with the programming rate of 10 DEG C/min from room temperature to 800
DEG C (reaction tube middle and lower part temperature) carries out temperature programming.Study according to the carbon monoxide in mass spectrometric data and carbonic anhydride ion peak
Their Conduce Disciplinarian.Its result is as shown in Figure 2.
Embodiment 5: reclaimable catalyst regenerative process research under gas with various atmosphere
Gas circuit (1) uses high pure nitrogen, and gas circuit (2) uses purity oxygen, by the mass flowmenter modulation in two gas circuits
The volumn concentration of oxygen in mixed gas, total gas flow is 20L/min.Reaction tube (9) uses 310S stainless steel
Material, its underpart cylindrical drum diameter D1 is 20mm, and ratio of height to diameter is 15, and Upper cylindrical cylinder diameter D2 is 40mm, and ratio of height to diameter is 3, D2:D1
=2；Taper seat is 30 ° with the angle α of vertical line, and now in reaction tube, the empty tower gas velocity of bottom is 1.06m/s, the void tower on top
Gas speed is 0.26m/s.Gas distributor uses orifice plate, and opening diameter is 0.5mm, and percent opening is 25/cm2；Gas-solid separator
Using aperture is the ceramic porous material of 90nm.The outside of reaction tube (9) uses electric furnace to heat, anti-by being distributed in
Should thermocouple feedback control heating-up temperature within pipe and the rate of heat addition, and be capable of temperature programming control.Analyze detection system
System uses on-line mass spectroscopy.
Experimental simulation process is as follows:
Experiment 1
Precise reclaimable catalyst 50g is placed in reaction tube (9), opens the first venting valve (4-1) and the second venting valve
(4-2) flow, regulating the second mass flowmenter (5-2) and the 3rd mass flowmenter (5-3) is respectively 19L/min and 1L/
Min, making the volume content of oxygen in mixed gas is 5%.Rotary four-way valve (7) connects reaction tube (9) to gaseous mixture, same in this
Time open reversal valve (13) to mass spectrum (15-2) on-line analysis.Open heating furnace (10), with the programming rate of 10 DEG C/min from room
Temperature carries out temperature programming to 680 DEG C (reaction tube middle and lower part temperature), and stablizes 680 DEG C 10 minutes.Obtain reclaimable catalyst at oxygen
Air volume content be 5% atmosphere in regenerate data, its result is shown in mass spectrum A in Fig. 3.
Experiment 2
Precise reclaimable catalyst 50g is placed in reaction tube (9), opens the first venting valve (4-1) and the second venting valve
(4-2) flow, regulating the second mass flowmenter (5-2) and the 3rd mass flowmenter (5-3) is respectively 18L/min and 2L/
Min, making the volume content of oxygen in mixed gas is 10%.Repeat above-mentioned experimentation, it is thus achieved that reclaimable catalyst is at carrier of oxygen
Long-pending content be 10% atmosphere in regenerate data, its result is shown in mass spectrum B in Fig. 4.
Experiment 3
Precise reclaimable catalyst 50g is placed in reaction tube (9), opens the first venting valve (4-1) and the second venting valve
(4-2) flow, regulating the second mass flowmenter (5-2) and the 3rd mass flowmenter (5-3) is respectively 17L/min and 3L/
Min, making the volume content of oxygen in mixed gas is 15%.Repeat above-mentioned experimentation, it is thus achieved that reclaimable catalyst is at carrier of oxygen
Long-pending content be 15% atmosphere in regenerate data, its result is shown in mass spectrum C in Fig. 5.
Experiment 4
Precise reclaimable catalyst 50g is placed in reaction tube (9), opens the first venting valve (4-1) and the second venting valve
(4-2) flow, regulating the second mass flowmenter (5-2) and the 3rd mass flowmenter (5-3) is respectively 16L/min and 4L/
Min, making the volume content of oxygen in mixed gas is 20%.Repeat above-mentioned experimentation, it is thus achieved that reclaimable catalyst is at carrier of oxygen
Long-pending content be 20% atmosphere in regenerate data, its result is shown in mass spectrum D in Fig. 6.
The above four groups of data of contrast, can obtain reclaimable catalyst regeneration rule under gas with various atmosphere.Its contrast
Mass spectrum A～D in result such as Fig. 3～6.
It should be pointed out that, that the above is only the preferred embodiment of the present invention, for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a catalytic cracking regenerator experimental simulation method, it is characterised in that said method comprising the steps of:
Gas 1 is passed through reaction tube, and the flow velocity of regulation gas 1 makes the catalyst in reaction tube be in fluidized state；
Reacting by heating pipe reaches reaction temperature simultaneously, hereafter keeps or temperature programming；
After reaching reaction temperature, gas 2 and gas 1 on-line mixing, mixed gas subsequently enters reactor；
Mixed gas is reacted with catalyst；
Reacted gas is through gas solid separation；
Gas after gas solid separation is measured and/or analyzes.
Catalytic cracking regenerator experimental simulation method the most according to claim 1, it is characterised in that gas 1 is nitrogen, helium
One in gas, argon；Gas 2 is air or oxygen.
Catalytic cracking regenerator experimental simulation method the most according to claim 2, it is characterised in that gas 1 and gas 2 mix
After conjunction, the volume content of oxygen is 0%～100%.
Catalytic cracking regenerator experimental simulation method the most according to claim 1, it is characterised in that described reaction tube bottom
Void tower linear speed be 0.1m/s～3m/s；The void tower linear speed on described reaction tube top is 0.01m/s～3m/s.
5. according to the catalytic cracking regenerator experimental simulation method described in claim 1-4 any one, it is characterised in that mixing
Gas is 400 DEG C～1100 DEG C with the reaction temperature of catalyst.
6. according to the catalytic cracking regenerator experimental simulation method described in claim 1-4 any one, it is characterised in that described
Gas dosing method is draining gas collection；Described analysis method is one or both in gas chromatogram or mass spectrum.
7. a catalytic cracking regenerator experimental simulation device, it is characterised in that include gas circuit (1), gas circuit (2), be arranged on gas
Venting valve (4) on road (1) and gas circuit (2) and mass flowmenter (5), mixing valve (6), cross valve (7), connect gas circuit (1) with
The gas circuit (3) of cross valve (7), gas distributor (8), reaction tube (9), heating furnace (10), gas-solid separator (11), exsiccator
(12), reversal valve (13), exhaust collection and quantifier (14) and analysis detecting system (15), described gas circuit (1) and gas circuit (2) are all
Being connected on mixing valve (6), described mixing valve (6) is connected to the gas distribution of described reaction tube (9) bottom through cross valve (7)
On device (8), the gas-solid separator (11) at described reaction tube (9) top is connected with exsiccator (12), and described exsiccator (12) passes through
Reversal valve (13) and exhaust collection and quantifier (14) and/or analyze detecting system (15) and be connected；
Wherein, described reaction tube (9) uses variable diameter design, and on it, the ratio of cylindrical drum diameter D2 and lower cylindrical drum diameter D1 is 1
～6；The ratio of height to diameter of upper cylindrical drum is 0.5～100；The ratio of height to diameter of lower cylindrical drum is 1～1000；Taper seat and the angle of vertical line
α is 0 °～60 °.
Catalytic cracking regenerator experimental simulation device the most according to claim 7, it is characterised in that described reaction tube (9)
The ratio of upper cylindrical drum diameter D2 and lower cylindrical drum diameter D1 is 1.5～3；Taper seat is 27 °～35 ° with the angle α of vertical line.
Catalytic cracking regenerator experimental simulation device the most according to claim 7, it is characterised in that described reaction tube (9) is adopted
Use exotic material.
10. according to the catalytic cracking regenerator experimental simulation device described in claim 7-9 any one, it is characterised in that described
Reaction tube (9) uses quartz glass or 310S stainless steel material；Described gas distributor (8) uses orifice plate or metal sintering plate；
Described gas-solid separator (11) uses ceramic porous material or metal sintering plate.
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