CN102952563A - Method for making Fischer-Tropsch synthetic reaction stable - Google Patents
Method for making Fischer-Tropsch synthetic reaction stable Download PDFInfo
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Abstract
A method for making a Fischer-Tropsch synthetic reaction stable. A catalyst for Fischer-Tropsch synthesis is activated and enters an initial phase of a Fischer-Tropsch synthetic reaction; at the reaction initial phase, an inert medium is introduced into synthesis gas so as to allow a mixture flow containing hydrogen, carbon monoxide and the inert medium to contact with the Fischer-Tropsch synthesis catalyst bed layer for reaction; with the activity of the Fischer-Tropsch synthesis catalyst being in a steady state, the amount of the inert medium in the reactant flow is decreased gradually till the Fischer-Tropsch synthetic reaction is in a steady-state phase, wherein at the reaction initial phase, the reaction condition is the same as the reaction condition at the steady-state phase. With the method, the risk of overtemperature at the reaction initial phase is reduced; hot spot areas are reduced; the Fischer-Tropsch synthetic reaction can go into a steady-state phase stably; and guarantee for the long-period running of Fischer-Tropsch synthesis equipment is provided.
Description
Technical field
The present invention relates to a kind of Fischer-Tropsch synthesis method, more particularly, is a kind of method that Fischer-Tropsch synthesis is steadily carried out.
Background technology
Go out synthetic gas take the resource of the carbon containing such as Sweet natural gas, pitch, coal, biomass and hydrogen as raw material production, again take synthetic gas as raw material by the synthetic liquefied hydrocarbon of producing of Fischer-Tropsch, be the technology of a good petroleum replacing.
By Fischer-Tropsch synthesis, can change the synthetic gas of hydrogen and carbon monoxide composition into liquid hydrocarbon or solid hydrocarbons.Because Fischer-Tropsch synthesis is strong heat release and temperature sensitive reaction, in order to guarantee the smooth running of Fischer-Tropsch synthesis, the control of the operational condition such as temperature needs careful operation in the reaction process.Usually, the activated rear initial activity of fischer-tropsch synthetic catalyst is higher, the Fischer-Tropsch synthesis initial stage easily cause the catalyzer local reaction violent, have more hot spot region, have the risk that overtemperature occurs.In the prior art, Fischer-Tropsch synthesis is transitioned into steady-state process by the initial activity higher stage normally to carry out under the lower temperature and pressure by contrast with the homeostatic reaction temperature of Fischer-Tropsch synthesis and homeostatic reaction pressure, progressively improve afterwards temperature of reaction and reaction pressure, with tide over the higher initial stage of fischer-tropsch synthetic catalyst activity, reach slow down the catalyzer local reaction violent, reduce focus, prevent the purpose of overtemperature.
Disclose among the US2904576 and used the fluidization iron catalyst by the technique of the synthetic hydrocarbon of synthetic gas.By under relatively low pressure (namely being no more than 5 normal atmosphere) and lower air speed, making catalyzer contact to regulate the initial activity of catalyzer with synthetic gas.Along with the reduction of catalyst activity, pressure and air speed increase gradually, realize desired pressure and the air speed of hydrocarbon synthesis reaction until reach.
Disclose among the US2602810 a kind of under steady state conditions by with synthetic gas with the recycle stream combination of being rich in hydrogen and regulate H
2/ CO mol ratio reaches 15 Fischer-Tropsch synthesis process at least.Pressurize and circulate by hydrogen, at first regulate temperature and reach the required temperature of Fischer-Tropsch synthesis, then under low synthetic gas flow and high hydrogen flowing quantity, make Fischer-Tropsch synthesis be transitioned into steady-state process by the starting stage gradually.Along with catalyst activity reduces gradually, progressively increase the flow of synthetic gas, hydrogen flowing quantity decreases simultaneously.
A kind of technique of Fischer-Tropsch synthesis has been described in WO03068715A1.After catalyzer is activated, initial flow and H when the synthetic gas flow is lower than the steady stage
2Under the condition of the mol ratio when/CO mol ratio is higher than the steady stage synthetic gas is introduced reactor, along with the gradually reduction of catalyst activity, progressively the synthetic gas flow is adjusted to the value of steady stage and with the H in the synthetic gas
2/ CO mol ratio is down to the value of steady stage.
Above-mentioned prior art has adopted at the pressure that is lower than steady-state process and air speed and the H that is higher than steady-state process
2Under the conditions such as/CO mol ratio, make Fischer-Tropsch synthesis be transitioned into gradually the method for steady-state process by the reaction starting stage, above-mentioned prior art has comprised the adjustment of more operational condition, certainly will bring operational condition than great fluctuation process, be unfavorable for steadily carrying out of Fischer-Tropsch synthesis.
Summary of the invention
The purpose of this invention is to provide a kind of method that makes Fischer-Tropsch synthesis steadily be entered steady-state process by the reaction starting stage, too much with operational condition adjustment in the solution prior art, easily cause the larger technical problem of operational condition fluctuation.
Method provided by the invention is: enter the Fischer-Tropsch synthesis starting stage after fischer-tropsch synthetic catalyst is activated, in the reaction starting stage, in synthetic gas, introduce inert media, the mixture flow of hydrogen, carbon monoxide and inert media is contacted with the fischer-tropsch synthetic catalyst bed reacts, along with the fischer-tropsch synthetic catalyst activity develops towards stable state, progressively reduce the amount of inert media in the reactant flow, until Fischer-Tropsch synthesis enters steady-state process, wherein, in the reaction starting stage, its reaction conditions is identical with the reaction conditions of steady-state process.
Preferably, in the reaction starting stage, temperature of reaction, total reactor pressure, flow of reaction mixture gas hourly space velocity, circulation gas flow are identical with temperature of reaction, total reactor pressure, flow of reaction mixture gas hourly space velocity, the circulation gas flow of steady-state process.In the reaction starting stage, the mol ratio of hydrogen and carbon monoxide is constant in the mixture flow of reactor inlet, and is identical with the mol ratio of hydrogen and carbon monoxide in the steady-state process reactant flow.The mol ratio of hydrogen and carbon monoxide is preferably regulated by replenishing new hydrogen or emission.When the mol ratio of hydrogen and carbon monoxide reduces, reach requirement by replenishing new hydrogen.
Described inert media is selected from one or more in methane, ethane, propane, carbonic acid gas, the nitrogen.Preferred described inert media is nitrogen.
Along with the interpolation of one or more inert medias, synthetic gas pressure only has dividing potential drop in the present invention reacts the flow of reaction mixture of starting stage.The catalyzer local reaction was violent when this had just been avoided using whole synthetic gas, had reduced the hot spot region, had reduced the risk that is transitioned into the steady-state process overtemperature by the reaction starting stage.In the reaction starting stage, the inert media volume accounts for the 10%-90% of mixture flow cumulative volume in the mixture flow, preferred 40%-80%.
In the method for the present invention, reaction starting stage (being that catalyst activation finishes to reach period before the stable state to catalyst activity), keep the total reactor pressure substantially constant, identical with the steady-state process total reactor pressure or basic identical; The temperature of reaction substantially constant is identical with the steady-state process temperature of reaction or basic identical; The gas hourly space velocity substantially constant of flow of reaction mixture, identical or basic identical with the gas hourly space velocity of steady-state process reactant flow, and the mol ratio of hydrogen and carbon monoxide is constant in the maintenance flow of reaction mixture, and is identical or basic identical with the mol ratio of hydrogen and carbon monoxide in the steady-state process reactant flow; Circulation gas flow substantially constant is identical or basic identical with the circulation gas flow of steady-state process.
In the method for the invention, along with Fischer-Tropsch synthesis develops towards stable state, progressively improve the synthetic gas dividing potential drop.This is to realize by the flow of inert media in the flow that progressively increases synthetic gas in the flow of reaction mixture and the reduction flow of reaction mixture, and the amount of inert media is reduced to 0 the most at last.All stage keeps the flow substantially constant of flow of reaction mixture.
Synthetic gas dividing potential drop of the present invention is defined as: the flow of synthetic gas dividing potential drop=synthetic gas/(flow of the flow+inert media of synthetic gas) * 100%, wherein flow is all with volumetric flow meter.
Among the present invention, improve the dividing potential drop of synthetic gas by 2～50 stages, preferred 5～30 stages are improved the synthetic gas dividing potential drop.Each amplitude that improves the synthetic gas dividing potential drop is not more than 20% of total reactor pressure, preferably is not more than 5%.Twice raising synthetic gas dividing potential drop timed interval is no less than 5h.
Term of the present invention " stable state " is the known terms of this area.Even for steady-state process, the less variation in all chemical reactions also is common, but steady-state process is well known in the art, and wherein expected results is relatively predictable in time." stable state " relates to the whole of synthesizer design and condition separately, comprises pressure and temperature etc.These conditions are primary conditions of setting for this device, and its selection is known to those skilled in the art.
" stable state " is used for pressure and temperature and catalyst activity similarly among the present invention.In conversion reactor, pressure is usually directed to reactor outlet pressure, and temperature is temperature of reaction.Along with catalyzer was brought into use from the initial stage, this higher activity reduces towards the stable state development naturally with catalyst activity.Therefore, this initial stage catalyst activity can be in the 101-150% scope of steady state catalytic agent activity, preferably in the scope of 105-120%.
The reaction conditions of Fischer-Tropsch synthesis steady-state process is: reaction pressure 0.5-5.0MPa, temperature of reaction 150-300 ℃, gas hourly space velocity 500-5000h
-1, H
2/ CO raw materials components mole ratio 1: 1-3: 1, recycle ratio is 1-20.The reaction conditions of preferred Fischer-Tropsch synthesis steady-state process is: reaction pressure 1.5-3.5MPa, temperature of reaction 180-250 ℃, gas hourly space velocity 500-3000h
-1, H
2/ CO raw materials components mole ratio 1.8: 1-2.5: 1, recycle ratio is 3-15.The flow of the flow of described recycle ratio=circulation gas/fresh feed gas.
Described reactor is conventional fixed-bed reactor, paste state bed reactor and the fluidized-bed reactor that is used for Fischer-Tropsch synthesis, preferred fixed-bed reactor.
Described fischer-tropsch synthetic catalyst is Co base fischer-tropsch synthetic catalyst.In the Fischer-Tropsch building-up process, owing to using cobalt-base catalyst, can have low water-gas shift activity and high heavy hydrocarbon selectivity, thereby more and more be applied in the Fischer-Tropsch synthesis, cobalt-base catalyst only has the processing through activated media to become simple substance cobalt and just has the Fischer-Tropsch synthesis activity, and the catalyzer initial activity after activated is higher, usually Fischer-Tropsch synthesis before reaching stable state, the steady-state process of being allowed for access after need spending the active higher starting stage.Because Fischer-Tropsch synthesis is strong heat release and temperature sensitive reaction, the fixed-bed reactor heat transfer property is poor, in fixed bed Fischer-Tropsch synthesis process, after catalyzer is activated, because the starting stage activity is higher, if misoperation, easily cause the catalyzer local reaction violent even cause and the risk of overtemperature cause catalyst activity reduction even structure to be destroyed, and then device is forced to shut-down, this will cause larger financial loss, and this is disadvantageous economically.
Co of the present invention base fischer-tropsch synthetic catalyst is to contain the oxide compound of Co and carrier or composite oxides etc., and carrier component is one or more that are selected from aluminium, silicon, zirconium, titanium, the carbon.Take total catalyst weight as benchmark, in oxide compound, the content of Co is the 5-50 % by weight, and the content of carrier is the 50-95 % by weight.Preferably, the content of Co is the 5-25 % by weight, and the content of carrier is the 75-95 % by weight.
A kind of preferred embodiment in, described Co based Fischer-Tropsch synthesis catalyst is by the method preparation that comprises with the solution impregnating carrier that contains the cobalt metal component.The described solution that contains the cobalt metal component, can be the aqueous solution by the compound that contains the cobalt metal component and water preparation, can be by the organic solution that contains the preparation of cobalt metal component compound and organic solvent, also can be the solution by the mixed solvent preparation that contains cobalt metal component and water and organic solvent.Wherein, the compound of described metallic components preferably contains the salt of cobalt metal component, for example, is selected from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, cobaltous dihydroxycarbonate, one or more in Cobaltous diacetate, the citric acid cobalt.Described organic solvent is water soluble or the organism that is partially soluble in water, for example, is selected from one or more in alcohol, aldehyde, acid, the amine.
Described carrier component can be the carrier that is suitable for arbitrarily preparing fischer-tropsch synthetic catalyst, and they can be commercially available commodity, also can adopt any one existing method preparation.Preferred carrier is selected from one or more in aluminum oxide, silicon oxide one aluminum oxide, pure aluminium silicate, silicon oxide, zirconium white, titanium oxide, the gac.
The method of described dipping is not particularly limited, and is preferably the spray dipping method.After dipping was finished, the inventive method also comprised the step of drying, roasting or not roasting.The method of the method for described drying and condition, roasting and condition are this area customary way and condition, such as bake drying, vacuum drying method.Described dipping can be once also can be repeatedly.When dipping for repeatedly the time, each dipping carries out drying, roasting or not roasting afterwards.For example, described being immersed in drum-type (or converter type) spray equipment carried out.Comprise the cylinder (or converter type) that at room temperature carrier is placed spray equipment, start cylinder (or converter type) device, carrier rolls with cylinder (or converter type), and the solution that will contain the cobalt metal component under the carrier rolling condition sprays on carrier through atomizing nozzle.Spray complete after, cylinder (or converter type) device continues rolling 10-1000 minute.Afterwards, descended preferred 100-250 ℃ dry 1-50 hour in 50-350 ℃.At 150-800 ℃ of lower roasting 1-50 hour, preferred 300-600 ℃, roasting time was 1-12 hour subsequently.
Described Co based Fischer-Tropsch synthesis catalyst also contains auxiliary agent, for being selected from one or more in Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, RE, Re, Hf, Ce, Mn, Fe, V, Pt, Pd, Rh, the Ir element, and take total catalyst weight as benchmark, in oxide compound, the content of auxiliary agent is the 0.1-15 % by weight.Preferably, auxiliary agent is one or more that are selected from Re, W, Ce, Ru, the Pd element, and take total catalyst weight as benchmark, in oxide compound, the content of auxiliary agent is preferably the 0.1-10 % by weight.
When described Co based Fischer-Tropsch synthesis catalyst contained above-mentioned adjuvant component, the preparation method of described catalyzer also was included in the step of introducing described adjuvant component in the catalyzer.They can be to introduce before or after introducing the cobalt metal component, also can be to introduce simultaneously with the cobalt metal component.When adjuvant component was introduced separately into, the present invention was for the not restriction of introducing method of described auxiliary agent.For example, the described compound that contains adjuvant component is mixed with the aqueous solution, adopts afterwards the method dipping of conventional dipping.When described auxiliary agent and described cobalt metal component were introduced simultaneously, the method for described introducing was pickling process, namely with the compound that contains adjuvant component and the compound preparation mixing solutions that contains the cobalt metal component, adopted afterwards the method for dipping to introduce.Described dipping can be once to finish, and also can be repeatedly.When dipping for repeatedly the time, each dipping carries out drying, roasting or not roasting afterwards.
The carrier of described Co based Fischer-Tropsch synthesis catalyst is looked different the forming composition that require can be made into various easy handlings, such as microballoon, sphere, tablet or bar shaped etc.Moulding according to a conventional method, such as the preparation of the method for extruded moulding.When adopting the method moulding of extrusion moulding, can add an amount of extrusion aid and/or tackiness agent, then extrusion moulding.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, are not repeated herein.
According to method provided by the invention, described Co based Fischer-Tropsch synthesis catalyst need to be under hydrogen atmosphere before being used for Fischer-Tropsch synthesis, the cobalt of oxidation state is activated, activation condition is: activation temperature is 150 ℃ to 900 ℃, be preferably 200 ℃ to 600 ℃, soak time is 1-100 hour, be preferably 1-48 hour, described activation can be carried out in pure hydrogen, also can in hydrogen and inert media gas mixture, carry out, as carrying out in the gas mixture of hydrogen and nitrogen, hydrogen partial pressure power is 0.1-5MPa, is preferably 0.5-2MPa.
In the method for the present invention, after the fischer-tropsch synthetic catalyst activation finished, preferred inert media was introduced reactive system, replaced, until the activated media massfraction in the system＜1% is preferably 0%, and then introduced synthetic gas, entered the reaction starting stage.Wherein inert media is one or more that are selected from methane, ethane, propane, carbonic acid gas, the nitrogen, is preferably nitrogen.
Advantage of the present invention:
1, the present invention is by the starting stage at Fischer-Tropsch synthesis, under the condition identical with steady-state process temperature of reaction, total reactor pressure and flow of reaction mixture gas hourly space velocity, circulation gas flow, in kept certain synthetic gas by hydrogen and carbon monoxide proportion of composing, introduce the method for inert media, by reducing the synthetic gas dividing potential drop, the Fischer-Tropsch synthesis starting stage can be reduced effectively, the local vigorous reaction that occurs of catalyzer when using whole synthetic gas, thereby reduced focus, reduce the bed temperature difference, and improved C
5+The selectivity of heavy hydrocarbon has reduced the Fischer-Tropsch synthesis process and the starting stage has been transitioned into the risk of steady-state process overtemperature by reaction, thereby promoted the smooth running of reaction process, for the long-term operation of Fischer-Tropsch synthesizer provides guarantee.
2, the present invention passes through to use lower initial synthetic gas dividing potential drop in reactor, and does not need the operation by reducing temperature of reaction and flow of reaction mixture gas hourly space velocity, circulation gas flow and adopting higher hydrogen gas and carbon monoxide mol ratio.Therefore, relatively high temperature of reaction and gas hourly space velocity are to the condensation of water in preventing from reacting and in time take water out of reactor and play very good effect, are conducive to prevent catalyzer generation hydrothermal deactivation.
3, the present invention is in temperature of reaction and total reactor pressure, flow of reaction mixture gas hourly space velocity and circulation gas flow and hydrogen and the constant lower operation of carbon monoxide mol ratio near stable state, after reaching stable state, do not need to adjust again the relating operation condition of reactive system, thereby can reduce the risk that causes overtemperature owing to the fluctuation of operational condition.Method provided by the invention has further guaranteed the smooth running of Fischer-Tropsch synthesis process.
Embodiment
The below is described in more detail the present invention with reference to embodiment, but this is not limitation of the present invention.
CO transformation efficiency, CH
4Selectivity, C
5+The selectivity definition is as follows:
The mole number of CO * 100% in mole number/material mixed gas of CO transformation efficiency=reacted CO
CH
4Selectivity=generation CH
4The mole number * 100% of mole number/ reacted CO
C
5+Selectivity=(mole number that has reacted CO deducts CH in the gaseous product
4And C
2-C
4The mole number of middle C)/ react the mole number of CO * 100%
Embodiment 1
Take by weighing 500g γ-Al
2O
3Carrier (Chang Ling catalyst plant product, granularity 16-26 order) places retort furnace with this carrier, in 600 ℃ of roastings 3 hours.
Take by weighing above-mentioned γ-Al
2O
3The carrier 30 as one kind gram is got the solution that 5.5 gram Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs are dissolved into 8.1 milliliters, adopts spray method to spray on described carrier this solution under stirring, then in baking oven, dried by the fire 4 hours under 120 ℃, the 500 ℃ of roastings in retort furnace that continue 4 hours repeat operation secondary, obtain fischer-tropsch synthetic catalyst A.
Activation condition is carried out in fischer-tropsch synthetic catalyst A activation under pure hydrogen atmosphere: 400 ℃ of temperature, pressure 0.5MPa, gas hourly space velocity 500h
-1, 24 hours time.
Catalyzer when temperature is reduced to 212 ℃, is introduced first N behind overactivation
2Replace, until H in the system
2Massfraction＜1% is introduced the mixture flow of synthetic gas and nitrogen afterwards, and the volume fraction 40% of synthetic gas, nitrogen volume fraction are 60%, and starts recycle compressor after pressure risen to 2.5MPa, sets up gas circulation, and circulating flow rate is 94L/h.Then progressively reduce N
2Shared volume fraction in mixture flow, N
2Volume fraction minimizing amplitude is 3%/time (in the flow of reaction mixture cumulative volume), minute 20 operations, and the timed interval of twice operation is no less than 5h, until the nitrogen volume fraction reduces to 0.
Other operational conditions of Fischer-Tropsch synthesis starting stage and steady-state process are: 212 ℃ of temperature of reaction, reaction total pressure 2.5MPa enters the H in the unstripped gas of reactor
2/ CO raw materials components mole ratio is 2, and the gas hourly space velocity of fresh feed gas is 500h
-1, (comprising: the lower carbon number hydrocarbons of unstripped gas and generation) loop back reactor and further react, recycle ratio is 13.5 to the unreacted gas that flows out from reactor.Reaction result is as shown in table 1.
Comparative Examples 1
Repeat above-described embodiment 1.After difference is that catalyzer is activated, when temperature is reduced to 50 ℃ and pressure and is 0.5MPa, introduces synthetic gas, and start recycle compressor, set up gas circulation, circulating flow rate is 94L/h.Then progressively improve temperature of reaction to 212 ℃ and improve reaction pressure to 2.5MPa.Rate of pressure rise is 0.1MPa/5min, and 170 ℃ of former temperature rise rates are 2 ℃/h, and 170 ℃ of later temperature rise rates are 0.5 ℃/h.Other operational conditions are the H that enters in the unstripped gas of reactor
2/ CO raw materials components mole ratio is 2, and the gas hourly space velocity of fresh feed gas is 500h
-1(comprising: the lower carbon number hydrocarbons of unstripped gas and generation) loop back reactor and further react, recycle ratio is 13.5 to the unreacted gas that flows out from reactor.The result is as shown in table 1.
From table 1 reaction result as can be known, adopt method of the present invention, reduced the bed temperature difference, the bed temperature difference of embodiment 1 only is 4 ℃, and the bed temperature difference of Comparative Examples 1 is 8.5 ℃, thereby has reduced focus; Improved C
5 +Selectivity, the C of embodiment 1
5 +Selectivity be 86.03%, than the C of Comparative Examples 1
5 +The selectivity height nearly 1.5 percentage points.Therefore, method provided by the invention has promoted steadily carrying out of Fischer-Tropsch synthesis, has reduced the risk of overtemperature.
Table 1
| Test event | Embodiment 1 | Comparative Examples 1 |
| CO transformation efficiency/% | 89.91 | 88.45 |
| CH 4Selectivity/% | 8.82 | 9.75 |
| C 5 +Selectivity/% | 86.03 | 84.59 |
| The bed temperature difference/℃ | 4 | 8.5 |
| The overtemperature situation | Without overtemperature | Without overtemperature |
Embodiment 2
Take by weighing 500g γ-Al
2O
3Carrier (Chang Ling catalyst plant product, granularity 16-26 order) places retort furnace with this carrier, in 600 ℃ of roastings 3 hours.
Take by weighing above-mentioned γ-Al
2O
3The carrier 30 as one kind gram is got the solution that 5.5 gram Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs are dissolved into 8.1 milliliters, adopts spray method to spray on described carrier this solution under stirring, then in baking oven, dried by the fire 4 hours under 120 ℃, the 500 ℃ of roastings in retort furnace that continue 4 hours repeat operation three times, obtain fischer-tropsch synthetic catalyst B.
Activation condition is carried out in fischer-tropsch synthetic catalyst B activation under pure hydrogen atmosphere: 400 ℃ of temperature, pressure 0.5MPa, gas hourly space velocity 500h
-1, 24 hours time.
Fischer-tropsch synthetic catalyst B when temperature is reduced to 218 ℃, introduces first N behind overactivation
2Replace, until H in the system
2Massfraction＜1% is introduced the mixture flow of synthetic gas and nitrogen afterwards, and the volume fraction 20% of synthetic gas, nitrogen volume fraction are 80%, and starts compressor after pressure risen to 2.5MPa, sets up gas circulation, and circulating flow rate is 94L/h.Then progressively reduce N
2Shared volume fraction in mixture flow, N
2Volume fraction minimizing amplitude is 5%/time (in the flow of reaction mixture cumulative volume), minute 16 operations, and the timed interval of twice operation is no less than 5h, until the nitrogen volume fraction reduces to 0.
Other operational conditions of Fischer-Tropsch synthesis starting stage and steady-state process are: 218 ℃ of temperature of reaction, reaction total pressure 2.5MPa; Enter the H in the unstripped gas of reactor
2/ CO raw materials components mole ratio is 2, and the gas hourly space velocity of fresh feed gas is 750h
-1(comprising: the lower carbon number hydrocarbons of unstripped gas and generation) loop back reactor and further react, recycle ratio is 13.5 to the unreacted gas that flows out from reactor.The result is as shown in table 2.
Comparative Examples 2
Repeat above-described embodiment 2.After difference is that fischer-tropsch synthetic catalyst B is activated, when temperature is reduced to 50 ℃ and pressure and is 0.5MPa, introduces synthetic gas, and start compressor, set up gas circulation, circulating flow rate is 94L/h.Then progressively temperature of reaction is increased to 218 ℃ and reaction pressure and is increased to 2.5MPa.Rate of pressure rise is 0.1MPa/5min, and 170 ℃ of former temperature rise rates are 2 ℃/h, and 170 ℃ of later temperature rise rates are 0.5 ℃/h.Other operational conditions are the H that enters in the unstripped gas of reactor
2/ CO raw materials components mole ratio is 2, and the gas hourly space velocity of fresh feed gas is 750h
-1(comprising: the lower carbon number hydrocarbons of unstripped gas and generation) loop back reactor and further react, recycle ratio is 13.5 to the unreacted gas that flows out from reactor.The result is as shown in table 2.
From table 2 reaction result as can be known, overtemperature occurs in Comparative Examples 2 when temperature of reaction rises to 215 ℃, thereby has stopped experiment.Therefore, adopt method of the present invention, can promote the smooth running of Fischer-Tropsch synthesis, reduced the risk of overtemperature, be conducive to the running period of extension fixture.
Table 2
Claims (19)
1. method that Fischer-Tropsch synthesis is steadily carried out, enter the Fischer-Tropsch synthesis starting stage after fischer-tropsch synthetic catalyst is activated, it is characterized in that, in the reaction starting stage, in synthetic gas, introduce inert media, make hydrogen, the mixture flow of carbon monoxide and inert media contacts with the fischer-tropsch synthetic catalyst bed reacts, along with the fischer-tropsch synthetic catalyst activity develops towards stable state, progressively reduce the amount of inert media in the reactant flow, until Fischer-Tropsch synthesis enters steady-state process, wherein, in the reaction starting stage, its reaction conditions is identical with the reaction conditions of steady-state process.
2. in accordance with the method for claim 1, it is characterized in that, in the reaction starting stage, temperature of reaction, total reactor pressure, flow of reaction mixture gas hourly space velocity, circulation gas flow are identical with temperature of reaction, total reactor pressure, flow of reaction mixture gas hourly space velocity, the circulation gas flow of steady-state process.
3. in accordance with the method for claim 1, it is characterized in that, in the reaction starting stage, the mol ratio of hydrogen and carbon monoxide is constant in the mixture flow of reactor inlet, and is identical with the mol ratio of hydrogen and carbon monoxide in the steady-state process reactant flow.
4. in accordance with the method for claim 1, it is characterized in that, described inert media is selected from one or more in methane, ethane, propane, carbonic acid gas, the nitrogen.
5. in accordance with the method for claim 4, it is characterized in that, described inert media is nitrogen.
6. in accordance with the method for claim 1, it is characterized in that, in the reaction starting stage, the inert media volume accounts for the 10%-90% of mixture flow cumulative volume in the mixture flow.
7. in accordance with the method for claim 1, it is characterized in that, in the reaction starting stage, the inert media volume accounts for the 40%-80% of mixture flow cumulative volume in the mixture flow.
8. in accordance with the method for claim 1, it is characterized in that, in the reaction starting stage, improve the dividing potential drop of synthetic gas by 2～50 stages, the amplitude that at every turn improves the synthetic gas dividing potential drop is not more than 20% of total reactor pressure.Twice raising synthetic gas dividing potential drop timed interval is no less than 5h.
9. in accordance with the method for claim 1, it is characterized in that, in the reaction starting stage, improve the dividing potential drop of synthetic gas by 5～30 stages, the amplitude that at every turn improves the synthetic gas dividing potential drop is not more than 5% of total reactor pressure.
10. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of Fischer-Tropsch synthesis steady-state process is: reaction pressure 0.5-5.0MPa, temperature of reaction 150-300 ℃, gas hourly space velocity 500-5000h
-1, H
2/ CO raw materials components mole ratio 1: 1-3: 1, recycle ratio is 1-20.
11. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of Fischer-Tropsch synthesis steady-state process is: reaction pressure 1.5-3.5MPa, temperature of reaction 180-250 ℃, gas hourly space velocity 500-3000h
-1, H
2/ CO raw materials components mole ratio 1.8: 1-2.5: 1, recycle ratio is 3-15.
12. in accordance with the method for claim 1, it is characterized in that, described fischer-tropsch synthetic catalyst is Co base fischer-tropsch synthetic catalyst.
13. in accordance with the method for claim 12, it is characterized in that, Co base fischer-tropsch synthetic catalyst is oxide compound or the composite oxides that contain Co and carrier, and carrier component is one or more that are selected from aluminium, silicon, zirconium, titanium, the carbon; Take total catalyst weight as benchmark, in oxide compound, the content of Co is the 5-50 % by weight, and the content of carrier is the 50-95 % by weight.
14. in accordance with the method for claim 13, it is characterized in that, Co base fischer-tropsch synthetic catalyst, take total catalyst weight as benchmark, in oxide compound, the content of Co is the 5-25 % by weight, the content of carrier is the 75-95 % by weight.
15. in accordance with the method for claim 12, it is characterized in that, also contain auxiliary agent in the described Co base fischer-tropsch synthetic catalyst, auxiliary agent is one or more that are selected from Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, RE, Re, Hf, Ce, Mn, Fe, V, Pt, Pd, Rh, the Ir element; Take total catalyst weight as benchmark, in oxide compound, the content of auxiliary agent is the 0.1-15 % by weight.
16. in accordance with the method for claim 15, it is characterized in that, auxiliary agent is one or more that are selected from Re, W, Ce, Ru, the Pd element, and take total catalyst weight as benchmark, in oxide compound, the content of auxiliary agent is preferably the 0.1-10 % by weight.
17. in accordance with the method for claim 1, it is characterized in that, described fischer-tropsch synthetic catalyst is in the situation that have hydrogen to exist to activate, and its priming reaction condition is: 150 ℃-900 ℃ of activation temperatures, soak time 1-100 hour, hydrogen partial pressure power was 0.1-5MPa.
18. in accordance with the method for claim 17, it is characterized in that, the priming reaction condition of described fischer-tropsch synthetic catalyst is: 200 ℃-600 ℃ of activation temperatures, soak time 1-48 hour, hydrogen partial pressure power 0.5-2MPa.
19. in accordance with the method for claim 1, it is characterized in that, after the fischer-tropsch synthetic catalyst activation finishes, inert media is introduced reactive system, replace, until the activated media massfraction in the system＜1%, and then the introducing synthetic gas, enter the reaction starting stage.
Priority Applications (1)
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| CN105636691A (en) * | 2013-07-31 | 2016-06-01 | 沙特基础工业公司 | Catalyst for conversion of synthesis gas |
| CN109718773A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109908930A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | A kind of fischer-tropsch synthetic catalyst and preparation method thereof |
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| CN101326145A (en) * | 2005-12-09 | 2008-12-17 | 国际壳牌研究有限公司 | Method to start a process for producing hydrocarbons from synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105636691A (en) * | 2013-07-31 | 2016-06-01 | 沙特基础工业公司 | Catalyst for conversion of synthesis gas |
| CN109718773A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109908930A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | A kind of fischer-tropsch synthetic catalyst and preparation method thereof |
| CN109908930B (en) * | 2017-12-13 | 2021-10-08 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and preparation method thereof |
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