CN105080570B - Fluid bed syngas directly prepares the renovation process of low-carbon alkene ferrum-based catalyst - Google Patents
Fluid bed syngas directly prepares the renovation process of low-carbon alkene ferrum-based catalyst Download PDFInfo
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Abstract
The present invention relates to the renovation process that a kind of fluid bed syngas directly prepares low-carbon alkene ferrum-based catalyst.Following steps are included to the catalyst in-situ regeneration of activity decrease in fluid bed：Remove the mink cell focus wax of at least part catalyst surface absorption under constant-pressure and high-temperature using inert gas first；Secondly first is carried out to the catalyst of activity decrease using the mixed air of inert gas and hydrogen to regenerate；Second is carried out in suitable condition to the catalyst of activity decrease using the gaseous mixture of inert gas and carbon monoxide and low-carbon alkene again to regenerate.The activity of catalyst by above-mentioned regeneration can be completely recovered to the level before activity decrease, and fluid bed situ regenerates, and very simply can be switched to reproduced state from reactiveness, simply be switched to reactiveness after the completion of regeneration again.The invention is applied to but is not limited to the regenerative process that extensive fluid bed syngas directly prepares catalyst when low-carbon alkene is produced.
Description
Technical field
The present invention relates to the renovation process that a kind of fluid bed syngas directly prepares low-carbon alkene ferrum-based catalyst.
Background technology
Fischer-Tropsch (Fascher-Tropsch) synthesis is that (main component is CO and H using synthesis gas2) in the effect of catalyst
The process of lower synthesis hydrocarbon, is an important channel of coal and natural gas indirect liquefaction.This method is nineteen twenty-three by Germany scientist
Frans Fischer and Hans Tropsch inventions, i.e. heterogeneous catalysis hydrogenation occurs on metallic catalyst for CO, raw
Into the process of the mixture based on linear paraffin and alkene.
Germany has just carried out the research and development to F- T synthesis in the twenties in last century, and realizes industry in 1936
Change, closed after World War II because can not economically be competed with petroleum industry；South Africa possesses abundant coal resources, but petroleum resources
Plaque is weary, and is limited for a long time by international community's economy and political sanction, forces it to develop coal-to-oil industry technology, and in 1955
Coal base F-T artificial oil factory (Sasol-1) of the First production capacity for 25~400,000 tons of product/years is built up.1973 and
The world oil crisis twice of 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, based on Strategic Technology deposit
Consideration, F-T synthetic technologys arouse the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol companies are again successive
Build up and Liang Zuomeiji artificial oils factory of having gone into operation.But plummeting for World oil price in 1986, has postponed F-T synthetic technologys at it
The heavy industrialization process of its country.Since twentieth century nineties, petroleum resources shortage and in poor quality increasingly, while coal
But it is continuously increased with natural gas proved reserves, fischer-tropsch technologies cause extensive concern again, Fiscber-Tropscb synthesis technology has also obtained considerable
Development.Fischer-tropsch catalysts conventional at present, from active component for be divided into two major classes：Ferrum-based catalyst and cobalt-based catalyst
Agent；And common synthesis technique is divided into two major classes if classifying from synthesis condition angle：High temperature fischer-tropsch synthesis technique and low temperature
Fischer-tropsch synthesis process；Synthesis technique is divided into three major types from used reactor difference if classifying：Fixed bed F- T synthesis
Technique, fluid bed fischer-tropsch synthesis process (has the recirculating fluidized bed of early stage and developed later on the basis of recirculating fluidized bed
It is fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technique.Fixed bed therein is generally used for Low Temperature Fischer Tropsch work with slurry bed system
Skill, is used for the production of mink cell focus and wax, and fluid bed is then more suitable for producing the high temperature fischer-tropsch work of the more hydro carbons of lightweight
Skill.In recent years, with the fast development of China's economy, the demand to oil product is growing day by day.The characteristics of China's energy is
The few gas oil starvation of rich coal, the coal environmental pollution caused of directly burning also is taken seriously increasingly.Exploitation is by coal/natural gas through synthesis gas
The process of oil product is converted into, can not only be reduced to external dependence on the energy, and for solving coal-fired caused ring
Border pollution problem has great importance.
What the fischer-tropsch catalysts of document and patent report were more in recent years applies to cryogenic high pressure paste state bed reactor
To produce high-carbon long chain hydrocarbons, general mostly is precipitated iron catalyst, or immersion-type Co catalysts.If Rentech companies of the U.S. are special
A kind of F- T synthesis precipitated iron suitable for paste state bed reactor is just reported in sharp USP5504118 and CN1113905A to be catalyzed
The preparation method of agent.The F- T synthesis of light hydrocarbon it is general it is many carries out in a fluidized bed reactor, be reaction temperature the characteristics of the technique
Degree is higher, and conversion ratio is higher, in the absence of the difficulty of solid-liquor separation.Currently reported is applied to many of fluid bed F- T synthesis
For molten iron type catalyst, occasionally there is some type of precipitated iron catalyst.Being referred to one kind if in patent CN1704161A is used for
A kind of precipitated iron for fluid bed is referred in the preparation of the molten iron type catalyst of F- T synthesis, patent CN1695804A to be catalyzed
Agent.
Preparing low-carbon olefin has i.e. specific under direct method and indirect method, i.e. so-called direct method specified conditions
High temperature fischer-tropsch synthesis under catalyst.Although there is some that fixed bed applications are used for into what low-carbon alkene was produced in high temperature fischer-tropsch at present
Attempt, such as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but be due to that Fischer-Tropsch synthesis is strong exothermal reaction, use fixed bed
When, hot difficulty is removed in reactor, easy temperature runaway makes catalyst easily inactivate, and these trials terminate in laboratory stage.
During plant running, with the extension of catalyst runs time, activity, the selectivity of catalyst can be
Reduction, it is necessary to be handled catalyst to improve the performance of catalyst after activity is reduced to a certain degree.Effectively live again
Change method is one of key technology of fischer-tropsch synthetic catalyst long-term operation.US6022755 discloses a kind of F- T synthesis and urged
The activation method of agent, this method is under F- T synthesis operator scheme, the content of CO in unstripped gas gradually to be reduced, to reactor
Export H2/ CO ratios operate the regular hour more than 10: 1 under this operating mode, catalyst performance is obtained part recovery.
US6486220 discloses a kind of activation method of fischer-tropsch synthetic catalyst, and this method is reclaimable catalyst in the gas containing steam
Activation process is carried out in atmosphere.Activation process condition is：250~350 DEG C of temperature, soak time at least 4h, activated gas volume are empty
Speed at least 0.5,10~350pisg of activation pressure, activated gas contain the hydrogen no more than 10 volume %.US2003166451 is public
A kind of renovation process of fischer-tropsch synthetic catalyst is opened, this method takes the hydrogen atmosphere including ammonia or weak organic acid is included
In catalyst is handled, the catalyst performance after processing obtain part recovery.But regenerated in fischer-tropsch synthetic catalyst
Cheng Zhong, when reaction atmosphere and operating condition regulation not at that time, it may appear that serious overheating problem, F- T synthesis can be caused on the contrary
Catalyst performance declines.We did not see that in-situ regeneration catalyst made its activity is basic to recover in fluid bed also so far
Report as before.
The content of the invention
The present invention provides the renovation process that a kind of fluid bed syngas directly prepares low-carbon alkene ferrum-based catalyst, i.e., in stream
Change the catalyst in-situ regeneration to activity decrease in bed, this method includes following steps：First using inert gas normal
The mink cell focus wax of at least part catalyst surface absorption is removed under super pressure-high temperature；Secondly using inert gas and the mixed air pair of hydrogen
The catalyst of activity decrease carries out first and regenerated；Again using inert gas and the gaseous mixture pair of carbon monoxide and low-carbon alkene
The catalyst of activity decrease carries out the second regeneration suitable.The activity of catalyst by above-mentioned regeneration can be substantially completely extensive
Again to the level before activity decrease, and fluid bed situ regenerates, and very simply can be switched to regeneration shape from reactiveness
State, is simply switched to reactiveness again after the completion of regeneration.The invention is applied to but to be not limited to extensive fluid bed syngas straight
Connect the regenerative process of catalyst when preparing low-carbon alkene production.
In order to solve the above technical problems, technical scheme is as follows：A kind of fluid bed syngas directly prepares low-carbon
The renovation process of alkene catalyst, in turn includes the following steps：
(1) after catalyst inactivation, stop reaction gas, switch to volume space velocity to be 300~10000h air inlet-1Displacement gas
Body, substitution gas are inert gas；
(2) complete after step (1), adjust the pressure of reactor to normal pressure, regulation temperature of reactor is 280~520 DEG C,
3~30h is stopped under this atmosphere and this temperature, pressure；
(3) complete after step (2), the pressure of reactor is raised to 0.01~5.0MPa, substitution gas are switched into regeneration
Gas I, the volume space velocity of regulation regeneration gas I is 300~10000h-1, reactor is then heated to 230~480 DEG C, herein
Atmosphere and stop 3~60 hours at a temperature of this；Regeneration gas I is the gaseous mixture of inert gas and hydrogen；
(4) keep volume space velocity, temperature and the pressure of step (3) constant, regeneration gas I is switched into regeneration gas
II, stop 4~60 hours；Regeneration gas II is the gaseous mixture of inert gas, carbon monoxide and low-carbon alkene.
In above-mentioned technical proposal, after the completion of step (4), keep system pressure constant, temperature of reactor is adjusted to 250~
430 DEG C, air speed is switched to be 300~16000h regeneration gas II-1Synthesis gas proceed by Fischer-Tropsch synthesis.
In above-mentioned technical proposal, the inert gas used in regeneration is preferably at least one in nitrogen, helium and argon gas
Kind；The preferred scope of the inert gas volume space velocity of (1) is 1000~8000h in step-1；Step (2) temperature of reactor it is excellent
It is 300~500 DEG C to select scope, and the preferred scope of residence time is 5~25h；The volume ratio of inert gas and hydrogen in step (3)
Preferably inert gas：H2=(0~10)：1, the preferred scope of volume space velocity is 1000~8000h-1, the preferred scope of temperature
For 245~460 DEG C, the preferred scope of pressure is 0.1~4.5MPa, 10~50h of preferred scope of residence time；Step (4) institute
The low-carbon alkene used is preferably selected from least one of ethene, propylene, butylene and isobutene；Indifferent gas in step (4)
The volume ratio of body and carbon monoxide and low-carbon alkene is preferably inert gas：Carbon monoxide：Low-carbon alkene=(0-10.0)：1.0：
(0.2-2.0)；The pressure of reactor is preferably 0.6~3.5MPa in step (3)；In step in (4) regeneration gas II stop
The preferred scope of time is 6~50h.
The catalyst used in the invention is the ferrum-based catalyst reacted 1500 hours, the main metal active constituent of catalyst
It is iron, auxiliary agent is selected from manganese, copper, zinc, cobalt, nickel, lanthanide rare, alkaline-earth metal, alkali metal etc., structural promoter is selected from silica,
Titanium dioxide, zirconium oxide, aluminum oxide, catalyst is applied to the distribution of particle sizes of fluid bed for the microspheroidal of spray drying forming
Profile.
Regeneration methods of the invention is not limited only to the regeneration for ferrum-based catalyst, due to the catalyst in F- T synthesis
Carbon distribution same type, therefore can be used in the regeneration of the fischer-tropsch synthetic catalyst of other systems.
Advantages of the present invention is as follows：In-situ regeneration in the fluidized-bed reactor of synthetic reaction is carried out in catalyst, in reaction
It was found that activity decrease, which exceedes tolerable scope, can be switched to regeneration at once, reaction can be very simply switched to after the completion of regeneration
State, it is simple to operate；The level that the activity of catalyst after regeneration can be returned to substantially completely before activity decrease, i.e. conversion ratio
With the selectivity of low-carbon alkene can substantially return to react initial conditions when conversion ratio and selectivity；In fluid bed again
Raw, good thermal diffusivity, it is to avoid the overheating problem that may occur on catalyst during regeneration；Can immediately it be put into after catalyst regeneration
To GTO it is synthetically produced in, it is adaptable to large-scale fluidized bed GTO devices.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 300h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 280 DEG C, in this atmosphere and this temperature, pressure
Lower stop 3h.
(3) temperature of adjustment reactor is 230 DEG C, and pressure is 0.01MPa；
(4) air speed is switched to be 300h air inlet-1The gaseous mixture of nitrogen and hydrogen, stops under this atmosphere and this temperature, pressure
Stay 3 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=10：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 0.2MPa；
(6) autogenous cutting will be activated and is changed to nitrogen and carbon monoxide and the gaseous mixture of ethene, nitrogen and carbon monoxide and ethene
Volume ratio be nitrogen：Carbon monoxide：Ethene=10：1：2, stop 4h；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 250 DEG C, unstripped gas is switched into air speed
For 300h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its volume
Than for H2：CO=1.8:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Embodiment 2】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 10000h-1Helium；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 520 DEG C, in this atmosphere and this temperature, pressure
Lower stop 30h；
(3) temperature of adjustment reactor is 480 DEG C, and pressure is 5.0MPa；
(4) air speed is switched to be 10000h air inlet-1Hydrogen, is stopped 60 hours under this atmosphere and this temperature, pressure；
(5) keep temperature above constant with air speed, reactor pressure is risen into 10MPa；
(6) autogenous cutting will be activated and is changed to helium and carbon monoxide and the gaseous mixture of propylene, helium and carbon monoxide and propylene
Volume ratio be nitrogen：Carbon monoxide：Ethene=10：1：0.2, stop 60h；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 430 DEG C, unstripped gas is switched into air speed
For 16000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=5:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Embodiment 3】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 1000h-1Argon gas；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 300 DEG C, in this atmosphere and this temperature, pressure
Lower stop 5h.
(3) temperature of adjustment reactor is 245 DEG C, and pressure is 0.1MPa；
(4) air speed is switched to be 1000h air inlet-1The gaseous mixture of argon gas and hydrogen, under this atmosphere and this temperature, pressure
Stop 10 hours, the wherein volume ratio of argon gas and hydrogen is argon gas：H2=1：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 0.6MPa；
(6) will activate the gaseous mixture that autogenous cutting is changed to argon gas and carbon monoxide and n-butene, argon gas and carbon monoxide with just
The volume ratio of butylene is argon gas：Carbon monoxide：N-butene=10：1：1, stop 6h；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 260 DEG C, unstripped gas is switched into air speed
For 500h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its volume
Than for H2：CO=2.0:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Embodiment 4】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 8000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 500 DEG C, in this atmosphere and this temperature, pressure
Lower stop 25h.
(3) temperature of adjustment reactor is 460 DEG C, and pressure is 4.5MPa；
(4) air speed is switched to be 8000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 50 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=1：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 7.5MPa；
(6) activation autogenous cutting is changed to the volume ratio of the gaseous mixture of carbon monoxide and isobutene, carbon monoxide and isobutene
For carbon monoxide：Isobutene=1：1, stop 50h；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 420 DEG C, unstripped gas is switched into air speed
For 15000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=4.8:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Embodiment 5】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 6000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 480 DEG C, in this atmosphere and this temperature, pressure
Lower stop 15h.
(3) temperature of adjustment reactor is 400 DEG C, and pressure is 2.5MPa；
(4) air speed is switched to be 6000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 36 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=1：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 3.5MPa；
(6) will activate the gaseous mixture that autogenous cutting is changed to nitrogen and carbon monoxide and low-carbon alkene, nitrogen and carbon monoxide with
The volume ratio of low-carbon alkene is nitrogen：Carbon monoxide：Low-carbon alkene=3：1：1, stop 30h, wherein low-carbon alkene be ethene with
Propylene by volume 1：1 mixing；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 350 DEG C, unstripped gas is switched into air speed
For 8000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=2:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Embodiment 6】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 6000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 450 DEG C, in this atmosphere and this temperature, pressure
Lower stop 15h.
(3) temperature of adjustment reactor is 400 DEG C, and pressure is 2.5MPa；
(4) air speed is switched to be 6000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 36 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=5：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 3.5MPa；
(6) will activate the gaseous mixture that autogenous cutting is changed to nitrogen and carbon monoxide and low-carbon alkene, nitrogen and carbon monoxide with
The volume ratio of low-carbon alkene is nitrogen：Carbon monoxide：Low-carbon alkene=3：1：1, stop 30h, wherein low-carbon alkene be ethene with
N-butene by volume 1：1 mixing；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 350 DEG C, unstripped gas is switched into air speed
For 8000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=3:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Embodiment 7】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 6000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 480 DEG C, in this atmosphere and this temperature, pressure
Lower stop 15h.
(3) temperature of adjustment reactor is 400 DEG C, and pressure is 2.5MPa；
(4) air speed is switched to be 6000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 36 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=1：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 3.5MPa；
(6) will activate the gaseous mixture that autogenous cutting is changed to nitrogen and carbon monoxide and low-carbon alkene, nitrogen and carbon monoxide with
The volume ratio of low-carbon alkene is nitrogen：Carbon monoxide：Low-carbon alkene=3：1：1, stop 30h, wherein low-carbon alkene be ethene with
Propylene and isobutene by volume 1：1：1 mixing；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 350 DEG C, unstripped gas is switched into air speed
For 8000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=2.5:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Comparative example 1】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 6000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 600 DEG C, in this atmosphere and this temperature, pressure
Lower stop 15h.
(3) temperature of adjustment reactor is 500 DEG C, and pressure is 2.5MPa；
(4) air speed is switched to be 6000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 36 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=1：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 3.5MPa；
(6) will activate the gaseous mixture that autogenous cutting is changed to nitrogen and carbon monoxide and low-carbon alkene, nitrogen and carbon monoxide with
The volume ratio of low-carbon alkene is nitrogen：Carbon monoxide：Low-carbon alkene=3：1：1, stop 30h, wherein low-carbon alkene be ethene with
Propylene by volume 1：1 mixing；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 350 DEG C, unstripped gas is switched into air speed
For 8000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=2:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Comparative example 2】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 6000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 200 DEG C, in this atmosphere and this temperature, pressure
Lower stop 15h.
(3) temperature of adjustment reactor is 220 DEG C, and pressure is 2.5MPa；
(4) air speed is switched to be 6000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 36 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=1：1；
(5) keep temperature above constant with air speed, reactor pressure is risen into 3.5MPa；
(6) will activate the gaseous mixture that autogenous cutting is changed to nitrogen and carbon monoxide and low-carbon alkene, nitrogen and carbon monoxide with
The volume ratio of low-carbon alkene is nitrogen：Carbon monoxide：Low-carbon alkene=3：1：1, stop 30h, wherein low-carbon alkene be ethene with
Propylene by volume 1：1 mixing；
(7) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 350 DEG C, unstripped gas is switched into air speed
For 8000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=2:1.
The subordinate list that the performance of catalyst after regeneration is seen below.
【Comparative example 3】
(1) by 1.5 inches, equipped with the original ferrum-based catalysts of 100g, (catalyst is prepared for co-precipitation spray drying, composition
It is 100Fe/80Mn/5K/80SiO by atomic ratio measuring2) and reacted 1500 hours or so, the fluid bed that activity has declined
The air inlet of reactor switches to air speed 6000h-1Nitrogen；
(2) pressure of adjustment reactor is to normal pressure, and adjustment temperature of reactor is 480 DEG C, in this atmosphere and this temperature, pressure
Lower stop 15h.
(3) temperature of adjustment reactor is 400 DEG C, and pressure is 2.5MPa；
(4) air speed is switched to be 6000h air inlet-1The gaseous mixture of nitrogen and hydrogen, under this atmosphere and this temperature, pressure
Stop 36 hours, the wherein volume ratio of nitrogen and hydrogen is N2：H2=1：1；
(5) activation is finished, and keeps system pressure constant, temperature of reactor is adjusted into 350 DEG C, unstripped gas is switched into air speed
For 8000h-1Synthesis gas proceed by Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, its body
Product is than being H2：CO=2:1.
The subordinate list 1 that the performance of catalyst after regeneration is seen below.
Table 1
It is that (appreciation condition is the evaluation result of fresh catalyst that # is corresponding：350 DEG C, 1.5MPa, air speed 8000h-1, H2/
CO (volume)=2/1).
Claims (10)
1. a kind of fluid bed syngas directly prepares the renovation process of light olefins catalyst, in turn include the following steps：
(1) after catalyst inactivation, stop reaction gas, switch to volume space velocity to be 300~10000h air inlet-1Substitution gas, put
Ventilation body is inert gas；
(2) complete after step (1), adjust the pressure of reactor to normal pressure, regulation temperature of reactor is 280~520 DEG C, herein gas
3~30h is stopped under atmosphere and this temperature, pressure；
(3) complete after step (2), the pressure of reactor is raised to 0.01~5.0MPa, substitution gas are switched into regeneration gas
I, the volume space velocity of regulation regeneration gas I is 300~10000h-1, reactor is then heated to 230~480 DEG C, in this atmosphere
Stopped 3~60 hours with a temperature of this；Regeneration gas I is the gaseous mixture of inert gas and hydrogen；
(4) keep step (3) volume space velocity, temperature and by pressure adjust to 0.6~7.5MPa, regeneration gas I is switched
For regeneration gas II, stop 4~60 hours；Regeneration gas II is the gaseous mixture of inert gas, carbon monoxide and low-carbon alkene.
2. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
It is after the completion of step (4), keeps system pressure constant, temperature of reactor is adjusted to 250~430 DEG C, by regeneration gas II
It is 300~16000h to switch to air speed-1Synthesis gas proceed by Fischer-Tropsch synthesis.
3. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
It is at least one of nitrogen, helium and argon gas to be the inert gas used in regenerating.
4. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
The volume space velocity for being in step the inert gas of (1) is 1000~8000h-1。
5. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
It is 300~500 DEG C, 5~25h of residence time to be step (2) temperature of reactor.
6. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
The volume ratio for being inert gas and hydrogen in step (3) is inert gas：H2=(0~10)：1, and inert gas is not 0,
Volume space velocity is 1000~8000h-1, temperature is 245~460 DEG C, and pressure is 0.1~4.5MPa, stops 10~50h.
7. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
It is selected from least one of ethene, propylene, butylene and isobutene to be low-carbon alkene used in step (4).
8. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
The volume ratio for being inert gas and carbon monoxide in step (4) and low-carbon alkene is inert gas：Carbon monoxide：Low-carbon alkene
Hydrocarbon=(0-10.0)：1.0：(0.2-2.0)；Wherein inert gas content is not 0.
9. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, its feature
The residence time for being in step regeneration gas II in (4) is 6~50h.
10. fluid bed syngas according to claim 6 directly prepares the renovation process of light olefins catalyst, its feature
The pressure for being reactor in step (4) is 0.6~3.5MPa.
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| CN101703937A (en) * | 2009-09-29 | 2010-05-12 | 武汉凯迪科技发展研究院有限公司 | Method for regenerating cobalt-base catalyst for slurry-phase Fischer-Tropsch synthesis |
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| CN101703937A (en) * | 2009-09-29 | 2010-05-12 | 武汉凯迪科技发展研究院有限公司 | Method for regenerating cobalt-base catalyst for slurry-phase Fischer-Tropsch synthesis |
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