CN104845661A - Catalytic cracking reactivator test simulation method and device - Google Patents
Catalytic cracking reactivator test simulation method and device Download PDFInfo
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Abstract
The invention discloses a catalytic cracking reactivator test simulation method. The method includes mixing a gas 1 and a gas 2 online to enter a reactor; allowing the catalyst in a reaction tube to be in a fluidizing state through the mixed gas; allowing the mixed gas to react with the catalyst; performing gas-solid separation on the reacted gas; metering and/or analyzing the separated gas. The fluidizing principle is utilized, on the set operation condition, the catalyst can be maintained in a fine fluidizing state in the reaction tube, the reactivating process for catalytic cracking of the catalyst to reactivate in the industrial state can be simulated effectively, and the important significance is provided for predicting and indicating the actual industry process.
Description
Technical field
The present invention relates to a kind of method and the device that carry out simulated experiment, be specifically related to a kind of experimental simulation method and device of catalytic cracking regenerator.
Background technology
Catalytic cracking technology is one of important technical of refining of petroleum, and its process-technology-evolutions is relatively ripe, is also one of important crude oil secondary processing means, provides the gasoline of domestic market 70% ~ 80% and the diesel oil of 30%.
Catalytic cracking flow process mainly comprises three parts:
1. the catalytic cracking of stock oil;
2. catalyst regeneration;
3. product separation.
The catalyzer used in catalytic cracking because of in reaction process surface can adhere to coke (catalyzer is now called coked catalyst or reclaimable catalyst) and active to reduce, so must manipulation of regeneration be carried out.Catalyzer after regeneration enters the carrying out of catalyzed reaction in reactor again.Therefore, cracking catalyst constantly circulates between reactor and revivifier.Usually when leaving reactor, on reclaimable catalyst, carbon content is about 1wt%, must in revivifier burning-off carbon deposit to recover the activity of catalyzer.Below 0.2wt% is down to for molecular sieve catalyst general requirement carbon content, super-stable Y molecular sieves catalyzer is then required to be down to below 0.05wt%.
In catalytic cracking unit, the Main Function of revivifier utilizes coke on air (industrial be called main air) burning-off coked catalyst to recover the activity of catalyzer, also provides the heat needed for catalytic cracking reaction simultaneously.Therefore, catalyst regeneration is link very important in catalytic cracking process, must attach great importance to the regeneration issues of catalyzer when studying catalytic cracking.Simulation test is carried out to catalytic cracking regenerator, predicts and instruct actual industrial process also just to seem particularly important.
The device and method of experimental simulation catalytic cracking has had a lot of report, such as WO9960396, EP1393062, US6069012, CN2538415.But aforesaid method is mainly simulated and is studied the catalytic cracking reaction of stock oil (i.e. first part of catalytic cracking flow process), and can not simulate well the response situation in catalytic cracking regenerator and study.
At present, in laboratory conditions, for the regenerative process of catalytic cracking catalyst, the research work carried out mainly comprises: the coke content on reclaimable catalyst and the Nomenclature Composition and Structure of Complexes of coke, different catalysts burn reaction kinetics and burn mechanism etc.These research work all adopt Static Analysis Method, and namely coked catalyst is in static state, under the condition of constant temperature or temperature programming, and the rule that the oxygen in research coke and carrier gas reacts.Reactor used in these research process generally adopts silica glass U-shaped pipe or straight tube, a certain amount of catalyzer is placed in reaction tubes, pipe external application resistance wire or outsourcing electric furnace heat, burn in containing the carrier gas of oxygen, studied the regenerative process of reclaimable catalyst by the content and Changing Pattern thereof measuring carbonic acid gas and carbon monoxide in tail gas.Such as, disclose a kind of Quick-acting precision carbometer in CN2268256Y, its catalyst sample is laid in sampler, then sampler is pushed the silica tube being tied with high power electric furnace silk to burn in device and burn, determined the carbon content on coked catalyst by the concentration measuring carbonic acid gas in tail gas.According to the process described by this patent, catalyzer remains static in reaction tubes, due to the restriction by reaction tubes size, catalyzer can not be made to be in monolayer of particles state, catalyzer can only be spread out as far as possible, and guarantee catalyzer fully contacts with gas.Patent CN104280511A discloses a kind of cast iron and determines carbon analyzer, also can be used for the mensuration of coke content on spent catalytic cracking catalyst, utilize non-constant voltage method of reading, eliminate " drop " phenomenon existed in constant voltage method of reading, but its method and principle and patent CN2268256Y similar, be also a kind of Static Analysis Method.
But in actual industrial process, in catalytic cracking unit, in revivifier, coked catalyst is not remain static.Catalyzer is under certain gas flow rate, and bed no longer maintains fixing stationary state.Now, catalyzer is suspended in air-flow, demonstrates quite irregular motion, is referred to as fluidized state.No matter be single hop regeneration, two-stage regeneration, or fast fluidized bed regeneration, coked catalyst, under the effect of Air for burning coke, is all in fluidized state.Operating gas velocity general control is in 0.5 ~ 1.5m/s (void tower linear speed) scope, and the 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 revivifier not only has a direct impact the effective concentration (comprising effective oxygen concn and effective carbon concentration) of reactant, and to gas (oxygen in gas phase) Gu mass transfer between-(coke on granules of catalyst) two-phase and heat transfer have an impact, and then the burning carbon speed of whole regenerative process can be affected.Such as in bubbling fluidized bed revivifier, the resistance to mass transfer between bubble phase and Emulsion Phase can produce material impact to coke-burning rate.Therefore, efficiency is burnt for research industrial catalyticing cracking device revivifier, except needing the factors such as the carbon content of consideration regeneration temperature, oxygen partial pressure (or oxygen concn), catalyzer, also must consider the problem such as flowing, mass transfer, heat transfer in revivifier.
Regenerative response speed determines the efficiency of revivifier, and it directly produces material impact to the activity and selectivity of catalyzer, the throughput of device.Regenerative response speed depends on the rate of combustion of carbon in coke, and the principal element that carbon speed of reaction is burnt in impact has mass transfer between the carbon content of regeneration temperature, oxygen partial pressure (or oxygen concn), catalyzer, gas-particle two-phase and heat transfer situation etc.Above-mentioned Static Analysis Method, although the factors such as the carbon content on regeneration temperature, oxygen concn and catalyzer can be investigated on the impact of coke-burning rate, mass transfer between the gas-particle two-phase that caused by fluidized state and heat transfer cannot be investigated on the effective concentration of reactant and the impact of coke-burning rate.Therefore, be essentially different with the regenerative process under industrial condition.
As everyone knows, the exploitation of novel process and/or raw catalyst must be experienced and grope enlarged experiment from lab scale, then arrives the research process of industrial application.Therefore, can laboratory study data whether forward-looking (namely correctly reflect industrial practical situation) be the key of technological development.Therefore, adopt the catalytic cracked regenerated rule that obtains of prior art or revivifier technological mathematical model unpredictable and instruct actual industrial process.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of catalytic cracking regenerator experimental simulation method of realistic commercial run.The method utilizes fluidization principle, under the operational condition of setting, ensure that reclaimable catalyst is in good fluidized state in reaction tubes, thus reclaimable catalyst is fully contacted with fluidizing agent, reach stable and burn effect, thus the effective regenerative process of spent catalytic cracking catalyst under the industrial state of simulation, enable investigator in laboratory conditions, obtain the coke burning regeneration data more consistent with full scale plant, thus the Nomenclature Composition and Structure of Complexes realized coke content on spent catalytic cracking catalyst and coke, different catalysts is burnt reaction kinetics and is burnt the research of mechanism.
In order to realize above-mentioned purpose of the present invention, this catalytic cracking regenerator experimental simulation method comprises the following steps:
Gas 1 is passed into reaction tubes, and the flow velocity of adjustments of gas 1 makes the catalyzer in reaction tubes be in fluidized state;
Reacting by heating pipe makes it reach temperature of reaction simultaneously, after this keeps or temperature programming;
After reaching temperature of reaction, gas 2 and gas 1 on-line mixing, mixed gas enters reactor subsequently;
Mixed gas and catalyzer react;
Reacted gas is through gas solid separation;
Gas after gas solid separation is measured and/or analyzed.
Above-mentioned catalytic cracking regenerator experimental simulation method can carry out simulated experiment to conditions different in catalytic cracking easily.Such as: by controlling the loadings of reclaimable catalyst and gas flow rate to ensure that catalyzer is in different fluidized states in reaction tubes; By controlling composition and the flow of gas in gas 1 and gas 2, realize the regenerative process of reclaimable catalyst under gas with various atmosphere; By connecting different analysis and detection devices to realize the Nomenclature Composition and Structure of Complexes to the coke content on spent catalytic cracking catalyst and coke, different catalysts is burnt reaction kinetics and is burnt the research of mechanism.
Change reaction tubes fluidized state, the method regulating gas speed and change reclaimable catalyst loadings can be adopted.Along with the raising of gas speed, the states such as beds experience fixed bed, particulate expansion bed, bubbling bed, turbulent bed, fast bed.Therefore, the method for gas speed is preferably changed.
Report multiple method at present to determine fluidized state, comprise visual observation, non-uniform index method, bed expansion method, pressure surge method, gaseous tracer residence time method etc.Wherein pressure surge method is convenient to the feature of measurement and quantitative analysis owing to having, for preferred method is (see Kashkin VN, Lakhmostov VS, Zolotarskii IA, et al.Studiesontheonset velocityof turbulentfluidizationfor alpha-aluminaparticles [J] .Chemical EngineeringJournal, 2003,91,215-218.).
In above-mentioned catalytic cracking regenerator experimental simulation method, gas 1 is the one in nitrogen, helium or argon gas, and it is preferably nitrogen; Gas 2 is air or oxygen, and it is preferably oxygen.
In simulated experiment process, the volume content of oxygen in the rear gas of mixing can be regulated by the under meter in two gas circuits.The volume content of oxygen controls 0% ~ 100%, is preferably 0% ~ 21%.Reclaimable catalyst coke burning regeneration process under gas with various atmosphere can be realized like this, especially investigate oxygen concentration to the impact of burning speed of reaction.
In order to ensure that catalyzer is in the flow state of bubbling bed, turbulent bed or fast fluidized bed in reaction tubes, catalyzer can not be taken out of reaction tubes again simultaneously, in the lower cylindrical drum of reaction tubes, the void tower linear speed of gas is designed to 0.1m/s ~ 3m/s, and it is preferably 0.5m/s ~ 1.5m/s; In upper cylindrical drum, the void tower linear speed of gas is designed to 0.01m/s ~ 3m/s, and it is preferably 0.05m/s ~ 0.8m/s.The present invention can also change the flow state of catalyzer by regulating the flow velocity of gas in reaction tubes, thus the impact of speed of reaction is burnt in the mass transfer of investigation flowing, gas-solid two-phase and heat transfer on catalyzer.
The reaction tubes used in present method by temperature controller by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and temperature programming control can be realized, be convenient in experimentation, investigate the impact of different regeneration temperature on coke-burning rate, its temperature range controls at 400 ~ 1100 DEG C, and it is preferably 600 ~ 800 DEG C.
The method of gas dosing has much can be selected, such as draining water gathering of gas law.
Analytical procedure can select in gas-chromatography, mass spectrum one or both, it is preferably gas-chromatography and mass spectrometry.If adopt gas-chromatography, directly can determine the content of carbon monoxide, carbonic acid gas and the remaining oxygen in tail gas, the burning carbon amounts of whole simulation process can be calculated according to tail gas amount.If employing mass spectroscopy, then can reflect the Changing Pattern of various logistics in whole simulation process, be particularly suitable for Temperature Programmed Processes.
Another object of the present invention is to the device of the catalytic cracking regenerator experimental simulation that a kind of realistic reaction process is provided.As shown in Figure 1: this device, gas circuit (1) is comprised, gas circuit (2), be arranged on the venting valve (4) in gas circuit (1) and gas circuit (2) and mass flowmeter (5), mixing valve (6), four-way valve (7), connect the gas circuit (3) of gas circuit (1) and four-way valve (7), gas distributor (8), reaction tubes (9), process furnace (10), gas-solid separator (11), moisture eliminator (12), reversing valve (13), exhaust collection and gauger (14) and analyzing and testing system (15), described gas circuit (1) and gas circuit (2) are all connected on mixing valve (6), described mixing valve (6) is connected on the gas distributor (8) of described reaction tubes (9) bottom through four-way valve (7), the gas-solid separator (11) at described reaction tubes (9) top is connected with moisture eliminator (12), and described moisture eliminator (12) is connected with gauger (14) and/or analyzing and testing system (15) with exhaust collection by reversing valve (13).
In order to maintain the good fluidized state of reaction tubes inner catalyst before reaching preset temp, and do not cause the carrying out of regenerative response.Gas circuit (3) is set and connects the first pressure maintaining valve (4-1) and four-way valve (7), make the gas 1 in gas circuit (1) enter separately reaction tubes (9), maintain reaction tubes (9) interior fluidized state.Because gas 2 does not enter in reaction tubes (9), therefore regenerative response does not carry out.
Gas 1 and gas 2 are respectively through after gas circuit (1) and gas circuit (2) on-line mixing, reaction tubes (9) is entered through gas distributor (8), contact with the reclaimable catalyst in reaction tubes (9), catalyzer is made to be in fluidized state, concurrent raw burn Jiao reaction, gas after burning is separated by gas-solid separator (11) with catalyzer, tail gas carries out metering and gas compositional analysis by analyzing and testing system, thus realizes the method for above-mentioned catalytic cracking regenerator experimental simulation.
Said apparatus can pass through pressure maintaining valve (4) and gas meter (5) controls gas flow rate to ensure that catalyzer is in different fluidized states in reaction tubes.
The core component of this experimental installation is reaction tubes, needs to carry out careful design.In order to the flow state of industrial regeneration device inner catalyst fully can be simulated, reaction tubes adopts variable diameter design, and the ratio of upper cylindrical drum diameter D2 and lower cylindrical drum diameter D1 is 1 ~ 6, and it is preferably 1.5 ~ 3, the angle α of cone surface and vertical line is 0 ° ~ 60 °, and it is preferably 27 ° ~ 35 °.
Rational reaction tubes size is that catalyzer is at the normal important guarantee of internal fluidisation.The quiescent bed layer height of catalyzer, the relation between bed diameter and grain diameter must be considered, ensure that the constant pressure of bed is fallen, need to control suitable gas speed simultaneously.The formula can revised according to Romero and Johanson judges whether catalyzer is in above-mentioned good fluidized state.
Fr
mffred number, u
2 mf/ (gd
p)
Re
mfreynolds number under incipient fluidizing condition
ρ
ppellet density, kg/m
3
ρ
ffluidizing agent density, kg/m
3
H
mfunder incipient fluidizing condition bed height, m
D reaction tube diameter, m
U
mfunder incipient fluidizing condition bed superficial gas velocity, m/s
D
pparticle diameter, m
μ fluidizing agent viscosity, Pas
Because catalytic cracking catalyst regeneration temperature is generally more than 600 DEG C, experiment sometimes needs to reach more than 800 DEG C, and therefore reaction tubes material need select high temperature material.The quartz glass tube of traditional experiment device can be adopted, quartz glass tube resistance to elevated temperatures is excellent, and the softening point temperature of silica glass about 1730 DEG C, can use for a long time at 1100 DEG C, short period of time maximum operation (service) temperature can reach 1450 DEG C, and corrosion-resistant, Heat stability is good.But the physical strength of quartz glass tube is general.Also can adopt high temperature alloy steel 310S, resistant to elevated temperatures while, can physical strength be improved.
Reaction tubes outside can adopt high-power resistance silk to heat, also electrical heater can be adopted to heat, by temperature controller by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and temperature programming can be realized control, be convenient in experimentation, investigate the impact of different regeneration temperature on coke-burning rate.
In order to make the gas entering reaction tubes have one to be uniformly distributed diametrically, in bottom design gas distributor (8) of reaction tubes.Gas distributor (8) should ensure gas being uniformly distributed on reaction tubes cross section, reduces gas pressure drop again, can adopt orifice plate or metal sintering plate; The opening diameter of orifice plate is 0.1mm ~ 5mm, and it is preferably 0.5 ~ 1mm, and percentage of open area is 1 ~ 100/cm
2, it is preferably 9 ~ 25/cm
2; The aperture of metal sintering plate is 10nm ~ 100 μm, and it is preferably 1 ~ 20 μm.
Although have employed expanding design on the top of reaction tubes; greatly reduce gas flow rate; the meeting of major part granules of catalyst is the bottom of the reaction tubes that falls back because of the reduction of gas speed; but still have the outlet that a small amount of fine particle is distributed in reaction tubes; therefore in order to avoid granules of catalyst is taken out of reaction tubes, gas-solid separator (11) is devised at the offgas outlet place at reaction tubes top.Gas-solid separator should ensure that most fine particle is separated, and reduces the pressure drop of gas again, can adopt ceramic 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-chromatography, mass spectrum for analyzing and testing system, it is preferably gas-chromatography and mass spectrometry.If adopt gas-chromatography, directly can determine the content of carbon monoxide, carbonic acid gas and the remaining oxygen in tail gas, the burning carbon amounts of whole simulation process can be calculated according to tail gas amount.If employing mass spectroscopy, then can reflect the Changing Pattern of various logistics in whole simulation process, be particularly suitable for Temperature Programmed Processes.
The present invention utilizes reaction tubes and the gas distributor of fluidization principle design reducing, under the operational condition of setting, can ensure that reclaimable catalyst is in good fluidized state in reaction tubes, reclaimable catalyst is fully contacted with fluidizing agent, reach stable and burn effect, thus the regenerative process of spent catalytic cracking catalyst under effectively can simulating industrial state.The factors such as regeneration temperature, oxygen partial pressure (oxygen concn), catalyzer carbon content of not only can investigating on the impact of burning speed of reaction, but also can study Gas-particle Flows, gas-solid two alternate mass transfers and heat transfer to the impact of burning speed of reaction.Therefore, utilize suitable analyzing and testing system, the present invention can make investigator in laboratory conditions, obtain the coke burning regeneration data more consistent with full scale plant, thus the Nomenclature Composition and Structure of Complexes realized coke content and coke in spent catalytic cracking agent, different catalysts is burnt reaction kinetics and is burnt the research of mechanism.
Accompanying drawing explanation
Fig. 1 is core component and the schema of catalytic cracking regenerator experimental simulation device of the present invention.
Fig. 2 under the experiment condition described in example 4, CO and CO
2mass spectra peak variation with temperature rule.
Fig. 3 is CO and CO under experiment 1 condition described in example 5
2mass spectra peak contrast
Fig. 4 is CO and CO under experiment 2 condition described in example 5
2mass spectra peak contrast
Fig. 5 is CO and CO under experiment 3 condition described in example 5
2mass spectra peak contrast
Fig. 6 is CO and CO under experiment 4 condition described in example 5
2mass spectra peak contrast
Accompanying drawing identifier declaration:
1-gas circuit (1);
2-gas circuit (2);
3-gas circuit (3);
4-pressure maintaining valve, 4-1-the first pressure maintaining valve, 4-2-the second pressure maintaining valve;
5-mass flowmeter, 5-1-the first mass flowmeter, 5-2-the second mass flowmeter, 5-3-the 3rd mass flowmeter;
6-mixing valve;
7-four-way valve;
8-gas distributor;
9-reaction tubes;
10-process furnace;
11-gas-solid separator;
12-moisture eliminator;
13-reversing valve;
14-exhaust collection and gauger;
15-analyzing and testing system, 15-1-gas-chromatography, 15-2-mass spectrum.
Embodiment
The invention discloses a kind of catalytic cracking regenerator experimental simulation method and device, those skilled in the art can use for reference present disclosure, and suitable improving technique parameter realizes content of the present invention.It is important to note that all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in the present invention.Method of the present invention and device are described by preferred embodiment, related personnel obviously can not depart from content of the present invention, spirit and scope method and apparatus as herein described is changed or suitably change with combination, realize and apply the technology of the present invention.
Embodiment 1: the mensuration of reclaimable catalyst carbon content in bubbling bed fluidized state
As shown in Figure 1, gas circuit (1) adopts helium, and gas circuit (2) adopts air, and the volumn concentration being controlled oxygen in mixed gas by the mass flowmeter in two gas circuits is 1%, and total gas flow is 1.5L/min.Reaction tubes (9) adopts silica glass material, and its underpart cylindrical drum diameter D1 is 35mm, and aspect ratio is 100, and Upper cylindrical cylinder diameter D2 is 210mm, and aspect ratio is 10, D2:D1=6; The angle α of cone surface and vertical line is 60 °, and now in reaction tubes, the empty tower gas velocity of bottom is 0.1m/s, and the empty tower gas velocity on top is 0.01m/s.Gas distributor adopts orifice plate, and opening diameter is 0.5mm, and percentage of open area is 9/cm
2; Gas-solid separator employing aperture is the metal sintering plate of 10nm.The outside of reaction tubes (9) adopts electrical heater to heat, and by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and can realize multi-segment program intensification control.
Experimental simulation process is as follows: first precise reclaimable catalyst 5g is placed in reaction tubes (9), before temperature does not reach default regeneration temperature in reaction tubes, first makes catalyzer be in good bubbling bed fluidized state with helium.Open the first venting valve (4-1), the first mass flowmeter (5-1) is regulated to make the flow of helium be 1.5L/min, rotary four-way valve (7) connects reaction tubes (9) to gas circuit (3), makes the catalyzer in reaction tubes (9) be in bubbling bed fluidized state.Then open process furnace (10), make the temperature of reaction tubes middle and lower part reach 400 DEG C with the heat-up rate of 20 DEG C/min, and be stabilized in this temperature.Reach after preset temp until temperature, open the second venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 1.429L/min and 0.071L/min.Then rotary four-way valve (7) connects reaction tubes (9) to gas mixture, simultaneously opens reversing valve (13) and starts to collect tail gas to exhaust collection and gauger (14).Reaction times is 300s, then measures exhaust gas volumes and passes through the composition that chromatogram (15-1) analyzes tail gas.The burning carbon amounts in regenerative process can be determined according to the amount of tail gas and the composition of tail gas, thus calculate the carbon content on catalyzer.Its analytical results is as table 1:
Table 1
Embodiment 2: the mensuration of reclaimable catalyst carbon content in turbulent bed fluidized state
As shown in Figure 1, gas circuit (1) adopts high pure nitrogen, and gas circuit (2) adopts purity oxygen, and the volumn concentration being controlled oxygen in mixed gas by the mass flowmeter in two gas circuits is 10%, and total gas flow is 20L/min.Reaction tubes (9) adopts 310S stainless material, and its underpart cylindrical drum diameter D1 is 20mm, and aspect ratio is 15, and Upper cylindrical cylinder diameter D2 is 40mm, and aspect ratio is 3, D2:D1=2; The angle α of cone surface and vertical line is 30 °, and now in reaction tubes, the empty tower gas velocity of bottom is 1.06m/s, and the empty tower gas velocity on top is 0.26m/s.Gas distributor employing aperture is the metal sintering plate of 10 μm, and gas-solid separator adopts aperture to be the ceramic porous material of 100nm.The outside of reaction tubes (9) adopts electrical heater to heat, and by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and can realize multi-segment program intensification control.Analyzing and testing system adopts gas-chromatography, can the volume content of carbon monoxide and carbonic acid gas in on-line analysis tail gas.
Experimental simulation process is as follows: first precise reclaimable catalyst 50g is placed in reaction tubes (9), before temperature does not reach default regeneration temperature in reaction tubes, first makes catalyzer be in good turbulent bed fluidized state with pure nitrogen gas.Open the first venting valve (4-1), the first mass flowmeter (5-1) is regulated to make the flow of nitrogen be 20L/min, rotary four-way valve (7) connects reaction tubes (9) to gas circuit (3), makes the catalyzer in reaction tubes (9) be in turbulent bed fluidized state.Then open process furnace (10), make the temperature of reaction tubes middle and lower part reach 680 DEG C with the heat-up rate of 20 DEG C/min, and be stabilized in this temperature.Reach after preset temp until temperature, open venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 18L/min and 2L/min.Then rotary four-way valve (7) connects reaction tubes (9) to gas mixture, simultaneously opens reversing valve (13) and starts to collect tail gas to exhaust collection and gauger (14).Reaction times is 30s, then measures exhaust gas volumes and passes through the composition that chromatogram (15-1) analyzes tail gas.The burning carbon amounts in regenerative process can be determined according to the amount of tail gas and the composition of tail gas, thus calculate the carbon content on catalyzer.Its analytical results is as shown in table 2:
Table 2
Embodiment 3: the mensuration of reclaimable catalyst carbon content in fast fluidized bed fluidized state
As shown in Figure 1, gas circuit (1) adopts high-purity argon gas, and gas circuit (2) adopts purity oxygen, and the volumn concentration being controlled oxygen in mixed gas by the mass flowmeter in two gas circuits is 90%, and total gas flow is 60L/min.Reaction tubes (9) adopts 310S stainless material, and its underpart cylindrical drum diameter D1 is 20mm, and aspect ratio is 1, and Upper cylindrical cylinder diameter D2 is 25mm, and aspect ratio is 0.5, D2:D1=1.2; The angle α of cone surface and vertical line is 5 °, and now in reaction tubes, the empty tower gas velocity of bottom is 3m/s, and the empty tower gas velocity on top is 2m/s.Gas distributor employing aperture is the metal sintering plate of 20 μm, and gas-solid separator employing aperture is the ceramic porous material of 10 μm.The outside of reaction tubes (9) adopts electrical heater to heat, and by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and can realize multi-segment program intensification control.Analyzing and testing system adopts gas-chromatography, can the volume content of carbon monoxide and carbonic acid gas in on-line analysis tail gas.
Experimental simulation process is as follows: first precise reclaimable catalyst 150g is placed in reaction tubes (9), before temperature does not reach default regeneration temperature in reaction tubes, first makes catalyzer be in good fast fluidized bed fluidized state with pure argon.Open the first venting valve (4-1), the first mass flowmeter (5-1) is regulated to make the flow of argon gas be 60L/min, rotary four-way valve (7) connects reaction tubes (9) to gas circuit (3), makes the catalyzer in reaction tubes (9) be in fast fluidized bed fluidized state.Then open process furnace (10), make the temperature of reaction tubes middle and lower part reach 1100 DEG C with the heat-up rate of 20 DEG C/min, and be stabilized in this temperature.Reach after preset temp until temperature, open the second venting valve (4-2), the flow of the second quality of regulation under meter (5-2) and the 3rd mass flowmeter (5-3) is respectively 6L/min and 54L/min.Then rotary four-way valve (7) connects reaction tubes (9) to gas mixture, simultaneously opens reversing valve (13) and starts to collect tail gas to exhaust collection and gauger (14).Reaction times is 30s, then measures exhaust gas volumes and passes through the composition that chromatogram (15-1) analyzes tail gas.The burning carbon amounts in regenerative process can be determined according to the amount of tail gas and the composition of tail gas, thus calculate the carbon content on catalyzer.Its analytical results is as shown in table 3:
Table 3
Embodiment 4: carbon monoxide and the research of carbonic acid gas Conduce Disciplinarian in regenerative process
Gas circuit (1) adopts high pure nitrogen, and gas circuit (2) adopts purity oxygen, and the volumn concentration being controlled oxygen in mixed gas by the mass flowmeter in two gas circuits is 10%, and total gas flow is 20L/min.Reaction tubes (9) adopts 310S stainless material, and its underpart cylindrical drum diameter D1 is 20mm, and aspect ratio is 15, and Upper cylindrical cylinder diameter D2 is 40mm, and aspect ratio is 3, D2:D1=2; The angle α of cone surface and vertical line is 30 °, and now in reaction tubes, the empty tower gas velocity of bottom is 1.06m/s, and the empty tower gas velocity on top is 0.26m/s.Gas distributor employing aperture is the metal sintering plate of 1 μm, and gas-solid separator adopts aperture to be the ceramic porous material of 90nm.The outside of reaction tubes (9) adopts electrical heater to heat, and by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and can realize multi-segment program intensification control.Analyzing and testing system adopts on-line mass spectroscopy.
Experimental simulation process is as follows: first precise reclaimable catalyst 50g is placed in reaction tubes (9), open the first venting valve (4-1) and the second venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 18L/min and 2L/min.Then rotary four-way valve (7) connects reaction tubes (9) to gas mixture, simultaneously opens reversing valve (13) to mass spectrum (15-2) on-line analysis.Finally open process furnace (10), carry out temperature programming with the heat-up rate of 10 DEG C/min from room temperature to 800 DEG C (a reaction tubes middle and lower part temperature).According to the carbon monoxide in mass-spectrometric data and their Conduce Disciplinarian of carbonic anhydride ion peak research.Its result as shown in Figure 2.
Embodiment 5: the regenerative process research of reclaimable catalyst under gas with various atmosphere
Gas circuit (1) adopts high pure nitrogen, and gas circuit (2) adopts purity oxygen, and by the volumn concentration of oxygen in the mass flowmeter modulation mixed gas in two gas circuits, total gas flow is 20L/min.Reaction tubes (9) adopts 310S stainless material, and its underpart cylindrical drum diameter D1 is 20mm, and aspect ratio is 15, and Upper cylindrical cylinder diameter D2 is 40mm, and aspect ratio is 3, D2:D1=2; The angle α of cone surface and vertical line is 30 °, and now in reaction tubes, the empty tower gas velocity of bottom is 1.06m/s, and the empty tower gas velocity on top is 0.26m/s.Gas distributor adopts orifice plate, and opening diameter is 0.5mm, and percentage of open area is 25/cm
2; Gas-solid separator adopts aperture to be the ceramic porous material of 90nm.The outside of reaction tubes (9) adopts electrical heater to heat, and by being distributed in thermopair feedback control Heating temperature and the heating rate of reaction tubes inside, and can realize temperature programming control.Analyzing and testing system adopts on-line mass spectroscopy.
Experimental simulation process is as follows:
Experiment 1
Precise reclaimable catalyst 50g is placed in reaction tubes (9), open the first venting valve (4-1) and the second venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 19L/min and 1L/min, make the volume content of oxygen in mixed gas be 5%.Rotary four-way valve (7) connects reaction tubes (9) to gas mixture, simultaneously opens reversing valve (13) to mass spectrum (15-2) on-line analysis.Open process furnace (10), carry out temperature programming with the heat-up rate of 10 DEG C/min from room temperature to 680 DEG C (a reaction tubes middle and lower part temperature), and stablize 680 DEG C 10 minutes.Obtaining reclaimable catalyst is playback of data in the atmosphere of 5% at oxygen volume content, and it the results are shown in Figure the mass spectrum A in 3.
Experiment 2
Precise reclaimable catalyst 50g is placed in reaction tubes (9), open the first venting valve (4-1) and the second venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 18L/min and 2L/min, make the volume content of oxygen in mixed gas be 10%.Repeat above-mentioned experimentation, obtaining reclaimable catalyst is playback of data in the atmosphere of 10% at oxygen volume content, and it the results are shown in Figure the mass spectrum B in 4.
Experiment 3
Precise reclaimable catalyst 50g is placed in reaction tubes (9), open the first venting valve (4-1) and the second venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 17L/min and 3L/min, make the volume content of oxygen in mixed gas be 15%.Repeat above-mentioned experimentation, obtaining reclaimable catalyst is playback of data in the atmosphere of 15% at oxygen volume content, and it the results are shown in Figure the mass spectrum C in 5.
Experiment 4
Precise reclaimable catalyst 50g is placed in reaction tubes (9), open the first venting valve (4-1) and the second venting valve (4-2), regulate the flow of the second mass flowmeter (5-2) and the 3rd mass flowmeter (5-3) to be respectively 16L/min and 4L/min, make the volume content of oxygen in mixed gas be 20%.Repeat above-mentioned experimentation, obtaining reclaimable catalyst is playback of data in the atmosphere of 20% at oxygen volume content, and it the results are shown in Figure the mass spectrum D in 6.
The above four groups of data of contrast, can obtain the regeneration rule of reclaimable catalyst under gas with various atmosphere.Its comparing result is as mass spectrum A ~ D in Fig. 3 ~ 6.
Should be understood that; the above is only the preferred embodiment of the present invention, for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a catalytic cracking regenerator experimental simulation method, is characterized in that said method comprising the steps of:
Gas 1 is passed into reaction tubes, and the flow velocity of adjustments of gas 1 makes the catalyzer in reaction tubes be in fluidized state;
Reacting by heating pipe makes it reach temperature of reaction simultaneously, after this keeps or temperature programming;
After reaching temperature of reaction, gas 2 and gas 1 on-line mixing, mixed gas enters reactor subsequently;
Mixed gas and catalyzer react;
Reacted gas is through gas solid separation;
Gas after gas solid separation is measured and/or analyzed.
2. catalytic cracking regenerator experimental simulation method according to claim 1, is characterized in that gas 1 is the one in nitrogen, helium, argon gas; Gas 2 is air or oxygen.
3. catalytic cracking regenerator experimental simulation method according to claim 2, after it is characterized in that gas 1 and gas 2 mix, the volume content of oxygen is 0% ~ 100%.
4. catalytic cracking regenerator experimental simulation method according to claim 1, is characterized in that the void tower linear speed of described reaction tubes bottom is 0.1m/s ~ 3m/s; The void tower linear speed on described reaction tubes top is 0.01m/s ~ 3m/s.
5. the catalytic cracking regenerator experimental simulation method according to claim 1-4 any one, is characterized in that the temperature of reaction of mixed gas and catalyzer is 400 DEG C ~ 1100 DEG C.
6. the catalytic cracking regenerator experimental simulation method according to claim 1-4 any one, is characterized in that described gas dosing method is draining gas collection; Described analytical procedure is one or both in gas-chromatography or mass spectrum.
7. a catalytic cracking regenerator experimental simulation device, is characterized in that, comprises gas circuit (1), gas circuit (2), be arranged on the venting valve (4) in gas circuit (1) and gas circuit (2) and mass flowmeter (5), mixing valve (6), four-way valve (7), connect the gas circuit (3) of gas circuit (1) and four-way valve (7), gas distributor (8), reaction tubes (9), process furnace (10), gas-solid separator (11), moisture eliminator (12), reversing valve (13), exhaust collection and gauger (14) and analyzing and testing system (15), described gas circuit (1) and gas circuit (2) are all connected on mixing valve (6), described mixing valve (6) is connected on the gas distributor (8) of described reaction tubes (9) bottom through four-way valve (7), the gas-solid separator (11) at described reaction tubes (9) top is connected with moisture eliminator (12), and described moisture eliminator (12) is connected with gauger (14) and/or analyzing and testing system (15) with exhaust collection by reversing valve (13).
8. catalytic cracking regenerator experimental simulation device according to claim 7, it is characterized in that described reaction tubes (9) adopts variable diameter design, on it, the ratio of cylindrical drum diameter D2 and lower cylindrical drum diameter D1 is 1 ~ 6; The aspect ratio of upper cylindrical drum is 0.5 ~ 100; The aspect ratio of lower cylindrical drum is 1 ~ 1000; The angle α of cone surface and vertical line is 0 ° ~ 60 °.
9. catalytic cracking regenerator experimental simulation device according to claim 7, is characterized in that described reaction tubes (9) adopts high temperature material.
10. the catalytic cracking regenerator experimental simulation device according to claim 7-9 any one, is characterized in that described reaction tubes (9) adopts silica glass or 310S stainless material; Described gas distributor (8) adopts orifice plate or metal sintering plate; Described gas-solid separator (11) adopts ceramic porous material or metal sintering plate.
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