CN110361499A - The method of iron-base fischer-tropsch synthesis catalyst activity rating - Google Patents
The method of iron-base fischer-tropsch synthesis catalyst activity rating Download PDFInfo
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Abstract
The present invention relates to iron-base fischer-tropsch synthesis catalyst fields, disclose a kind of method of iron-base fischer-tropsch synthesis catalyst activity rating, method includes the following steps: (1) carries out reduction activation using iron-base fischer-tropsch synthesis catalyst of the also Primordial Qi to oxidation state, the iron-base fischer-tropsch synthesis catalyst that reduction activation degree is 80-90% is obtained；(2) iron-base fischer-tropsch synthesis catalyst that the reduction activation degree that step (1) obtains is 80-90% is subjected to Initial stability under the conditions of first living；(3) iron-base fischer-tropsch synthesis catalyst of Initial stability obtained by step (2) under the conditions of Fischer-Tropsch synthesis and is contained into H2Synthesis gas contact with CO carries out Fischer-Tropsch synthesis；(4) after to Fischer-Tropsch synthesis, the carbon deposition quantity of iron-base fischer-tropsch synthesis catalyst, the selectivity of deactivation rate and Fischer-Tropsch synthetic are tested.Method provided by the present invention can quickly filter out the iron-base fischer-tropsch synthesis catalyst of best performance.
Description
Technical field
The present invention relates to iron-base fischer-tropsch synthesis catalyst fields, and in particular to a kind of iron-base fischer-tropsch synthesis catalyst activity is commented
The method of valence.
Background technique
F- T synthesis (F-T) refers to the reaction for making CO hydro-conversion hydro carbons under catalyst (iron, cobalt, nickel, ruthenium etc.) effect.
With continuing to increase for contradiction between oil supply and demand, finding alternative petroleum resources becomes the project being concerned, new generation
Discipline natural gas and coal will become one of supplement and the alternative energy source of petroleum, and developing alternative energy source as raw material using natural gas and coal is one
The most important research contents of carbon geochemistry.The rich reserves of China's natural gas and coal have the space for developing one-carbon chemical, natural gas
The emphasis as new century petrochemical industry is utilized with New Coal Chemical.
In F-T synthetic catalyst, Fe base catalyst have both raw material is cheap and easy to get, product distribution is controllable, flexible operation and
The features such as Water gas shift/WGS (WGS) activity is adjustable, thus have received widespread attention and apply.According to reaction condition and purpose product
Difference, the ferrum-based catalyst for F- T synthesis can be divided into two kinds of catalyst of high temperature and low temperature, it may be assumed that precipitated iron catalyst and molten
Iron catalyst.Precipitated iron catalyst is suitable for Low Temperature Fischer Tropsch synthetic reaction, and product is based on the heavy hydrocarbons such as diesel oil, paraffin.It is right
In industrial application catalyst other than the selectivity that has needed and activity, with greater need for the stability and service life having had, with
This total oil yield to improve catalyst.
But the iron catalyst industrially applied has certain requirement to activity, stability and selectivity, it is therefore desirable to
Its stability, activity and selectivity are measured in the lab, and the superiority and inferiority of catalyst is understood with this.
Compared to the active phase of research iron-base fischer-tropsch synthesis catalyst, the inactivation of iron-base fischer-tropsch synthesis catalyst for
Industrial application has more specifically meaning.
The reason of may cause iron-base fischer-tropsch synthesis catalyst inactivation has following several:
(1) catalyst surface carbon distribution causes to inactivate.It is adsorbed on atomic carbon α-C, the widow on iron-base fischer-tropsch synthesis catalyst surface
Poly- carbon β-C, the carbon γ-C in cementite lattice and stable graphited carbon-coating δ-C, wherein α-C is more active, can
To add hydrogen to form methane in lower temperature, it may be possible to the precursor of hydrocarbons is generated, and δ-C is then possible to stop covering catalysis
The active site of agent causes to inactivate.The carbon distribution of catalyst surface can be removed by the methods of roasting, and catalyst is made to live again
Change.
(2) loss of effective active component leads to catalyst inactivation in catalyst.Long-lasting catalytic is heated, will lead to iron
The component volatilizations such as auxiliary agent sodium, potassium in base fischer-tropsch synthetic catalyst cause the loss of active component, subtract so as to cause active site
It is few, cause catalyst inactivation.
(3) active component is converted into inactive component and leads to catalyst inactivation in catalyst.Since Fischer-Tropsch synthesis is raw
At H2O and CO2Deng the product with certain oxidisability, metallic iron or cementite can be oxidized to Fe2O3So that catalytic active site
Point is reduced, and catalyst activity is caused to reduce.
(4) transformation of catalyst crystal form causes to inactivate.Long-lasting catalytic is heated, may result in iron-base fischer-tropsch synthesis and urges
The crystal form of effective active component changes in agent, such as Fe5C2To Fe2.2The transformation of C also results in the inactivation of catalyst.
(5) reduction of the specific surface area of catalyst crystal form leads to the inactivation of iron-base fischer-tropsch synthesis catalyst.F- T synthesis is anti-
It should be an exothermic process, temperature reaches 200 DEG C or more, and the crystal grain of catalyst can grow up during the reaction, causes to compare table
Area decline, reduces the activity of catalyst.
(6) components such as sulphur contained in reaction atmosphere lead to the poisoning and deactivation of catalyst.Due to the original of Fischer-Tropsch synthesis
Expect that gas from the steam reforming with coal, may result in and be mingled with micro element sulphur in unstripped gas, although iron-base fischer-tropsch synthesis is urged
Agent has the tolerance of good sulphur, but it is possible to leads to iron-base fischer-tropsch synthesis catalyst poisoning and deactivation, in unstripped gas
If containing H2The activity that S will lead to catalyst reduces, while the selectivity of low-carbon alkanes will increase.
The deactivation phenomenom of iron-base fischer-tropsch synthesis catalyst has been carried out largely there are many researcher at this stage
Research.
Document " Hydrocarbons via CO2Hydrogenation Over Iron Catalysts:The Effect
Different reducing process condition and process pair are described in of Potassium on Structure and Performance "
The influence of catalyst deactivation rate and phase transformation.The method of the document is that catalyst is carried out online reduction reaction, and constant
Fischer-Tropsch synthesis is completed under reaction condition, and is connected XRD and come the phase transformation of analysis of catalyst and the influence of inactivation.But it should
Document can not quickly and effectively judge the inactivation boundary of iron-base fischer-tropsch synthesis catalyst.
In addition, the catalytic activity of current iron-base fischer-tropsch synthesis catalyst has been obtained for a degree of improvement, enough
There is provided the other Fischer-Tropsch synthesis of technical grade continues how to lose iron-base fischer-tropsch synthesis catalyst rapidly using thousands of hours are up to
It is living, it simulates in laboratory and changes in each component inactivation of iron-base fischer-tropsch synthesis catalyst, realization fast and effeciently judges iron
The iron-base fischer-tropsch synthesis catalyst of the property superiority and inferiority of base fischer-tropsch synthetic catalyst, further screening best performance becomes this field
One urgent problem to be solved.
Summary of the invention
The purpose of the invention is to overcome the technology of existing evaluation iron-base fischer-tropsch synthesis catalyst performance can not be rapid
The inactivation border issue for effectively judging iron-base fischer-tropsch synthesis catalyst provides a kind of iron-base fischer-tropsch synthesis catalyst activity rating
Method, this method can be realized rapid deactivation iron-base fischer-tropsch synthesis catalyst, so as to save the property of catalyst in large quantities
It can evaluation time.
To achieve the goals above, the present invention provides a kind of methods of iron-base fischer-tropsch synthesis catalyst activity rating, should
Method the following steps are included:
(1) reduction activation is carried out using iron-base fischer-tropsch synthesis catalyst of the also Primordial Qi to oxidation state, obtains reduction activation degree
For the iron-base fischer-tropsch synthesis catalyst of 80-90%；
(2) iron-base fischer-tropsch synthesis catalyst that the reduction activation degree for obtaining step (1) is 80-90% is under the conditions of first living
Carry out Initial stability；
(3) by the iron-base fischer-tropsch synthesis catalyst of Initial stability obtained by step (2) under the conditions of Fischer-Tropsch synthesis with contain
There is H2Synthesis gas contact with CO carries out Fischer-Tropsch synthesis；
(4) after to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and Fischer-Tropsch of iron-base fischer-tropsch synthesis catalyst are tested
The selectivity of synthetic product.
More complicated phase transition can occur under synthesis gas atmosphere for iron-base fischer-tropsch synthesis catalyst.It is synthesized in iron-base fischer-tropsch
In the Fischer-Tropsch synthesis of catalyst, it is (main that iron-base fischer-tropsch synthesis catalyst is generally unsupported or support type iron oxide
If Fe2O3), by the reduction treatment of reducing atmosphere, portions turn is metallic state (α-Fe), when containing CO in reducing atmosphere,
Metallic iron and the iron oxide (Fe not being reduced2O3) cementite (Fe can be converted intoxCy), simultaneously as Fischer-Tropsch synthesis meeting
Water and carbon dioxide both products with oxidisability are generated, it can be by iron (Fe) or cementite (FexCy) it is oxidized to four oxidations
Three-iron (Fe2O3).Iron-base fischer-tropsch synthesis catalyst form at reaction conditions it is sufficiently complex, exist simultaneously iron oxide, metallic iron and
The a variety of object phases of cementite, wherein cementite includes the crystal phase of a variety of different iron-carbon ratios, the Fe including hexagonal phase2C (ε-carbonization
Object), Fe of the hexagonal phase to monoclinic phase transition2.2C (ε '-carbide), the Fe of orthorhombic crystal phase7C3(Eckstrom and Adcock-
Carbide), the Fe of monocline crystal phase5C2The Fe of (χ-carbide) and orthorhombic crystal phase3C (θ-cementite).The cementite of above-mentioned crystal phase
Species are likely to be detected in fischer-tropsch synthetic catalyst, while with the raising of reaction temperature, the carbon meeting in cementite
It is gradually precipitated, the Fe for being rich in carbon occurs2C is to poor carbon Fe3The transformation of C.Study iron-base fischer-tropsch synthesis catalyst at different conditions
Bulk structure variation has important significance of scientific research for the optimization of the performance of iron-base fischer-tropsch synthesis catalyst.
The present inventor probes into through a large number of experiments, it has unexpectedly been found that, when use reduction activation degree is 80-90%
Iron-base fischer-tropsch synthesis catalyst when being catalyzed Fischer-Tropsch synthesis, contain in the iron-base fischer-tropsch synthesis catalyst that is not restored sufficiently
There is the Fe of partial oxidation state2O3, when Fischer-Tropsch synthesis generates H2O and CO2Deng with certain oxidisability product when, the portion
Divide the Fe of oxidation state2O3Surface free energy is lower, can be used as crystal seed, provides the growth site of crystal, urges iron-base fischer-tropsch synthesis
Metallic iron or cementite in agent is by H2O and CO2When oxidation, crosses an energy barrier and directly generate Fe2O3, accelerate Fe2O3Life
Long rate.In addition, the partial pressure of higher oxidizing atmosphere (such as water vapour), can further result in iron-base fischer-tropsch synthesis catalyst
Rapid deactivation.The discovery of above-mentioned phenomenon is able to that the present inventor is allowed quickly and effectively to judge iron-base fischer-tropsch synthesis catalytic
The inactivation boundary of agent greatlys save the performance evaluation time of iron-base fischer-tropsch synthesis catalyst, using method provided by the invention,
The iron-base fischer-tropsch synthesis catalyst of best performance can be filtered out in the shorter time.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of method of iron-base fischer-tropsch synthesis catalyst activity rating, this method includes
Following steps:
(1) reduction activation is carried out using iron-base fischer-tropsch synthesis catalyst of the also Primordial Qi to oxidation state, obtains reduction activation degree
For the iron-base fischer-tropsch synthesis catalyst of 80-90%；
(2) iron-base fischer-tropsch synthesis catalyst that the reduction activation degree for obtaining step (1) is 80-90% is under the conditions of first living
Carry out Initial stability；
(3) by the iron-base fischer-tropsch synthesis catalyst of Initial stability obtained by step (2) under the conditions of Fischer-Tropsch synthesis with contain
There is H2Synthesis gas contact with CO carries out Fischer-Tropsch synthesis；
(4) after to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and Fischer-Tropsch of iron-base fischer-tropsch synthesis catalyst are tested
The selectivity of synthetic product.
According to the present invention, the iron-base fischer-tropsch synthesis catalyst of oxidation state is iron oxide (predominantly Fe2O3), in reduction activation
It can be reduced to α-Fe and cementite etc. in the process.In order to retain a part induction Fe2O3Accelerate the crystal seed of nucleation, step (1)
In, the insufficient progress of reduction activation is carried out using iron-base fischer-tropsch synthesis catalyst of the also Primordial Qi to oxidation state, so that obtained iron
The reduction activation degree of base fischer-tropsch synthetic catalyst is 80-90%.Contain in the iron-base fischer-tropsch synthesis catalyst not restored sufficiently
There is part Fe2O3, when Fischer-Tropsch synthesis generates H2O and CO2Deng with certain oxidisability product when, the part Fe2O3Table
Face free energy is lower, can be used as crystal seed, provides the growth site of crystal, make metallic iron in iron-base fischer-tropsch synthesis catalyst or
Cementite is by H2O and CO2When oxidation, crosses an energy barrier and directly generate Fe2O3, accelerate Fe2O3Growth rate.
According to the present invention, the iron-base fischer-tropsch synthesis catalyst that reduction activation degree is 80-90% in order to obtain, and oxidation state
Iron-base fischer-tropsch synthesis catalyst in oxygen be removed with the reduction of iron oxide, while the obtained iron of reduction being made to be converted into expense
Hold in the palm the active phase cementite (Fe of synthetic reactionxCy), it is described to be synthesized using iron-base fischer-tropsch of the also Primordial Qi to oxidation state in step (1)
The condition that catalyst carries out reduction activation preferably includes: the temperature of reduction activation is 200-280 DEG C, and the pressure of reduction activation is
0.5-4MPa, the also gas hourly space velocity of Primordial Qi are 2000-10000h-1, the time of reduction activation is 1-6h.
It is further preferred that in step (1), it is described to be carried out using iron-base fischer-tropsch synthesis catalyst of the also Primordial Qi to oxidation state
The condition of reduction activation may include: that the temperature of reduction activation is 250-280 DEG C, and the pressure of reduction activation is 0.5-2.5MPa,
The gas hourly space velocity of reduction activation is 5500-10000h-1, the time of reduction activation is 2-4h.
According to the present invention, the reduction activation degree is obtained according to the conversion ratio of also Primordial Qi during the reduction activation, example
The degree that reduction activation carries out can be such as determined using the moisture in absorbed on silica gel tail gas, it can also be using online gas-chromatography point
The conversion ratio of analysis method measurement CO determines the degree that reduction activation carries out.During the reduction activation, inertia can also be passed through
Gas forms to demarcate the tail gas of reduction activation process, and using the conversion ratio of online gas chromatography measurement also Primordial Qi.
Preferably, the inert gas can be any one in helium, neon, argon gas and nitrogen, and the inert gas is passed through
Amount can be the 1-20 volume % of reducing atmosphere.
According to the present invention, in step (1), during the reduction activation, the also Primordial Qi can be pure H2, pure CO and conjunction
At at least one of gas, preferably synthetic gas.When it is described also Primordial Qi is synthesis gas when, H in synthesis gas2With the volume ratio of CO
It can be 1-100:1, preferably 1-50:1, more preferably 2-50:1.
A kind of preferred embodiment according to the present invention, it is described that the iron-based of oxidation state is taken using also Primordial Qi in step (1)
The process that Tropsch synthesis catalyst carries out reduction activation may include: to mix the paraffin of the fischer-tropsch synthetic catalyst of oxidation state and melting
Uniformly slurries are made in conjunction, are filled into paste state bed reactor, are first passed through inert gas purge, are then introduced into also Primordial Qi；Adjustment is anti-
Answer device pressure to reduction activation pressure 0.5-4MPa, also Primordial Qi air speed is 2000-10000h-1, it is gradually heated to reduction activation temperature
200-280 DEG C, reduction activation 1-6h of degree is then introduced into also Primordial Qi.During above-mentioned reduction activation, the also Primordial Qi is to close
H at gas, in synthesis gas2Volume ratio with CO can be 1-100:1, preferably 1-50:1, more preferably 2-50:1.
According to the present invention, since there are induction periods for iron-base fischer-tropsch synthesis catalyst, if being directly 80- by reduction activation degree
90% iron-base fischer-tropsch synthesis catalyst is applied to Fischer-Tropsch synthesis, when will lead to the activity of catalyst with Fischer-Tropsch synthesis
Between first slowly rise, then rapid increase, phenomena such as destruction so as to cause catalyst structure, therefore, the reduction activation
The iron-base fischer-tropsch synthesis catalyst that degree is 80-90% is applied to need to carry out Initial stability before Fischer-Tropsch synthesis, described first
Living stablize preferably contains H CO concentration is higher2It is carried out in the presence of the synthesis gas of CO, such as the condition just living can be with
It include: to contain H in CO concentration for 0.01-20 volume %2In the presence of the synthesis gas of CO, it is by the reduction activation degree
The iron-base fischer-tropsch synthesis catalyst of 80-90% keeps 3-10h at 230-280 DEG C, 2-6MPa.
According to the present invention, the Fischer-Tropsch synthesis is with H2It is that raw material generates under fischer-tropsch synthetic catalyst effect with CO
Hydro carbons, oxygen-bearing organic matter, H2O and CO2Process, the key reaction on iron-base fischer-tropsch synthesis catalyst is as follows:
nCO+(2n+1)H2→CnH2n+2+nH2O (1)
nCO+2nH2→CnH2n+nH2O (2)
nCO+2nH2→CnH(2n+1)OH+(n-1)H2O (3)
CO+H2O→H2+CO2 (4)
2CO→C+CO2 (5)
Wherein, reaction (1)~(3) are the main reaction of F- T synthesis, it then follows carbochain Growth Mechanism, iron-base fischer-tropsch synthesis catalytic
Agent has F- T synthesis and Water gas shift/WGS catalytic activity simultaneously, thus reacts the reaction of Water gas shift/WGS (WGS) representated by (4)
As one of the key reaction using iron-base fischer-tropsch synthesis catalyst, thus it is possible to vary H in reaction process2/ CO partial pressure when water
Partial pressure, carbon disproportionated reaction (5) will lead to catalyst surface coking, cause catalyst inactivation.
According to the present invention, in step (3), in order to carry out with making F- T synthesis main reaction amplitude peak, the F- T synthesis
The condition of reaction preferably includes: temperature is 250-300 DEG C, pressure 2-9MPa, H2Volume ratio with CO is 1.5-5:1, with H2With
The total amount meter of CO, the volume space velocity of the Fischer-Tropsch synthesis are 10000-20000h-1, the time of the synthetic reaction is 150-
300h。
It is further preferred that it is 270-290 DEG C that the condition of the Fischer-Tropsch synthesis, which may include: temperature, pressure 3-
5MPa, H2Volume ratio with CO is 2-4:1, with H2Synthesis gas volume space velocity with the total amount meter of CO, the Fischer-Tropsch synthesis is
15000-20000h-1, the time of the synthetic reaction is 150-300h.
According to the present invention, in order to further speed up iron-base fischer-tropsch synthesis catalyst inactivation, the F- T synthesis can be made anti-
Answer the partial pressure in system with higher oxidizing atmosphere.For example, the condition of the Fischer-Tropsch synthesis may be used also in step (3)
To include: to contain H to described2With water vapour is passed through in the synthesis gas of CO, the intake of the water vapour makes in the Fischer-Tropsch
In synthetic reaction system, the partial pressure of water vapour is 2-20%.
Due to being using reduction activation degree in the method for iron-base fischer-tropsch synthesis catalyst activity rating provided by the invention
The iron-base fischer-tropsch synthesis catalyst of 80-90% is catalyzed Fischer-Tropsch synthesis, and with higher during Fischer-Tropsch synthesis
Steam partial pressure, when carrying out Fischer-Tropsch synthesis, iron-base fischer-tropsch synthesis catalyst can fast deactivation, can will be industrially normal
The deactivation time for advising the fischer-tropsch synthetic catalyst used foreshortens to 150-300h by traditional 1000-1500h, is suitable for laboratory
The device of scale and industry test scale, and then realize the inactivation side for fast and effeciently judging iron-base fischer-tropsch synthesis catalyst
Boundary can filter out the iron-base fischer-tropsch synthesis catalyst of best performance in a relatively short period of time.
According to the present invention, after Fischer-Tropsch synthesis, the carbon for being adsorbed on fischer-tropsch synthetic catalyst surface has a variety of crystalline substances
Therefore type in step (4), can identify the object phase composition in iron-base fischer-tropsch synthesis catalyst using in situ X-ray diffraction diffraction approach,
Also, the carbon deposition quantity of the iron-base fischer-tropsch synthesis catalyst also can be tested to obtain by situ X-ray diffraction diffraction approach.
According to the present invention, Fischer-Tropsch synthetic mainly includes short-chain hydrocarbons, oxygen-bearing organic matter, H2O and CO2Equal gas-phase products,
Therefore, the selectivity of the Fischer-Tropsch synthetic tests to obtain by online gas chromatography.
According to the present invention, in step (1), the reduction activation can carry out in paste state bed reactor, such as can stir
It mixes in kettle reactor or fluidized-bed reactor and carries out, can also be carried out in fixed bed reactors.Since iron-base fischer-tropsch synthesis is urged
Agent after use Fischer-Tropsch synthetic and Chen Tie iron-base fischer-tropsch chemical conversion catalyst in wax it is more, in fluidized-bed reactor
Middle reaction is difficult to go on, and therefore, the reduction activation preferably carries out in stirred tank reactor or fixed bed reactors.
According to a kind of preferred embodiment, the reduction activation reaction is reacted in fluidized-bed reactor or stirred tank
Carried out in device, also, in the presence of inert gas and paraffin, using also Primordial Qi to the iron-base fischer-tropsch synthesis catalyst of oxidation state into
Row reduction activation.
According to another preferred embodiment, reduction activation reaction in fixed-bed micro-reactor into
Row, also, in the presence of inert gas and quartz sand, the iron-base fischer-tropsch synthesis catalyst of oxidation state is gone back using also Primordial Qi
Original activation.
According to the present invention, in step (3), the Fischer-Tropsch synthesis in stirred tank reactor or fixed bed reactors into
Row.
The method of iron-base fischer-tropsch synthesis catalyst activity rating provided by the present invention can be realized iron-base fischer-tropsch synthesis and urge
The rapid deactivation of agent, to greatly save the performance evaluation time of iron-base fischer-tropsch synthesis catalyst.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, the fischer-tropsch synthetic catalyst of oxidation state is Shenhua Group industry sizing catalysis
Agent, trade mark SFT418.Fe in the fischer-tropsch synthetic catalyst of the oxidation state2O3Content be 75 weight %, partial size be 40 μm-
150 μm, specific surface area 206m2/ g, pore volume 0.52mL/g, most probable pore size 10.18nm.
In following embodiment and comparative example, in situ X-ray diffraction diffraction (XRD) method uses Thermo X ' TRAX ray
Diffractometer carries out, CuK α target, tube current 40mA, tube voltage 45kV.Solid probe energy range 1.72-1.95V only includes
CuK alpha energy range and the fluorescence that can effectively inhibit iron.Slot set is combined into 2/4/0.5/0.2, and it is 2.5 ° that rope, which draws slit,.
Situ reactor is AntonPaarXRK900 reactor, and temperature accuracy verifies through quartzy Phase Change Experiment, error within ± 1 DEG C,
Temperature Programmed Processes are controlled by diffractometer professional software, experimental pressure 0.7MPa.Reaction gas is hydrogen and nitrogen mixture (body
Product is than being 3:1), flow velocity 0.5L/min, 2 DEG C/min of heating rate.Tracking test is by room temperature to 280 DEG C of intervals, 50 DEG C of Quick Acquisitions
One spectrogram adjusts interval time according to object facies evolution concrete condition after 300 DEG C and tracks phase transformation detection fast continuous scan,
0.05 ° of step-length, speed 10 °/min, 28-67 ° of scanning range.The acquisition step-scan of microstructure analysis spectrogram, 0.02 ° of step-length,
Flyback time 1s is walked, scanning range is confined to peak position.
In following embodiment and comparative example, the online gas chromatography is being purchased from agilent company model
It is carried out on 7890 gas chromatograph.
In following embodiment and comparative example, the choosing of the carbonaceous products of the conversion ratio and F- T synthesis of CO in F- T synthesis gas
Selecting property is calculated using carbon atom normalization method, is specifically defined are as follows:
The conversion ratio of CO=[1- (concentration × exhaust flow of CO in tail gas)/(concentration × air inflow of CO in air inlet)] ×
100%
CH4Selectivity=(CH in tail gas4Concentration × exhaust flow)/(concentration × air inflow × CO of CO in air inlet
Conversion ratio × 100%)
CO2Selectivity=(CO in tail gas2Concentration × exhaust flow)/(concentration × air inflow × CO of CO in air inlet
Conversion ratio × 100%)
In following embodiment and comparative example, the calculation method of the deactivation rate of iron-base fischer-tropsch synthesis catalyst are as follows:
Deactivation rate=(conversion ratio of initial reaction stage CO-last stage reaction CO conversion ratio)/reaction time × 100
Embodiment 1
The fischer-tropsch synthetic catalyst of 10g oxidation state is uniformly mixed with the 300mL paraffin melted, slurries are made, is filled into and stir
It mixes in kettle reactor, is first passed through inert gas Ar purging, be then introduced into also Primordial Qi (H2With the synthesis gas of CO, wherein in synthesis gas
H2Volume ratio with CO is 20:1)；Stirred tank reactor pressure is adjusted to reduction activation pressure 0.5MPa, control also Primordial Qi air speed
For 6000h-1, first with the heating rate of 40-45 DEG C/h temperature in stirred tank reactor is risen to 200 DEG C by 30 DEG C, then again with
Temperature in stirred tank reactor is risen to 260 DEG C by 200 DEG C by the heating rate of 5-10 DEG C/h, and reduction activation 3h is then introduced into and contains
The also Primordial Qi of inert gas Ar, wherein the percentage by volume of inert gas Ar is 10%, remaining is also Primordial Qi.
The degree that reduction activation carries out is determined using the conversion ratio of online gas chromatography measurement CO.To described iron-based
The reduction activation degree of fischer-tropsch synthetic catalyst reaches 80%, and temperature is slowly dropped to 250 DEG C, and being passed through CO concentration is 5 volume %
Contain H2With the synthesis gas of CO, make the iron-base fischer-tropsch synthesis catalyst of the reduction activation degree 80% at 250 DEG C, 3MPa
Keep 8h.
Then, temperature in stirred tank reactor is increased to 270 DEG C, Xiang Suoshu stirred tank reactor is passed through containing water vapour
And H2With the synthesis gas of CO, Fischer-Tropsch synthesis is carried out, control stirred tank reactor entrance synthesis gas air speed is 18000h-1,
V (H in synthesis gas2)/V (CO)=4.5, the partial pressure of water vapour are 5%, reaction pressure 2MPa, reaction time 260h.
After to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and Fischer-Tropsch for testing iron-base fischer-tropsch synthesis catalyst are closed
At the selectivity of product, the results are shown in Table 1.
Embodiment 2
The fischer-tropsch synthetic catalyst of 2g oxidation state is uniformly mixed with 10mL quartz sand, is filled into fixed bed reactors,
First it is passed through inert gas N2Purging is then introduced into also Primordial Qi (H2With the synthesis gas of CO, wherein H in synthesis gas2With the volume ratio of CO
For 30:1)；Fixed-bed micro-reactor pressure is adjusted to reduction activation pressure 2.5MPa, control also Primordial Qi air speed is 6200h-1,
Temperature in fixed-bed micro-reactor is first risen to 200 DEG C by 30 DEG C with the heating rate of 40-45 DEG C/h, then again with 5-10
DEG C/temperature in fixed-bed micro-reactor rises to 260 DEG C by 200 DEG C by the heating rate of h, reduction activation 4h is then introduced into and contains
Inert gas N2Also Primordial Qi, wherein inert gas N2Percentage by volume be 15%, remaining for also Primordial Qi.
The degree that reduction activation reaction carries out is determined using the moisture in absorbed on silica gel tail gas.It is synthesized to the iron-base fischer-tropsch
The reduction activation degree of catalyst reaches 85%, and temperature is slowly dropped to 250 DEG C, and is passed through CO concentration and contains H for 4 volume %2
With the synthesis gas of CO, the iron-base fischer-tropsch synthesis catalyst of the reduction activation degree 85% is made to keep 7h at 250 DEG C, 5MPa.
Then, temperature in fixed bed reactors is increased to 260 DEG C, Xiang Suoshu fixed bed reactors are passed through containing water vapour
And H2With the synthesis gas of CO, Fischer-Tropsch synthesis is carried out, control reaction entrance synthesis gas air speed is 15000h-1, V in synthesis gas
(H2)/V (CO)=2.5, the partial pressure of water vapour are 5%, reaction pressure 3MPa, reaction time 260h.
After to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and Fischer-Tropsch for testing iron-base fischer-tropsch synthesis catalyst are closed
At the selectivity of product, the results are shown in Table 1.
Embodiment 3
The fischer-tropsch synthetic catalyst of 10g oxidation state is uniformly mixed with the 300mL paraffin melted, slurries are made, is filled into and stir
It mixes in kettle reactor, is first passed through inert gas Ar purging, be then introduced into also Primordial Qi (H2With the synthesis gas of CO, wherein in synthesis gas
H2Volume ratio with CO is 50:1)；Stirred tank reactor pressure is adjusted to reduction activation pressure 3MPa, control also Primordial Qi air speed is
8000h-1, temperature in stirred tank reactor is first risen to 200 DEG C by 30 DEG C with the heating rate of 40-45 DEG C/h, then again with 5-
Vulcanization bed reactor temperature is risen to 280 DEG C by 200 DEG C by the heating rate of 10 DEG C/h, and reduction activation 3h is then introduced into containing lazy
Property gas Ar also Primordial Qi H2With the synthesis gas of CO, wherein the percentage by volume of inert gas Ar is 10%, remaining is also Primordial Qi H2
With the synthesis gas of CO.
The degree that reduction activation carries out is determined using the conversion ratio of online gas chromatography measurement CO.To described iron-based
The reduction activation degree of fischer-tropsch synthetic catalyst reaches 90%, and temperature is slowly dropped to 260 DEG C, and being passed through CO concentration is 2.5 bodies
Product %'s contains H2With the synthesis gas of CO, make the iron-base fischer-tropsch synthesis catalyst of the reduction activation degree 90% 260 DEG C,
7h is kept under 6MPa.
Then, temperature in stirred tank reactor is increased to 280 DEG C, Xiang Suoshu stirred tank reactor is passed through containing water vapour
And H2With the synthesis gas of CO, Fischer-Tropsch synthesis is carried out, control stirred tank reactor entrance synthesis gas air speed is 20000h-1,
V (H in synthesis gas2)/V (CO)=3.5, the partial pressure of water vapour are 10%, reaction pressure 4MPa, reaction time 260h.
After to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and Fischer-Tropsch for testing iron-base fischer-tropsch synthesis catalyst are closed
At the selectivity of product, the results are shown in Table 1.
Embodiment 4
The fischer-tropsch synthetic catalyst of 10g oxidation state is filled into fluidized-bed reactor, inert gas N is passed through2Purging, leads
Enter also Primordial Qi (H2With the synthesis gas of CO, wherein H in synthesis gas2Volume ratio with CO is 50:1)；Adjust fluidized-bed reactor pressure
For power to reduction activation pressure 0.5MPa, control also Primordial Qi air speed is 6000h-1, first with the heating rate of 40-45 DEG C/h by fluidized bed
Reactor temperature rises to 200 DEG C by 30 DEG C, then again with the heating rate of 5-10 DEG C/h by temperature in fluidized-bed reactor by
200 DEG C rise to 260 DEG C, reduction activation 3h.
The degree that reduction activation reaction carries out is determined using the moisture in absorbed on silica gel tail gas.It is synthesized to the iron-base fischer-tropsch
The reduction activation degree of catalyst reaches 80%, and temperature is slowly dropped to 100 DEG C, is 80% iron-based to take by the reduction activation degree
Tropsch synthesis catalyst is transferred in the stirred tank reactor of the paraffin of filling 300mL melting, carries out Initial stability and F- T synthesis
Reaction.
After the iron-base fischer-tropsch synthesis catalyst that the reduction activation degree is 80% is transferred in stirred tank reactor, first it is passed through
N2Purging then passes to CO concentration as 2.5 volume % and contains H2With the synthesis gas of CO, stirred tank pressure is charged to 3MPa.Then
Reactor temperature is risen to 200 DEG C with the heating rate of 40-45 DEG C/h, then will be reacted with the heating rate of 5-10 DEG C/h again
Temperature rises to 250 DEG C by 200 DEG C in device, makes the iron-base fischer-tropsch synthesis catalyst of the reduction activation degree 80% at 250 DEG C
Keep 8h.
Then, temperature in stirred tank reactor is increased to 270 DEG C, Xiang Suoshu stirred tank reactor is passed through containing water vapour
And H2With the synthesis gas of CO, Fischer-Tropsch synthesis is carried out, control stirred tank reaction entrance synthesis gas air speed is 18000h-1, close
At V (H in gas2)/V (CO)=3.5, the partial pressure of water vapour are 5%, reaction pressure 3MPa, reaction time 260h.
After to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and Fischer-Tropsch for testing iron-base fischer-tropsch synthesis catalyst are closed
At the selectivity of product, the results are shown in Table 1.
Embodiment 5
According to the method for embodiment 3, unlike, during carrying out Fischer-Tropsch synthesis, in the synthesis gas that is passed through not
Containing water vapour, the carbon deposition quantity of iron-base fischer-tropsch synthesis catalyst, the selectivity of deactivation rate and Fischer-Tropsch synthetic are tested, as a result
As shown in table 1.
Comparative example 1
According to the method for embodiment 3, the difference is that, in the reduction activation process for the fischer-tropsch synthetic catalyst for carrying out oxidation state
In, the time of reduction activation is 16h, obtains the iron-base fischer-tropsch synthesis catalyst that reduction activation degree is 100%, tests iron-base fischer-tropsch
The selectivity of the carbon deposition quantity of synthetic catalyst, deactivation rate and Fischer-Tropsch synthetic, the results are shown in Table 1.
Comparative example 2
According to the method for embodiment 3, the difference is that, in the reduction activation process for the fischer-tropsch synthetic catalyst for carrying out oxidation state
In, the time of reduction activation is 16h, obtains the iron-base fischer-tropsch synthesis catalyst that reduction activation degree is 100%, and carrying out Fischer-Tropsch
In synthetic reaction process, without containing water vapour in the synthesis gas that is passed through, carbon deposition quantity, the inactivation of iron-base fischer-tropsch synthesis catalyst are tested
The selectivity of rate and Fischer-Tropsch synthetic, the results are shown in Table 1.
Comparative example 3
According to the method for embodiment 3, the difference is that, in the reduction activation process for the fischer-tropsch synthetic catalyst for carrying out oxidation state
In, the time of reduction activation is 1h, obtains the iron-base fischer-tropsch synthesis catalyst that reduction activation degree is 75%, and test iron-base fischer-tropsch closes
At the selectivity of the carbon deposition quantity of catalyst, deactivation rate and Fischer-Tropsch synthetic, the results are shown in Table 1.
Comparative example 4
According to the method for embodiment 3, the difference is that, in the reduction activation process for the fischer-tropsch synthetic catalyst for carrying out oxidation state
In, the time of reduction activation is 8h, obtains the iron-base fischer-tropsch synthesis catalyst that reduction activation degree is 95%, and test iron-base fischer-tropsch closes
At the selectivity of the carbon deposition quantity of catalyst, deactivation rate and Fischer-Tropsch synthetic, the results are shown in Table 1.
Table 1
It can be seen that the side using iron-base fischer-tropsch synthesis catalyst activity rating provided by the invention by the result of table 1
The deactivation rate of method, iron-base fischer-tropsch synthesis catalyst is higher, can be realized rapid deactivation iron-base fischer-tropsch synthesis catalyst, so as to
The enough performance evaluation time for saving catalyst in large quantities.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method of iron-base fischer-tropsch synthesis catalyst activity rating, which is characterized in that method includes the following steps:
(1) reduction activation is carried out using iron-base fischer-tropsch synthesis catalyst of the also Primordial Qi to oxidation state, obtaining reduction activation degree is 80-
90% iron-base fischer-tropsch synthesis catalyst；
(2) iron-base fischer-tropsch synthesis catalyst that the reduction activation degree that step (1) obtains is 80-90% is carried out under the conditions of first living
Initial stability；
(3) iron-base fischer-tropsch synthesis catalyst of Initial stability obtained by step (2) under the conditions of Fischer-Tropsch synthesis and is contained into H2With
The synthesis gas contact of CO carries out Fischer-Tropsch synthesis；
(4) after to Fischer-Tropsch synthesis, the carbon deposition quantity, deactivation rate and F- T synthesis of iron-base fischer-tropsch synthesis catalyst are tested
The selectivity of product.
2. according to the method described in claim 1, wherein, in step (1), described use goes back Primordial Qi to the iron-base fischer-tropsch of oxidation state
The condition of synthetic catalyst progress reduction activation includes: that the temperature of reduction activation is 200-280 DEG C, and the pressure of reduction activation is
0.5-4MPa, the also gas hourly space velocity of Primordial Qi are 2000-10000h-1, the time of reduction activation is 1-6h.
3. according to the method described in claim 1, wherein, in step (1), the reduction activation degree is according to the reduction activation
The conversion ratio of also Primordial Qi obtains in journey.
4. according to the method described in claim 1, wherein, in step (2), the condition just living includes: to be in CO concentration
0.01-20 volume %'s contains H2In the presence of the synthesis gas of CO, the iron-base fischer-tropsch for being 80-90% by the reduction activation degree
Synthetic catalyst keeps 3-10h at 230-280 DEG C, 2-6MPa.
5. according to the method described in claim 1, wherein, in step (3), the condition of the Fischer-Tropsch synthesis includes: temperature
It is 250-300 DEG C, pressure 2-9MPa, H2Volume ratio with CO is 1.5-5:1, with H2With the total amount meter of CO, the F- T synthesis
The synthesis gas volume space velocity of reaction is 10000-20000h-1, the time of the synthetic reaction is 150-300h.
6. method according to claim 1 or 5, wherein in step (3), the condition of the Fischer-Tropsch synthesis further include:
Contain H to described2With water vapour is passed through in the synthesis gas of CO, the intake of the water vapour makes in the F- T synthesis
In reaction system, the partial pressure of water vapour is 2-20%.
7. according to the method described in claim 1, wherein, in step (4), the carbon deposition quantity of the iron-base fischer-tropsch synthesis catalyst is logical
In situ X-ray diffraction diffraction approach is crossed to test to obtain.
8. according to the method described in claim 1, wherein, in step (4), the selectivity of the Fischer-Tropsch synthetic passes through online
Gas chromatography is tested to obtain.
9. according to the method described in claim 1, wherein, in step (1), the reduction activation is in fluidized-bed reactor, stirring
It is carried out in any one reactor in kettle reactor and fixed bed reactors.
10. according to the method described in claim 1, wherein, in step (3), the Fischer-Tropsch synthesis is in stirred tank reactor
Or it is carried out in fixed bed reactors.
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| CN111659432A (en) * | 2020-05-22 | 2020-09-15 | 北京化工大学 | CO2Iron-based catalyst for preparing ethanol by hydrogenation, preparation method and application |
| CN114436750A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Pretreatment method of reaction system for directly preparing olefin from synthesis gas |
| CN115400696A (en) * | 2021-05-28 | 2022-11-29 | 国家能源投资集团有限责任公司 | Method and device for preparing high value-added chemicals from synthesis gas |
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