CN105080570A - In-fluid-bed reactivation method for catalyst for direct preparation of low-carbon olefins from synthesis gas - Google Patents
In-fluid-bed reactivation method for catalyst for direct preparation of low-carbon olefins from synthesis gas Download PDFInfo
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Abstract
The invention relates to an in-fluid-bed reactivation method for catalyst for direct preparation of low-carbon olefins from synthesis gas. In-fluid-bed reactivation method for catalyst with reduced activity comprises following steps: removing heavy wax adsorbed at least part of catalyst surface under high temperature and normal pressure by inert gas, then regenerating for a first time the catalyst with reduced activity by mixed gas of inert gas and hydrogen gas, and reactivating for the second time the catalyst with mixture of inert gas, carbon oxide and low carbon olefin in a proper condition. The activity of the reactivated catalyst can be restored to a level before the activity declines. The reactivation in fluid bed can be easily switched from reaction state to reactivation state, and then switched to the reaction state after the reactivation. The reactivation method is suitable for but is not limited to catalyst reactivation for large-scaled fluid bed synthetic gas for direct preparation for low carbon olefin.
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 utilizes synthesis gas (main component is CO and H
2) under the effect of catalyst, synthesize the process of hydrocarbon, be an important channel of coal and natural gas indirect liquefaction.To be nineteen twenty-three invented by Germany scientist FransFischer and HansTropsch the method, and namely heterogeneous catalysis hydrogenation occurs CO on metallic catalyst, generates based on the process of the mixture of linear paraffin and alkene.
Germany has just carried out the research and development to F-T synthesis in the twenties in last century, and achieves industrialization in 1936, closes after World War II because competing with petroleum industry economically; South Africa has abundant coal resources, but petroleum resources plaque is weary, and be subject to the restriction of international community's economy and political sanction for a long time, force its Development of Coal oils preparation industry technology, and built up in 1955 the coal-based F-T artificial oil factory (Sasol-1) that First production capacity is 25 ~ 400,000 tons of product/years.Twice world oil crisis of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, based on the consideration of Strategic Technology deposit, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol company builds up again and two coal-based artificial oil factories of having gone into operation in succession.But plummeting of World oil price in 1986, has postponed the heavy industrialization process of F-T synthetic technology in other country.Since twentieth century nineties, petroleum resources are shortage and in poor quality increasingly, and coal and natural gas proved reserves but constantly increase simultaneously, and fischer-tropsch technologies causes extensive concern again, and Fiscber-Tropscb synthesis technology have also been obtained significant progress.Fischer-tropsch catalysts conventional at present, is divided into two large classes: ferrum-based catalyst and cobalt-base catalyst active component; And common synthesis technique is divided into two large classes from the words that synthesis condition angle is classified: high temperature fischer-tropsch synthesis technique and Low Temperature Fischer Tropsch synthesis technique; Synthesis technique is divided into three major types from the used reactor difference words of classifying: fixed bed fischer-tropsch synthesis process, fluid bed fischer-tropsch synthesis process (have early stage recirculating fluidized bed and developed out afterwards on recirculating fluidized bed basis fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technique.Fixed bed wherein and slurry bed system are generally applied to low temperature fischer-tropsch process, are used for the production of mink cell focus and wax, and fluid bed is then more suitable for the high temperature fischer-tropsch technique of the hydro carbons producing comparatively lightweight.In recent years, along with the fast development of China's economy, be grow with each passing day to the demand of oil product.The feature of China's energy is rich coal weak breath oil starvation, and the coal environmental pollution caused of directly burning also comes into one's own increasingly.Exploitation is the process of oil product by coal/natural gas via Synthetic holography, not only can reduce to external dependence on the energy, and has great importance for solving the coal-fired problem of environmental pollution caused.
What the fischer-tropsch catalysts of document and patent report was many in recent years is be applicable to cryogenic high pressure paste state bed reactor to produce high-carbon long chain hydrocarbon, generally mostly is precipitated iron catalyst, or immersion-type Co catalysts.As Rentech company of the U.S. just reports a kind of preparation method being applicable to the F-T synthesis precipitated iron catalyst of paste state bed reactor in patent USP5504118 and CN1113905A.How the F-T synthesis of light hydrocarbon is general carries out in a fluidized bed reactor, and the feature of this technique is that reaction temperature is higher, and conversion ratio is higher, there is not the difficulty of solid-liquor separation.The currently reported molten iron type that the mostly is catalyst being applied to fluid bed F-T synthesis, occasionally has the precipitated iron catalyst of some types.As being just referred to a kind of preparation of the molten iron type catalyst for F-T synthesis in patent CN1704161A, in patent CN1695804A, be referred to a kind of precipitated iron catalyst for fluid bed.
Preparing low-carbon olefin has direct method and indirect method, the high temperature fischer-tropsch synthesis under so-called direct method i.e. specified conditions namely under specific catalyst.Although there are some fixed bed applications to be used for the trial of low-carbon alkene production in high temperature fischer-tropsch at present, as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but because Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, remove heat difficulty in reactor, easy temperature runaway, make the easy inactivation of catalyst, these trials all terminate in laboratory stage.
In plant running process, along with the prolongation of catalyst runs time, the activity of catalyst, selectively all to decrease, when activity is reduced to a certain degree, need the performance processing to improve catalyst to catalyst.Effective process for reactivation is one of key technology of fischer-tropsch synthetic catalyst long-term operation.US6022755 discloses a kind of activation method of fischer-tropsch synthetic catalyst, the method is under F-T synthesis operator scheme, reduces the content of CO in unstripped gas gradually, to reactor outlet H2/CO ratio more than 10: 1, operate the regular hour under this operating mode, make catalyst performance obtain part and recover.US6486220 discloses a kind of activation method of fischer-tropsch synthetic catalyst, and the method is that reclaimable catalyst carries out activation process in containing the atmosphere of steam.Activation process condition is: temperature 250 ~ 350 DEG C, soak time at least 4h, activated gas volume space velocity at least 0.5, activation pressure 10 ~ 350pisg, activated gas contain the hydrogen being no more than 10 volume %.US2003166451 discloses a kind of renovation process of fischer-tropsch synthetic catalyst, and the method is taked including ammonia or weak organic acid processes catalyst in interior hydrogen atmosphere, and the catalyst performance after process obtains part and recovers.But in fischer-tropsch synthetic catalyst regenerative process, when reaction atmosphere and operating condition regulated not at that time, there will be serious overheating problem, and fischer-tropsch synthetic catalyst hydraulic performance decline can be caused on the contrary.We did not also see that in fluid bed, in-situ regeneration catalyst made its active basic report recovered as before so far.
Summary of the invention
The invention provides the renovation process that a kind of fluid bed syngas directly prepares low-carbon alkene ferrum-based catalyst, namely in fluid bed to the catalyst in-situ regeneration of activity decrease, the method comprises following step: first adopt inert gas remove under constant-pressure and high-temperature at least part of catalyst surface absorption mink cell focus wax; Secondly the mixed air of inert gas and hydrogen is adopted to carry out the first regeneration to the catalyst of activity decrease; The gaseous mixture of inert gas and carbon monoxide and low-carbon alkene is again adopted to carry out the second regeneration to the catalyst of activity decrease at suitable.Level before the activity of the catalyst of above-mentioned regeneration can return to activity decrease substantially completely, and the regeneration of fluid bed situ, can be switched to reproduced state from reactiveness very simply, simply be switched to reactiveness again after having regenerated.This invention is applicable to but is not limited to extensive fluid bed syngas directly prepare the regenerative process of catalyst when low-carbon alkene is produced.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows: a kind of fluid bed syngas directly prepares the renovation process of light olefins catalyst, in turn includes the following steps:
(1) after catalysqt deactivation, stop reaction gas, air inlet switched to volume space velocity to be 300 ~ 10000h
-1substitution gas, substitution gas is inert gas;
(2), after completing steps (1), regulate the pressure of reactor to normal pressure, regulate temperature of reactor to be 280 ~ 520 DEG C, under this atmosphere and this temperature, pressure, stop 3 ~ 30h;
(3) after completing steps (2), the pressure of reactor is raised to 0.01 ~ 5.0MPa, substitution gas is switched to regeneration gas I, the volume space velocity regulating regeneration gas I is 300 ~ 10000h
-1, then reactor is heated to 230 ~ 480 DEG C, stops 3 ~ 60 hours under this atmosphere and this temperature; Regeneration gas I is the gaseous mixture of inert gas and hydrogen;
(4) keep the volume space velocity of step (3), temperature and pressure constant, regeneration gas I is switched to regeneration gas II, stops 4 ~ 60 hours; Regeneration gas II is the gaseous mixture of inert gas, carbon monoxide and low-carbon alkene.
In technique scheme, after step (4) completes, keeping system pressure is constant, temperature of reactor is adjusted to 250 ~ 430 DEG C, is switched to by regeneration gas II air speed to be 300 ~ 16000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis.
In technique scheme, the inert gas used in regeneration is preferably at least one in nitrogen, helium and argon gas; In step, the preferable range of the inert gas volume space velocity of (1) is 1000 ~ 8000h
-1; The preferable range of step (2) temperature of reactor is 300 ~ 500 DEG C, and the preferable range of the time of staying is 5 ~ 25h; In step (3), the volume ratio of inert gas and hydrogen is preferably inert gas: H
2=(0 ~ 10): 1, the preferable range of volume space velocity is 1000 ~ 8000h
-1, the preferable range of temperature is 245 ~ 460 DEG C, and the preferable range of pressure is 0.1 ~ 4.5MP, the preferable range 10 ~ 50h of the time of staying; The low-carbon alkene that step (4) uses preferably is selected from least one in ethene, propylene, butylene and isobutene; Inert gas in step (4) and the volume ratio of carbon monoxide and low-carbon alkene are preferably inert gas: carbon monoxide: low-carbon alkene=(0-10.0): 1.0:(0.2-2.0); In step (3), the pressure of reactor is preferably 0.6 ~ 3.5MPa; In step, in (4), the preferable range of the time of staying of regeneration gas II is 6 ~ 50h.
The catalyst used in this invention is the ferrum-based catalyst of reacted 1500 hours, and the main metal active constituent of catalyst is iron, and 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, zirconia, aluminium oxide, catalyst is the profile that the microspheroidal of spray drying forming is applicable to the distribution of particle sizes of fluid bed.
Regeneration methods of the invention is not limited only to the regeneration for ferrum-based catalyst, due to the carbon distribution same type of catalyst in F-T synthesis, therefore can be used in the regeneration of the fischer-tropsch synthetic catalyst of other systems.
Advantage of the present invention is as follows: in-situ regeneration in the fluidized-bed reactor that catalyst carries out synthetic reaction, find in reaction that activity decrease exceedes tolerable scope and can be switched to regeneration at once, reactiveness can be switched to very simply after having regenerated, simple to operate; The activity of the catalyst after regeneration can return to the level before activity decrease substantially completely, i.e. conversion ratio and low-carbon alkene selective can return to conversion ratio when reacting initial conditions and selective substantially; Regeneration in fluid bed, good thermal diffusivity, contingent overheating problem on catalyst when avoiding regeneration; Immediately can put into after catalyst regeneration in the synthesis production of GTO, be applicable to large-scale fluidized bed GTO device.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 300h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 280 DEG C, under this atmosphere and this temperature, pressure, stop 3h.
(3) temperature adjusting reactor is 230 DEG C, and pressure is 0.01MPa;
(4) air speed air inlet is switched to be 300h
-1the gaseous mixture of nitrogen and hydrogen, stop 3 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=10:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 0.2MP;
(6) activation autogenous cutting is changed to the gaseous mixture of nitrogen and carbon monoxide and ethene, the volume ratio of nitrogen and carbon monoxide and ethene is nitrogen: carbon monoxide: ethene=10:1:2, stops 4h;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 250 DEG C, and unstripped gas being switched air speed is 300h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=1.8:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[embodiment 2]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 10000h
-1helium;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 520 DEG C, under this atmosphere and this temperature, pressure, stop 30h;
(3) temperature adjusting reactor is 480 DEG C, and pressure is 5.0MPa;
(4) air speed air inlet is switched to be 10000h
-1hydrogen, stops 60 hours under this atmosphere and this temperature, pressure;
(5) keep temperature above and air speed constant, reactor pressure is risen to 10MP;
(6) activation autogenous cutting is changed to the gaseous mixture of helium and carbon monoxide and propylene, the volume ratio of helium and carbon monoxide and propylene is nitrogen: carbon monoxide: ethene=10:1:0.2, stops 60h;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 430 DEG C, and unstripped gas being switched air speed is 16000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=5:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[embodiment 3]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 1000h
-1argon gas;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 300 DEG C, under this atmosphere and this temperature, pressure, stop 5h.
(3) temperature adjusting reactor is 245 DEG C, and pressure is 0.1MPa;
(4) air speed air inlet is switched to be 1000h
-1the gaseous mixture of argon gas and hydrogen, stop 10 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of argon gas and hydrogen is argon gas: H
2=1:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 0.6MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of argon gas and carbon monoxide and n-butene, the volume ratio of argon gas and carbon monoxide and n-butene is argon gas: carbon monoxide: n-butene=10:1:1, stops 6h;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 260 DEG C, and unstripped gas being switched air speed is 500h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=2.0:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[embodiment 4]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 8000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 500 DEG C, under this atmosphere and this temperature, pressure, stop 25h.
(3) temperature adjusting reactor is 460 DEG C, and pressure is 4.5MPa;
(4) air speed air inlet is switched to be 8000h
-1the gaseous mixture of nitrogen and hydrogen, stop 50 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=1:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 7.5MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of carbon monoxide and isobutene, the volume ratio of carbon monoxide and isobutene is carbon monoxide: isobutene=1:1, stops 50h;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 420 DEG C, and unstripped gas being switched air speed is 15000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=4.8:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[embodiment 5]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 6000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 480 DEG C, under this atmosphere and this temperature, pressure, stop 15h.
(3) temperature adjusting reactor is 400 DEG C, and pressure is 2.5MPa;
(4) air speed air inlet is switched to be 6000h
-1the gaseous mixture of nitrogen and hydrogen, stop 36 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=1:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 3.5MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of nitrogen and carbon monoxide and low-carbon alkene, the volume ratio of nitrogen and carbon monoxide and 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 mix;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 350 DEG C, and unstripped gas being switched air speed is 8000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=2:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[embodiment 6]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 6000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 450 DEG C, under this atmosphere and this temperature, pressure, stop 15h.
(3) temperature adjusting reactor is 400 DEG C, and pressure is 2.5MPa;
(4) air speed air inlet is switched to be 6000h
-1the gaseous mixture of nitrogen and hydrogen, stop 36 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=5:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 3.5MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of nitrogen and carbon monoxide and low-carbon alkene, the volume ratio of nitrogen and carbon monoxide and 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 mix;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 350 DEG C, and unstripped gas being switched air speed is 8000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=3:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[embodiment 7]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 6000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 480 DEG C, under this atmosphere and this temperature, pressure, stop 15h.
(3) temperature adjusting reactor is 400 DEG C, and pressure is 2.5MPa;
(4) air speed air inlet is switched to be 6000h
-1the gaseous mixture of nitrogen and hydrogen, stop 36 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=1:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 3.5MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of nitrogen and carbon monoxide and low-carbon alkene, the volume ratio of nitrogen and carbon monoxide and 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 mix;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 350 DEG C, and unstripped gas being switched air speed is 8000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=2.5:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[comparative example 1]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 6000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 600 DEG C, under this atmosphere and this temperature, pressure, stop 15h.
(3) temperature adjusting reactor is 500 DEG C, and pressure is 2.5MPa;
(4) air speed air inlet is switched to be 6000h
-1the gaseous mixture of nitrogen and hydrogen, stop 36 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=1:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 3.5MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of nitrogen and carbon monoxide and low-carbon alkene, the volume ratio of nitrogen and carbon monoxide and 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 mix;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 350 DEG C, and unstripped gas being switched air speed is 8000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=2:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[comparative example 2]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 6000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 200 DEG C, under this atmosphere and this temperature, pressure, stop 15h.
(3) temperature adjusting reactor is 220 DEG C, and pressure is 2.5MPa;
(4) air speed air inlet is switched to be 6000h
-1the gaseous mixture of nitrogen and hydrogen, stop 36 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=1:1;
(5) keep temperature above and air speed constant, reactor pressure is risen to 3.5MPa;
(6) activation autogenous cutting is changed to the gaseous mixture of nitrogen and carbon monoxide and low-carbon alkene, the volume ratio of nitrogen and carbon monoxide and 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 mix;
(7) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 350 DEG C, and unstripped gas being switched air speed is 8000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=2:1.
The subordinate list that the performance of the catalyst after regeneration sees below.
[comparative example 3]
(1) by 1.5 inches, the original ferrum-based catalyst of 100g is housed, and (this catalyst is the preparation of co-precipitation spraying dry, and forming by atomic ratio measuring is 100Fe/80Mn/5K/80SiO
2) and reacted 1500 hours, the air inlet of the active fluidized-bed reactor declined to some extent switches to air speed 6000h
-1nitrogen;
(2) adjust the pressure of reactor to normal pressure, adjustment temperature of reactor is 480 DEG C, under this atmosphere and this temperature, pressure, stop 15h.
(3) temperature adjusting reactor is 400 DEG C, and pressure is 2.5MPa;
(4) air speed air inlet is switched to be 6000h
-1the gaseous mixture of nitrogen and hydrogen, stop 36 hours under this atmosphere and this temperature, pressure, wherein the volume ratio of nitrogen and hydrogen is N
2: H
2=1:1;
(5) activate complete, keeping system pressure is constant, temperature of reactor is adjusted to 350 DEG C, and unstripped gas being switched air speed is 8000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis, wherein synthesis gas is the gaseous mixture of hydrogen and carbon monoxide, and its volume ratio is H
2: CO=2:1.
The subordinate list 1 that the performance of the catalyst after regeneration sees below.
Table 1
(appreciation condition is the evaluation result of what # was corresponding is fresh catalyst: 350 DEG C, 1.5MPa, air speed 8000h
-1, H
2/ CO (volume)=2/1).
Claims (10)
1. fluid bed syngas directly prepares a renovation process for light olefins catalyst, in turn includes the following steps:
(1) after catalysqt deactivation, stop reaction gas, air inlet switched to volume space velocity to be 300 ~ 10000h
-1substitution gas, substitution gas is inert gas;
(2), after completing steps (1), regulate the pressure of reactor to normal pressure, regulate temperature of reactor to be 280 ~ 520 DEG C, under this atmosphere and this temperature, pressure, stop 3 ~ 30h;
(3) after completing steps (2), the pressure of reactor is raised to 0.01 ~ 5.0MPa, substitution gas is switched to regeneration gas I, the volume space velocity regulating regeneration gas I is 300 ~ 10000h
-1, then reactor is heated to 230 ~ 480 DEG C, stops 3 ~ 60 hours under this atmosphere and this temperature; Regeneration gas I is the gaseous mixture of inert gas and hydrogen;
(4) keep volume space velocity, the temperature of step (3) and pressure is adjusted to 0.6 ~ 7.5MPa, regeneration gas I being switched to regeneration gas II, stops 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, after it is characterized in that step (4) completes, keeping system pressure is constant, temperature of reactor is adjusted to 250 ~ 430 DEG C, is switched to by regeneration gas II air speed to be 300 ~ 16000h
-1synthesis gas start to carry out Fischer-Tropsch synthesis.
3. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that in regenerating, the inert gas that uses is nitrogen, at least one in helium and argon gas.
4. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that the volume space velocity of the inert gas of (1) in step is 1000 ~ 8000h
-1.
5. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that step (2) temperature of reactor is 300 ~ 500 DEG C, the time of staying 5 ~ 25h.
6. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that the volume ratio of inert gas and hydrogen in step (3) is inert gas: H
2=(0 ~ 10): 1, volume space velocity is 1000 ~ 8000h
-1, temperature is 245 ~ 460 DEG C, and pressure is 0.1 ~ 4.5MP, stops 10 ~ 50h.
7. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that the low-carbon alkene that step (4) uses is be selected from least one in ethene, propylene, butylene and isobutene.
8. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that the volume ratio of inert gas in step (4) and carbon monoxide and low-carbon alkene is inert gas: carbon monoxide: low-carbon alkene=(0-10.0): 1.0:(0.2-2.0).
9. fluid bed syngas according to claim 1 directly prepares the renovation process of light olefins catalyst, it is characterized in that the time of staying of regeneration gas II in (4) in step is 6 ~ 50h.
10. fluid bed syngas according to claim 6 directly prepares the renovation process of light olefins catalyst, it is characterized in that the pressure of reactor in step (4) is 0.6 ~ 3.5MPa.
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| CN107684932A (en) * | 2017-10-11 | 2018-02-13 | 武汉凯迪工程技术研究总院有限公司 | Slurry bed system Co based Fischer-Tropsch synthesis catalyst regenerated offline method and its device |
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