CN105087042A - Fischer-Tropsch synthesis method - Google Patents
Fischer-Tropsch synthesis method Download PDFInfo
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- CN105087042A CN105087042A CN201410195735.4A CN201410195735A CN105087042A CN 105087042 A CN105087042 A CN 105087042A CN 201410195735 A CN201410195735 A CN 201410195735A CN 105087042 A CN105087042 A CN 105087042A
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Abstract
The present invention provides a Fischer-Tropsch synthesis method. The method comprises: under Fischer-Tropsch synthesis conditions and in the presence of a Fischer-Tropsch synthesis catalyst, reacting synthesis gas in a supercritical medium. The supercritical medium is at least one medium selected from C3-C10 alkane, C3-C10 olefin, C6-C10 aromatic hydrocarbon and light oil produced by Fischer-Tropsch synthesis. By using the Fischer-Tropsch synthesis method provided by the present invention, a higher conversion rate of CO and higher C5+ selectivity can be obtained.
Description
Technical field
The present invention relates to a kind of method of F-T synthesis.
Background technology
In fixed-bed reactor, Fischer-Tropsch synthesis (F-T) is a gas-solid-liquid multiphase reaction system.Although fixed bed F-T synthesis is considered to " gas-phase reaction ", but because of generation and the capillary condensation effect of F-T synthesis medium high carbon product, the heavy hydrocarbon product generated in reaction process is filled in granules of catalyst duct with the form of liquid phase wax usually, and covers the surface of catalyzer.Like this, when granules of catalyst exceedes certain size, each reactive component of F-T synthesis will have a strong impact on the selectivity of chemical reaction rate and product in intragranular Liquid Phase Diffusion, and the impact of diffusion control on catalytic performance is difficult to avoid.In the internal diffusion process of reactant, H
2velocity of diffusion faster than the velocity of diffusion of CO, therefore, CO is obviously better than H in the diffusional limitation effect of granules of catalyst inside
2.Because the particle diameter of granules of catalyst is different, result in the difference of granule interior CO concentration gradient, have impact on the combination of CO and metal active centres position, make the H/C adsorbed on active centre than increasing, carbon chain growth probability reduces, and thus reduces C
5+selectivity.
In addition, F-T synthesis is strong exothermal reaction, if accumulation of heat is too much, not only can reduces the selectivity of hydro carbons, also can cause catalyst carbon deposit, pulverizing, make bed temperature runaway.For fixed bed FischerTropsch synthesis catalyst, reaction, mass transfer, heat transfer process coexist on fischer-tropsch synthetic catalyst.
In the hydrocarbon product of F-T synthesis, most hydrocarbon is straight chain hydrocarbon.By design, regulation and control catalyst reaction active centre type, can be that raw material one step obtains the higher gasoline section of isomeric hydrocarbon selectivity or diesel oil section cut hydrocarbon with synthetic gas, enormously simplify production process, reduce production cost.Research shows, the distribution of F-T synthetic product can be regulated by regulation and control catalyst active center, such as, loaded catalyst is introduced the material (as molecular sieve) with acid active centre can make catalyzer have CO hydrogenation sites and isomery, cracking activity center simultaneously, molecular sieve and fischer-tropsch catalysts are used jointly, the distribution of classical Fischer-Tropsch synthetic can be changed, improve the yield of gasoline fraction and diesel oil distillate in Fischer-Tropsch synthetic.
Fuel87 (2008) 534-538KaoruFujimoto discloses the three components Co/Al of capsule-type
2o
3/ H-Beta catalyzer, the core of this catalyzer is Co/Al
2o
3, skin is the H-Beta molecular sieve of load P d.Result shows, Co/Al
2o
3cO transformation efficiency be up to 97.63%, and Co/Al
2o
3the CO transformation efficiency of/H-Beta is up to 85.25%, Co/Al
2o
3the CO transformation efficiency of/Pd/H-Beta is up to 32.35%, and in product, more than C4 isomeric hydrocarbon selectivity raises successively, Co/Al
2o
3in the product of/H-Beta, more than C2 ethylenic alkoxy rate is the highest.As can be seen here, adopt after adding molecular sieve in such a way, although the isomeric hydrocarbon selectivity in product can be improved, the transformation efficiency of composite molecular sieve catalyst obviously reduces.Therefore, exploitation activity and stereoselectivity composite molecular sieve catalyst all is preferably necessary very much.In addition, in Fischer-Tropsch synthesis, the hole of the hydro carbons meeting covering catalyst particle of macromolecule, makes catalyzer pyrolysis carbon distribution, causes catalyst deactivation.After particularly adding molecular sieve, there is alkene oligomerization reaction on solid acid catalyst surface and generate superpolymer in low-carbon alkene, not only may block duct, also may cause the inactivation of catalyzer.
Summary of the invention
The object of the invention is to overcome the CO transformation efficiency and/or C that adopt existing Fischer-Tropsch synthesis method to obtain
5+the defect that selectivity is lower, and provide and a kind ofly can obtain higher CO transformation efficiency and C
5+the optionally method of F-T synthesis.
The invention provides a kind of method of F-T synthesis, under the method is included in F-T synthesis condition and under fischer-tropsch synthetic catalyst existence, reacted in supercritical medium by synthetic gas, described supercritical medium is selected from C
3-C
10alkane, C
3-C
10alkene, C
6-C
10aromatic hydrocarbons and F-T synthesis generate light oil at least one.
The present inventor finds through further investigation, on the one hand, supercritical medium has larger heat transfer, mass transfer and extraction rate, utilizes the These characteristics of supercritical medium can solve the problem of the thermophoresis of F-T synthesis gas-phase reaction and the blocking of liquid phase reaction catalyst pores; On the other hand, supercritical medium has very strong dissolving power, and the inactive carbon laydown that can reaction be generated in time and macromolecule wax, from catalyst surface desorption, avoid the vicious cycle of catalyst carbon deposit and the inactivation of catalyzer.Therefore, in supercritical medium, carry out Fischer-Tropsch synthesis, the carbon deposit of catalyst surface can be inhibited, catalyzer can active sites increase, thus make CO transformation efficiency and C
5+selectivity is improved.
A preferred embodiment of the invention, when the active ingredient in fischer-tropsch synthetic catalyst distributes in shell on carrier, shell combines firmly with core, the long period of this fischer-tropsch synthetic catalyst structure distribution can be kept thus to stablize, thus ensure that there is when being applied in Fischer-Tropsch synthesis the higher active also higher CO transformation efficiency of acquisition and C
5+selectivity.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Under the method for F-T synthesis provided by the invention is included in F-T synthesis condition and under fischer-tropsch synthetic catalyst exists, reacted in supercritical medium by synthetic gas, described supercritical medium is selected from C
3-C
10alkane, C
3-C
10alkene, C
6-C
10aromatic hydrocarbons and F-T synthesis generate light oil at least one.
Described C
3-C
10the specific examples of alkane include but not limited to: n-propane, isopropyl alkane, normal butane, 2-methylpropane, Skellysolve A, 2-methylbutane, normal hexane, 2-methyl hexane, 3-methyl hexane, 1,2-dimethylpentane, normal heptane, octane, 2,3,4-trimethylpentane, 2, at least one in 2,4-trimethylpentane, n-nonane and n-decane.
Described C
3-C
10the specific examples of alkene include but not limited to: positive propylene, iso-butylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, cis-2-amylene, trans-2-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 2-methyl isophthalic acid-heptene, 3-methyl isophthalic acid-heptene, 4-methyl isophthalic acid-heptene, 5-methyl isophthalic acid-heptene, 6-methyl isophthalic acid-heptene, 2-methyl-2-heptene, 3-methyl-2-heptene, 4-methyl-2-heptene, 5-methyl-2-heptene, 6-methyl-2-heptene, 2-methyl-3-heptene, 3-methyl-3-heptene, 4-methyl-3-heptene, 5-methyl-3-heptene, 6-methyl-3-heptene, 1,2-dimethyl-1-hexene, 1,3-dimethyl-1-hexene, Isosorbide-5-Nitrae-dimethyl-1-hexene, 1,5-dimethyl-1-hexene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 5,5-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 3,5-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 2,3-dimethyl-2-hexene, 2,4-dimethyl-2-hexene, 2,5-dimethyl-2-hexene, 2,4-dimethyl-2-hexene, 3,5-dimethyl-2-hexene, 4,4-dimethyl-2-hexene, 5,5-dimethyl-2-hexene, 4,5-dimethyl-2-hexene, 2,2-dimethyl-3-hexene, 2,3-dimethyl-3-hexene, 2,4-dimethyl-3-hexene, 2,5-dimethyl-3-hexene, at least one in 3,4-dimethyl-3-hexene and 3,5-dimethyl-3-hexene.
Described C
6-C
10the specific examples of aromatic hydrocarbons include but not limited to: one or more in benzene, toluene, 1,2-dimethylbenzene, 1,3-dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, 1，3，5-trimethyl-benzene, ethylbenzene and propyl benzene.
The light oil that described F-T synthesis generates refers to the cut of gasoline fraction section in Fischer-Tropsch synthesis product (initial boiling point (IBP)-200 DEG C).
According to the method for F-T synthesis provided by the invention, preferably, described supercritical medium is selected from least one in the light oil of Skellysolve A, normal hexane and F-T synthesis generation, and more preferably, described supercritical medium is the light oil that F-T synthesis generates.When described supercritical medium is the light oil of F-T synthesis generation, high CO transformation efficiency and C can be obtained
5+selectivity.
The consumption of the present invention to described supercritical medium is not particularly limited, and such as, the consumption of described supercritical medium can make the dividing potential drop produced by it be 1-20MPa, is preferably 2-18MPa, is more preferably 3-10MPa.In the present invention, pressure all refers to gauge pressure.
According to the method for F-T synthesis provided by the invention, the kind of described fischer-tropsch synthetic catalyst can be the routine selection of this area, and such as, described fischer-tropsch synthetic catalyst generally includes carrier and the active metal component of load on carrier.Wherein, described carrier can be selected from least one in aluminum oxide, silicon oxide, titanium oxide, zirconium white and gac, and described active metal component can be selected from least one component in Fe, Co and Ru.Preferably, described fischer-tropsch synthetic catalyst is the compound fischer-tropsch synthetic catalyst containing molecular sieve, can improve the yield of gasoline fraction and diesel oil distillate in Fischer-Tropsch synthetic like this.More preferably, the described compound fischer-tropsch synthetic catalyst containing molecular sieve comprises carrier and load active metal component on the carrier, described carrier contains with the gross weight of the described carrier 5-90 % by weight that is benchmark, the molecular sieve being preferably 10-30 % by weight, described active metal component on the carrier in shell distribution, adopt so preferred active metal component be shell distribute fischer-tropsch synthetic catalyst can obtain higher CO transformation efficiency and C
5+selectivity.Wherein, on described carrier except the molecular sieve containing 5-90 % by weight, preferably 10-30 % by weight, also containing at least one in aluminum oxide, silicon oxide, titanium oxide, zirconium white and gac.In addition, described carrier can exist with existing different shape, such as, can be spherical, tablets or bar shaped, preferably spherical.
" shell distribute catalyst " is also called eggshell type catalyst with non-uniform distribution by those skilled in the art usually, be called for short egg-shell catalyst, it is defined as well known to those skilled in the art, such as can see (the definition in 199-200 page in " catalyst support preparation and utilisation technology " book that Zhu Hongfa writes (petroleum industry press 2002 May the 1st edition).Generally speaking, described " egg-shell catalyst " refers to that the shell factor sigma of catalyzer is a class catalyzer of 0≤σ < 0.95.Wherein, shell factor sigma is the active metal component ratio of (except center) concentration on heart place concentration and a certain position in the catalyst; On a certain position, concentration refers to the mean value along neighbouring 20 the numerical point counting rates of certain point of carrier radial direction in SEM-EDX (ScanningElectronMicroscope-EnergyDispersiveSpectrometry, lower same) characterization result; Center concentration refers to the mean value along 20 numerical point counting rates near the central point of carrier in SEM-EDX characterization result.Counting rate along the radial every bit of carrier in SEM-EDX characterization result is mutually corresponding with this constituent content, although the size of counting rate may not represent the real content of this element, the size of counting rate reflects this constituent content height.In shell, the distribution active metal component referred in catalyzer is mainly distributed in shell to active metal component of the present invention on the carrier.In the present invention, the thickness of described shell adopts SEM-EDX method to record, particularly, random selecting 30 compound fischer-tropsch synthetic catalysts also record its cross-sectional view and particle diameter with SEM, obtain the radial distribution of active ingredient along the radial scan of each compound fischer-tropsch synthetic catalyst respectively with EDX afterwards and obtain the thickness of 0≤σ≤0.5 part, the arithmetical av getting above-mentioned thickness is shell thickness of the present invention.
The present invention is not particularly limited containing the content of each component in the compound fischer-tropsch synthetic catalyst of molecular sieve described, such as, with the gross weight of the described compound fischer-tropsch synthetic catalyst containing molecular sieve for benchmark, the content of described carrier can be 30-99 % by weight, is preferably 40-95 % by weight; Can be 1-70 % by weight with the content of the described active metal component of oxide basis, be preferably 5-60 % by weight.
The kind of described molecular sieve can be the routine selection of this area, such as, the molecular sieve with ten-ring pore structure can be selected from, such as, one or more in SAPO-11, SAPO-41, ZSM-22, ZSM-5 etc., also the molecular sieve with twelve-ring pore structure can be selected from, such as, one or more in Y zeolite, β-molecular sieve, mordenite etc.Preferably, described molecular sieve is ZSM-22 molecular sieve and/or β-molecular sieve.
Described active metal component also can be that the routine of this area is selected, and such as, can be at least one in iron (Fe), cobalt (Co) and ruthenium (Ru), be preferably Co and/or Ru.As well known to those skilled in the art, the active metal component of described fischer-tropsch synthetic catalyst exists with the form of its oxide compound usually.In the present invention, the content of described active metal component is all with the oxide basis that this active metal component is corresponding.
The shell thickness of the present invention to the particle diameter of described carrier and shell distribution is not particularly limited, and such as, the particle diameter of described carrier can be 0.2-8mm, is preferably 0.5-6mm, is more preferably 1-4mm; The shell thickness of described shell distribution can be 0.06-2mm, is preferably 0.08-1.5mm, is more preferably 0.1-0.4mm.
The described compound fischer-tropsch synthetic catalyst containing molecular sieve can be commercially available, also can according to well known to a person skilled in the art that various method prepares.Such as, the described compound fischer-tropsch synthetic catalyst containing molecular sieve can prepare in accordance with the following methods: by the mixture extrusion moulding containing at least one in alumina precursor, siliconoxide precursor, titania precursor body, zirconium white presoma and gac and molecular sieve, then will extrude bar and carry out drying and roasting, obtain carrier; Then can by the existing various method preparing egg-shell catalyst by active metal component load on above-mentioned carrier, be specially as well known to those skilled in the art, therefore not to repeat here.Above-mentioned several presoma all can be commercially available, such as, SB powder, the C1 powder that can produce for Sasol company (former German condea company), the CL powder that Chang Ling catalyst plant is produced, at least one in the aluminum silicon powder SA40 of Research Institute of Petro-Chemical Engineering etc.
The present invention is not particularly limited described F-T synthesis condition, and such as, it can be 170-350 DEG C that described F-T synthesis condition generally includes temperature, is preferably 180-300 DEG C; Total pressure can be 1-20MPa, is preferably 2-18MPa; During the gas of synthetic gas, volume space velocity can be 3000-20000h
-1, be preferably 3500-18000h
-1.
As a rule, described fischer-tropsch synthetic catalyst just has catalytic activity after reduction, therefore, before Fischer-Tropsch synthesis, needs in presence of hydrogen, fischer-tropsch synthetic catalyst is carried out reduction activation.Wherein, it can be 200-1000 DEG C that the condition of described reduction activation generally includes reduction temperature, is preferably 200-800 DEG C; Recovery time can be 1-96 hour, is preferably 2-24 hour.Described reduction activation can be carried out in pure hydrogen, also can carry out in the gas mixture of hydrogen and rare gas element.Wherein, the various gases not participating in chemical reaction under above-mentioned reduction activation condition that described rare gas element is known to the skilled person, as nitrogen and/or zero group gas.When carrying out in the gas mixture of described reduction activation at hydrogen and rare gas element, the dividing potential drop of hydrogen can be 0.1-4MPa, is preferably 0.1-2MPa.
Described synthetic gas refers to H
2be the unstripped gas of main ingredient with CO, wherein, in order to make full use of synthetic gas, preferably, H in described synthetic gas
2be 1-3:1 with the mol ratio of CO.
In addition, the reactor that described F-T synthesis adopts can be fixed-bed reactor, paste state bed reactor, fluidized-bed reactor etc., is preferably fixed-bed reactor.
Below will be described the present invention by embodiment.
In following examples and comparative example, the particle diameter of carrier adopts scanning electronic microscope (SEM) to measure.The shell thickness of active metal component adopts SEM-EDX method to analyze, particularly, random selecting 30 compound fischer-tropsch synthetic catalysts also record its cross-sectional view and particle diameter with SEM, obtain the radial distribution of active ingredient along the radial scan of each compound fischer-tropsch synthetic catalyst respectively with EDX afterwards and obtain the thickness (shell factor sigma is the active metal component ratio of (except center) concentration on heart place concentration and a certain position in the catalyst) of 0≤σ≤0.5 part, the arithmetical av getting above-mentioned thickness is shell thickness of the present invention.
Embodiment 1
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
(1) preparation of fischer-tropsch synthetic catalyst:
By the circular orifice extruded moulding that the rear diameter of pseudo-boehmite (Sasol company C1 powder) mixing of the β-molecular sieve of 10 % by weight same 90 % by weight is 1.4 millimeters, then bar will be extruded in 120 DEG C of dryings 4 hours, again in 600 DEG C of roastings 4 hours, obtain carrier.Then prepare egg-shell catalyst according to method disclosed in CN101462079A embodiment 6, obtain fischer-tropsch synthetic catalyst A.The content adopting X-fluorescence method to measure active metal component cobalt in the fischer-tropsch synthetic catalyst obtained is 16 % by weight.Can be observed active metal component (broken then observe) on fischer-tropsch synthetic catalyst through naked eyes to distribute in eggshell, and to analyze with SEM-EDX the thickness that known shell distributes be 0.18mm.
(2) Fischer-Tropsch synthesis:
Fischer-Tropsch synthesis carries out in fixed-bed reactor, and the loadings of fischer-tropsch synthetic catalyst A is 5g.Before carrying out Fischer-Tropsch synthesis, first (represent that relative to every gram of catalyzer flow hourly be 1000 standard liters with 1000NL/g-cat/h, flow down together) injects hydrogen, and is warming up to 400 DEG C with the temperature rise rate of 4 DEG C/min, and keeps 5 hours at such a temperature.
Then, at 240 DEG C, with 5600h
-1gas time volume space velocity (GHSV) in these fixed-bed reactor, inject supercritical medium Skellysolve A, simultaneously with 4000h
-1gas time volume space velocity in these fixed-bed reactor, inject H
2with the mixed gas (H of CO
2/ CO mol ratio is 2:1), thus carry out Fischer-Tropsch synthesis, in reaction process, reaction pressure P (always)=6.0MPa, P (CO+H
2)=2.5MPa, the dividing potential drop produced by supercritical medium normal hexane is 3.5MPa.React after 24 hours, evaluated the transformation efficiency (X of CO by the reaction product in these fixed-bed reactor
cO), C
5(C above
5+) selectivity of hydro carbons
and CH
4selectivity
, its result is as shown in table 1 below.Particularly, X
cO, C
5+with
calculate respectively by following formula, lower same:
Wherein, V
1, V
2under being illustrated respectively in the normal conditions, entering the volume of the unstripped gas of reactive system in certain time period and flow out the exhaust gas volumes of reactive system; c
1, CO, c
2, COrepresent the content of CO in unstripped gas and tail gas respectively.N
confor being participated in the mole number of the CO of reaction in certain time period by reaction bed,
for generating CH
4, C
2hydrocarbon, C
3hydrocarbon and C
4the mole number sum of the CO of hydrocarbon,
for generating CO
2the mole number of CO,
for generating CH
4the mole number of CO.
In addition, in Fischer-Tropsch synthesis product, the analytical results of each cut is as shown in table 2; In Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by gas chromatography, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer, and acquired results is as shown in table 3.
Embodiment 2
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
(1) preparation of fischer-tropsch synthetic catalyst:
By the circular orifice extruded moulding that the rear diameter of pseudo-boehmite powder (the SB powder purchased from Sasol company) mixing of the ZSM-22 of 30 % by weight same 70 % by weight is 1.4 millimeters, then bar will be extruded in 120 DEG C of dryings 4 hours, again in 600 DEG C of roastings 4 hours, obtain carrier.Then prepare egg-shell catalyst according to method disclosed in CN101462079A embodiment 6, obtain fischer-tropsch synthetic catalyst B.The content adopting X-fluorescence method to measure active metal component cobalt in the fischer-tropsch synthetic catalyst obtained is 16 % by weight.Can be observed active metal component (broken then observe) on fischer-tropsch synthetic catalyst through naked eyes to distribute in eggshell, and to analyze with SEM-EDX the thickness that known shell distributes be 0.17mm.
(2) Fischer-Tropsch synthesis:
Fischer-Tropsch synthesis is carried out according to the method for embodiment 1, unlike, the fischer-tropsch synthetic catalyst B of fischer-tropsch synthetic catalyst A identical weight part is substituted.React after 48 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by gas chromatography, and acquired results is as shown in table 3; The coke content reacted after 48 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer, and acquired results is as shown in table 3.
Embodiment 3
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
(1) preparation of fischer-tropsch synthetic catalyst:
By the circular orifice extruded moulding that the rear diameter of pseudo-boehmite (Sasol company C1 powder) mixing of the β-molecular sieve of 10 % by weight same 90 % by weight is 1.4 millimeters, then bar will be extruded in 120 DEG C of dryings 4 hours, again in 600 DEG C of roastings 4 hours, obtain carrier.Then prepare egg-shell catalyst according to method disclosed in CN101462079A embodiment 6, and steeping fluid same concentrations, same volume nitric acid ruthenium solution substitute, obtain fischer-tropsch synthetic catalyst C.The content adopting X-fluorescence method to measure active metal component ruthenium in the fischer-tropsch synthetic catalyst obtained is 2 % by weight.Can be observed active metal component (broken then observe) on fischer-tropsch synthetic catalyst through naked eyes to distribute in eggshell, and to analyze with SEM-EDX the thickness that known shell distributes be 0.15mm.
(2) Fischer-Tropsch synthesis:
Fischer-Tropsch synthesis carries out in fixed-bed reactor, and the loadings of fischer-tropsch synthetic catalyst C is 5g.Before carrying out Fischer-Tropsch synthesis, first inject hydrogen with the flow of 1000NL/g-cat/h, and be warming up to 400 DEG C with the temperature rise rate of 4 DEG C/min, and keep 5 hours at such a temperature.
Then, at 260 DEG C, with 8800h
-1gas time volume space velocity in these fixed-bed reactor, inject the light oil (this light oil is the fischer-tropsch reaction product gasoline fraction section product that embodiment 1 obtains) that supercritical medium F-T synthesis generates, simultaneously with 4000h
-1gas time volume space velocity in these fixed-bed reactor, inject H
2with the mixed gas (H of CO
2/ CO mol ratio is 3:1), thus carry out Fischer-Tropsch synthesis, in reaction process, reaction pressure P (always)=8.0MPa, P (CO+H
2)=2.5MPa, the dividing potential drop that the light oil generated by supercritical medium F-T synthesis produces is 5.5MPa.React after 24 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer, and acquired results is as shown in table 3.
Embodiment 4
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
Prepare fischer-tropsch synthetic catalyst according to the method for embodiment 1 and carry out Fischer-Tropsch synthesis, the light oil that generates unlike the supercritical medium F-T synthesis of, supercritical medium Skellysolve A same volume (this light oil is gasoline fraction section product in the fischer-tropsch reaction product that obtains of embodiment 1) substitutes.React after 24 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer, and acquired results is as shown in table 3.
Embodiment 5
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
Prepare fischer-tropsch synthetic catalyst according to the method for embodiment 1 and carry out Fischer-Tropsch synthesis, unlike, the supercritical medium normal hexane of supercritical medium Skellysolve A same volume substitutes.React after 24 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer method, and acquired results is as shown in table 3.
Embodiment 6
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
Prepare fischer-tropsch synthetic catalyst according to the method for embodiment 2 and carry out Fischer-Tropsch synthesis, unlike, the supercritical medium normal hexane of supercritical medium Skellysolve A same volume substitutes.React after 48 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer method, and acquired results is as shown in table 3.
Embodiment 7
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
Fischer-Tropsch synthesis is carried out according to the method for embodiment 1, unlike, the catalyzer of described Fischer-Tropsch synthesis is non-egg-shell catalyst, and its concrete preparation method is as follows:
By the circular orifice extruded moulding that the rear diameter of pseudo-boehmite (Sasol company C1 powder) mixing of the β-molecular sieve of 10 % by weight same 90 % by weight is 1.4 millimeters, then bar will be extruded in 120 DEG C of dryings 4 hours, again in 600 DEG C of roastings 4 hours, obtain carrier.Then be in the cobalt nitrate aqueous solution of 238gCoO/L by saturated for above-mentioned for the 10g carrier 8mL of being immersed in concentration, then by the carrier after dipping prior to 120 DEG C of dryings 4 hours, then in 600 DEG C of roastings 4 hours, obtain fischer-tropsch synthetic catalyst D.The content of the active metal component cobalt adopting X-fluorescence method to measure in the fischer-tropsch synthetic catalyst obtained is 16 % by weight.Can be observed active metal component through naked eyes to be evenly distributed on this fischer-tropsch catalysts.
React after 24 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer method, and acquired results is as shown in table 3.
Embodiment 8
This embodiment is for illustration of the method for F-T synthesis provided by the invention.
Prepare fischer-tropsch synthetic catalyst according to the method for embodiment 1 and carry out Fischer-Tropsch synthesis, unlike, in the preparation process of fischer-tropsch synthetic catalyst, β-molecular sieve substitutes with the pseudo-boehmite (Sasol company C1 powder) of identical weight part.React after 24 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer method, and acquired results is as shown in table 3.
Comparative example 1
This comparative example is for illustration of the method for the F-T synthesis of reference.
Prepare fischer-tropsch synthetic catalyst according to the method for embodiment 1 and carry out Fischer-Tropsch synthesis, unlike, in Fischer-Tropsch synthesis process, do not inject supercritical medium normal hexane.React after 24 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the analytical results of each cut is as shown in table 2; In Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer method, and acquired results is as shown in table 2.
Comparative example 2
This comparative example is for illustration of the method for the F-T synthesis of reference.
Prepare fischer-tropsch synthetic catalyst according to the method for embodiment 2 and carry out Fischer-Tropsch synthesis, unlike, in Fischer-Tropsch synthesis process, do not inject supercritical medium normal hexane.React after 48 hours, evaluated transformation efficiency, the C of CO by the reaction product in fixed-bed reactor
5the selectivity of above hydro carbons and CH
4selectivity, its result is as shown in table 1 below.In addition, in Fischer-Tropsch synthesis product, the content of positive structure hydrocarbon and isomeric hydrocarbon is measured by vapor-phase chromatography method, and acquired results is as shown in table 3; The coke content reacted after 24 hours on fischer-tropsch synthetic catalyst is measured by sulphur carbon analyzer method, and acquired results is as shown in table 3.
Table 1
| Numbering | X CO，％ | S C5+，％ | S CH4，％ |
| Embodiment 1 | 84.77 | 81.11 | 10.16 |
| Embodiment 2 | 87.85 | 81.24 | 11.28 |
| Embodiment 3 | 62.23 | 89.30 | 5.12 |
| Embodiment 4 | 86.64 | 82.56 | 10.01 |
| Embodiment 5 | 82.53 | 81.41 | 10.24 |
| Embodiment 6 | 85.24 | 80.32 | 10.8 |
| Embodiment 7 | 75.03 | 75.47 | 17.25 |
| Embodiment 8 | 83.63 | 79.58 | 9.21 |
| Comparative example 1 | 83.17 | 75.10 | 17.40 |
| Comparative example 2 | 56.35 | 71.32 | 18.51 |
Table 2
Table 3
| Numbering | Positive structure hydrocarbon, % by weight | Isomeric hydrocarbon, % by weight | Carbon deposition quantity (% by weight) |
| Embodiment 1 | 52.20 | 47.80 | 0.83 |
| Embodiment 2 | 29.30 | 70.70 | 0.75 |
| Embodiment 3 | 58.89 | 41.11 | 1.02 |
| Embodiment 4 | 65.80 | 34.20 | 0.80 |
| Embodiment 5 | 63.15 | 36.85 | 0.85 |
| Embodiment 6 | 28.44 | 71.56 | 0.73 |
| Embodiment 7 | 52.79 | 47.21 | 0.89 |
| Embodiment 8 | 90.55 | 9.45 | 0.73 |
| Comparative example 1 | 52.42 | 47.58 | 2.36 |
| Comparative example 2 | 31.56 | 68.44 | 1.85 |
As can be seen from the above results, Fischer-Tropsch synthesis method provided by the invention is adopted can to obtain higher CO transformation efficiency and C
5+selectivity.As can be seen from the contrast of embodiment 1 and embodiment 4 and embodiment 7, when supercritical medium be the light oil that generates of F-T synthesis or distribute in shell on carrier when the active metal component in fischer-tropsch synthetic catalyst time, higher CO transformation efficiency and C can be obtained
5+selectivity.In addition, the products distribution adopting Fischer-Tropsch synthesis method provided by the invention can also make to obtain is to diesel oil and the skew of kerosene direction, and the coke content simultaneously on fischer-tropsch synthetic catalyst also can reduce, and has prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a method for F-T synthesis, under the method is included in F-T synthesis condition and under fischer-tropsch synthetic catalyst existence, reacted in supercritical medium by synthetic gas, described supercritical medium is selected from C
3-C
10alkane, C
3-C
10alkene, C
6-C
10aromatic hydrocarbons and F-T synthesis generate light oil at least one.
2. method according to claim 1, wherein, described supercritical medium is selected from least one in the light oil of Skellysolve A, normal hexane and F-T synthesis generation.
3. method according to claim 1 and 2, wherein, the consumption of described supercritical medium makes the dividing potential drop produced by it be 1-20MPa.
4. method according to claim 1 and 2, wherein, described fischer-tropsch synthetic catalyst is the compound fischer-tropsch synthetic catalyst containing molecular sieve.
5. method according to claim 4, wherein, the described compound fischer-tropsch synthetic catalyst containing molecular sieve comprises carrier and load active metal component on the carrier, described carrier contains with the molecular sieve of the gross weight of the described carrier 5-90 % by weight that is benchmark, the distribution in shell on the carrier of described active metal component.
6. method according to claim 5, wherein, with the gross weight of the described compound fischer-tropsch synthetic catalyst containing molecular sieve for benchmark, the content of described carrier is 30-99 % by weight, with the content of the described active metal component of oxide basis for 1-70 % by weight.
7. the method according to claim 5 or 6, wherein, at least one of described molecular screening in SAPO-11, SAPO-41, ZSM-22, ZSM-5, Y zeolite, β-molecular sieve and mordenite.
8. the method according to claim 5 or 6, described active metal component is at least one component in Fe, Co and Ru.
9. the method according to claim 5 or 6, wherein, the particle diameter of described carrier is 0.2-8mm, and the shell thickness of described shell distribution is 0.06-2mm.
10. method according to claim 1 and 2, wherein, it is 170-350 DEG C that described F-T synthesis condition comprises temperature, and total pressure is 2-20MPa, and during the gas of synthetic gas, volume space velocity is 3000-20000h
-1.
11. methods according to claim 10, wherein, H in described synthetic gas
2be 1-3:1 with the mol ratio of CO.
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| WO2019144950A1 (en) * | 2018-01-26 | 2019-08-01 | 中国科学院大连化学物理研究所 | Catalyst and method for directly converting synthesis gas into low-carbon olefin |
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| CN103695022B (en) * | 2013-12-09 | 2015-06-17 | 中国科学院山西煤炭化学研究所 | Fischer-Tropsch synthesis process applicable to fixed-bed reactor |
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