CN105312092A - Catalyst, preparation method thereof and Fischer-Tropsch synthesis method - Google Patents
Catalyst, preparation method thereof and Fischer-Tropsch synthesis method Download PDFInfo
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Abstract
The invention relates to a catalyst having an inner core-outer layer structure, a preparation method thereof and a Fischer-Tropsch synthesis method, wherein the catalyst includes an inner core and an outer layer coating the inner core. The inner core includes a first catalyst carrier and a purifying agent supported thereon. The outer layer includes a second catalyst carrier and a catalytic active metal component supported thereon. The first catalyst carrier and the second catalyst carrier are prepared from the same material. The catalyst has a tightly-combined inner core-outer layer structure, and not only has the purifying effect of a purifying agent, such as the desulfuration active metal component, but also has a catalytic reaction effect of catalyzing the active metal component. The two effects can synergistically improve the selectivity of the catalyst on C5+ hydrocarbons.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and Fischer-Tropsch synthesis method, particularly a kind of have the Catalysts and its preparation method of kernel-layer structure and adopt above-mentioned catalyst to carry out the method for F-T synthesis.
Background technology
In fixed bed reactors, Fischer-Tropsch (F-T) synthetic reaction 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 course of reaction is filled in catalyst granules duct with the form of liquid phase wax usually, and covers the surface of catalyst.Like this, when catalyst granules exceedes certain size, each reactive component of F-T synthesis will have a strong impact on the selective of chemical reaction rate and product in intragranular liquid phase diffusion, and diffusion controls to be difficult to avoid on the impact of catalytic performance.In reactant in diffusion process, H
2diffusion velocity faster than the diffusion velocity of CO, therefore, CO is obviously better than H in the diffusion restriction of catalyst granules inside
2.Because the particle diameter of catalyst granules 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 activated centre than increasing, carbon chain growth probability reduces, and thus reduces C
5+selective.
CN1988952A discloses a kind of layered catalyst for hydrodesulfurization reaction, comprise kernel and to be adhered on kernel and to have at least one to be selected from the skin of the refractory inorganic oxide of the metal component of cobalt, nickel, molybdenum and tungsten containing load on it, described kernel is selected from Alpha-alumina, θ-aluminium oxide, carborundum, metal, cordierite, zirconia, titanium oxide and composition thereof, and described skin is selected from gama-alumina, δ-aluminium oxide, θ-aluminium oxide, silica-alumina, zeolite, non-zeolite molecular sieve, titanium oxide and composition thereof.In addition, this patent application also disclose when kernel by refractory inorganic oxide (as titanium oxide) form time, outer refractory inorganic oxide must be different from inner refractory oxide, and internal layer refractory inorganic oxide has lower adsorption capacity relative to outer refractory inorganic oxide to catalytic metal precursor.
Active component mainly iron and the cobalt of fischer-tropsch synthetic catalyst.This type of catalyst is very responsive to sulfur poisoning, particularly for cobalt-base catalyst, requires the sulfur content in unstripped gas to take off to trace (requirement is less than 40ppb).In general, the agent of fixed bed upper catalyst is owing to preferentially touching poisonous substance, and easier inactivation is poisoning.In addition, because the existence of fischer-tropsch synthetic catalyst surface liquid film causes diffusional resistance, when adding gas, volume space velocity is very fast, and poisonous substance also can be made constantly to expand along beds.For general catalyst, if resistance to SO_2 is not good, within certain reaction time, the activity of catalyst can obviously reduce, thus loses stability and the economy of course of reaction.More seriously, the catalyst after being poisoned by sulfur is difficult to regeneration, can cause a large amount of losses of catalyst.
The sulfur poisoning of metallic catalyst is one of most thorny issue in catalytic field.The poisoning reduction not only causing himself service life of catalyst, reduces product quality simultaneously.That is familiar with catalytic action along with people deepens continuously, and the sulfur poisoning of catalyst is subject to people's attention day by day.Compared with metal oxide, because the electronegativity of sulphur is lower than oxygen, metal sulfide is more tending towards generating covalent compound.Limit by metal sulfide stability, in general, the sulphur of noxious metals position is difficult to remove completely.
In gas, Determination of Trace Sulfur and organic sulfur removes, based on solid dry method, dry desulfurization is widely used as meticulous desulfurization, if modern age is with in the large-scale ammonia plant that is raw material such as natural gas, light oil, the dry desulfurizations such as extensive use active carbon, zinc oxide, cobalt-molybdenum catalyst, make total sulfur content in unstripped gas be down to 1 below μ g/g.Containing a small amount of H
2the natural gas of S and RSH, can remove by alone ZnO.The natural gas that sulfur-bearing is higher, with active carbon and ZnO series connection desulfurization.If the COS in unstripped gas is more, first COS should be hydrolyzed, then remove with ZnO or active carbon, also before removing COS, first can remove partial vulcanization thing with iron oxide.If containing a small amount of mercaptan and thiophene, can remove by direct molecular sieve.(most typical be dimethyl sulphide [(CH to thioether
3)
2s]) Performance comparision stablize, more than 400 DEG C, just can resolve into alkene and H
2s.Thiophene (C
4h
4s) water insoluble, stable in properties, is heated to 500 DEG C of also difficult decomposition, there is the unstripped gas of this several sulfide first must use hydrogenation conversion catalyst, as catalyst such as Co-Mo, Ni-Mo, by after Organic sulfur hydro-conversion again with absorptions such as zinc oxide, use of also can connecting.To containing the higher liquid hydrocarbon of organic sulfur, first will through Co-Mo hydro-conversion, then through wet desulphurization, then remove with zinc oxide etc.
In existing Fischer-Tropsch synthesis process, in order to avoid the sulfur poisoning of fischer-tropsch synthetic catalyst, first sulfur content in unstripped gas is according to the method described above taken off to trace (be less than 40ppb) usually, and then carry out fischer-tropsch reaction under the existence of conventional fischer-tropsch synthetic catalyst.But even so, still inevitably there is the sulphur of trace in synthesis gas.The sulphur of these traces can have an impact to subsequent chemistry process, the particularly chemical process of those applied metal catalyst, and as synthetic ammonia and F-T synthesis etc., the impact be subject to is even more serious.Therefore the exploitation F-T synthetic catalyst that there is sulfur resistive and hold sulphur ability to raising catalyst stability, extending catalyst service life, improve integral production level and have significant positive role.
Summary of the invention
The object of the invention is to adopt existing method to carry out Fischer-Tropsch synthesis and there is the selective poor defect of fischer-tropsch synthetic catalyst to overcome, and provide a kind of can Optimization Technology, improve economy and the selective good Catalysts and its preparation method with kernel-layer structure and Fischer-Tropsch synthesis method.
The invention provides a kind of catalyst, wherein, described catalyst comprises kernel and is coated on the skin on described kernel, described kernel comprises the first catalyst carrier and the cleanser of load in described first catalyst carrier, described skin comprises the second catalyst carrier and the catalytically-active metals component of load in described second catalyst carrier, and described first catalyst carrier is identical with the material of the second catalyst carrier.
Present invention also offers a kind of preparation method of catalyst, the method comprises employing load has the first catalyst support powder of the compound of cleanser and/or the first catalyst carrier precursor powder to prepare kernel, and load had the second catalyst support powder of the compound of catalytically-active metals component and/or the second catalyst carrier precursor powder to be coated on described kernel, then drying and roasting is carried out, obtain the outer field catalyst comprising kernel and be coated on described kernel, described first catalyst support powder is identical with the second catalyst carrier precursor powder with the second catalyst support powder with the first catalyst carrier precursor powder.
In addition, present invention also offers a kind of Fischer-Tropsch synthesis method, the method comprises synthesis gas is synthesized liquid fuel under above-mentioned catalyst existent condition.
The present inventor finds through further investigation; on the carrier that the cleanser that can play the effect of purification raw material is two-layer inside and outside described catalyst with the catalytic metal active component load simultaneously can playing fcc raw material reagentia; the cleanser of kernel load such as desulfurizing agent can play the effect of purify protect to the catalyst in fixed bed downstream, reduce the inactivation that catalyst causes because of toxic poisoning.In addition, the ability of adsorbing hydrogen and dissociates hydrogen due to conventional cleanser (as desulfurizing agent) is very weak, and therefore the existence of cleanser (as desulfurizing agent) can not affect the catalytic performance of catalytic metal active component.The cleanser of kernel can avoid the waste of space and material; do not affect again the catalytic activity of catalyst; namely can by purify protect effect and synthetic reaction be organic reasonably integrates, thus play the operation cycle of extending catalyst, improve the good action of fixed-bed operation economy.
Moreover in existing layered catalyst, kernel and skin are different carrier materials, because both there are differences in hot property, cause calcined catalyst carrier kernel skin to combine not tight, easily produce the phenomenon of scaling.In addition, the preparation method of existing layered catalyst is: after obtained layered catalyst support, is loaded in catalyst carrier by the method for conventional impregnation by metal active constituent, like this, when flooding, and the easy inner layer migration of metal active constituent.And the kernel carrier of catalyst provided by the invention is identical with the material of outer carrier, and preferably adopt rolling ball method preparation outer, the catalyst obtained can be made like this to have the kernel-layer structure of combining closely, and due to play fcc raw material reagentia catalytically-active metals diversity in be distributed in skin, be conducive to C
5+the raising of hydrocarbon selective, is particularly suitable for the Fischer-Tropsch synthesis in producing, for the purpose of heavy paraffins.
Except Fischer-Tropsch synthesis catalyst, method for preparing catalyst provided by the invention is also applicable to other reactions, and as saturated in olefine selective hydrogenation, ethylene epoxy ethane etc. requires high catalytic reaction to material purity.
A preferred embodiment of the invention, when described catalyst is fischer-tropsch synthetic catalyst, and when the weight ratio of described desulphurizing activated metal component and catalytically-active metals component is 0.2-0.8:1, the catalyst obtained has higher C
5+hydrocarbon selective.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Catalyst provided by the invention comprises kernel and is coated on the skin on described kernel, described kernel comprises the first catalyst carrier and the cleanser of load in described first catalyst carrier, described skin comprises the second catalyst carrier and the catalytically-active metals component of load in described second catalyst carrier, and described first catalyst carrier is identical with the material of the second catalyst carrier.In the present invention, described cleanser can play the effect of purification raw material, and described catalytically-active metals component can play fcc raw material reagentia.
Described kernel and outer field thickness can be that the routine of this area is selected, but in order to make cleanser and catalytically-active metals component play better mating reaction, the average diameter of described kernel is preferably 1-6mm, is more preferably 1.5-4mm; Described outer field average thickness is preferably 0.05-3mm, is more preferably 0.1-1.5mm.In the present invention, described outer field thickness can adopt and ball be cut open rear slide measure and measure along catalyst radial direction or adopt the S-4700 type ESEM being configured with EDAX-9100 type X-ray energy spectrometer carry out section component analysis along catalyst radial direction and measure.
The kind of described cleanser can be selected according to needing in raw material the impurity purified, and such as, can be desulfurizing agent and/or deoxidier.In addition, the kind of described catalytically-active metals component can be selected in reaction as required.Such as, when described catalyst is fischer-tropsch synthetic catalyst, described cleanser is desulfurizing agent, and the desulphurizing activated metal component of described desulfurizing agent is selected from least one in zinc, iron, manganese molybdenum, cobalt molybdenum, iron molybdenum and cobalt nickel molybdenum, and described catalytically-active metals component is iron and/or cobalt.
For fischer-tropsch synthetic catalyst, with oxide basis and with the gross weight of described catalyst for benchmark, the total content of described desulphurizing activated metal component and catalytically-active metals component can be 1-80 % by weight, is preferably 1-60 % by weight, be more preferably 5-50 % by weight, most preferably be 10-40 % by weight.In addition, the weight ratio of described desulphurizing activated metal component and described catalytically-active metals component is particularly preferably 0.2-0.8:1, and described desulphurizing activated metal component and catalytically-active metals component can be made like this to play better mating reaction, thus obtains C
5+the fischer-tropsch synthetic catalyst that hydrocarbon selective is higher.
Described skin can also contain catalyst promoter.Those skilled in the art can according to the type of reaction and the suitable catalyst promoter of the type selecting of catalytically-active metals component.Such as, when described catalyst is fischer-tropsch synthetic catalyst, and described catalytically-active metals component is when being iron, described catalyst promoter can be at least one in the compound of IA race metal and the compound of I B-group metal, with oxide basis and with the gross weight of catalyst for benchmark, the content of the compound of IA race metal is 0-4 % by weight, the content of the compound of I B-group metal is 0-6 % by weight, is zero when the content of compound of IA race metal is different with the content of the compound of I B-group metal, or, when described catalyst is fischer-tropsch synthetic catalyst, and described catalytically-active metals component is when being cobalt, described catalyst promoter can be at least one in the compound of group VIII metal beyond the compound of group VIB metal and deironing and cobalt, with oxide basis and with the gross weight of catalyst for benchmark, the content of the compound of group VIB metal is 0-30 % by weight, the content of the compound of the group VIII metal beyond deironing and cobalt is 0-5 % by weight, the content of the compound of group VIB metal and deironing different with the content of the compound of the group VIII metal beyond cobalt time be zero.Particularly, the example of catalyst promoter comprises at least one in the compound of the metals such as palladium, ruthenium and tungsten.
The kind of described first catalyst carrier and described second catalyst carrier can be the normal selection of this area, such as, can be selected from least one in aluminium oxide, silica, alumina silicate, titanium oxide, zirconia and active carbon.
Described catalyst is except can be used in Fischer-Tropsch synthesis, other reactions can also be used for, as selective hydrogenation saturated reaction and the reaction of ethylene epoxy ethane etc., now, corresponding catalyst is respectively selective hydrogenation saturation catalyst and ethylene oxide catalyst.When described catalyst is selective hydrogenation saturation catalyst, cleanser can be desulfurizing agent and/or deoxidier, and catalytically-active metals component can be platinum and/palladium; With oxide basis and with the gross weight of catalyst for benchmark, the content of cleanser can be 0.1-10 % by weight, and the content of catalytically-active metals component can be 0.1-4 % by weight.When described catalyst is ethylene oxide catalyst, cleanser can be desulfurizing agent, and catalytically-active metals component can be silver; With oxide basis and with the gross weight of catalyst for benchmark, the content of cleanser can be 0.2-20 % by weight, and the content of catalytically-active metals component can be 4-60 % by weight.
The preparation method of catalyst provided by the invention comprises employing load has the first catalyst support powder of the compound of cleanser and/or the first catalyst carrier precursor powder to prepare kernel, and load had the second catalyst support powder of the compound of catalytically-active metals component and/or the second catalyst carrier precursor powder to be coated on described kernel, then drying and roasting is carried out, obtain the outer field catalyst comprising kernel and be coated on described kernel, described first catalyst support powder is identical with the second catalyst carrier precursor powder with the second catalyst support powder with the first catalyst carrier precursor powder.
The method adopting load to have the first catalyst support powder of cleanser and/or the first catalyst carrier precursor powder to prepare kernel can adopt the method for the various shaping of catalysts of this area routine to carry out, such as, can first will the slurry of the first catalyst support powder of the compound of cleanser and/or the first catalyst carrier precursor powder be had on screw extruder to be extruded into cylindrical bar containing load, then cylindrical bar balling-up in nodulizer of will extrude.Conventional extrusion aid and/or adhesive can be added in the first catalytic carrier powder and/or the first catalyst carrier precursor powder when shaping.The kind of described extrusion aid and/or adhesive and consumption are conventionally known to one of skill in the art, and therefore not to repeat here.
Load there are the second catalyst support powder of the compound of catalytically-active metals component and/or the second catalyst carrier precursor powder method be coated on described kernel that the method for the various shaping of catalysts of this area routine can be adopted to carry out, preferably, second catalyst fines and/or the second catalyst carrier precursor powder are immersed in the solution of the compound containing catalytically-active metals component and make wet-milling, then be coated on described kernel with rolling ball method; Or, second catalyst support powder and/or the second catalyst carrier precursor powder are immersed in the solution of the compound containing catalytically-active metals component also dry, again dried powder is carried out roasting or not roasting, then in the powder obtained, add water and make wet-milling, then be coated on described kernel with rolling ball method.Wherein, the concentration of the solution of the above-mentioned compound containing catalytically-active metals component can be 1-6mol/L.Described solution can be the aqueous solution, also can be organic solution, is preferably the aqueous solution.It can be 120-600 DEG C that the condition of described roasting comprises sintering temperature, is preferably 300-600 DEG C; Roasting time can be 1-48 hour, is preferably 2-12 hour.In addition, described second catalyst support powder and the second catalyst carrier precursor powder can be through roasting or unfired powder, are preferably unfired powder.
Moreover when adopting the second way to carry out coated, the step of described dipping, drying, roasting or not roasting can repeat 1-3 time, then adds water in the powder obtained and makes wet-milling, then be coated on described kernel by the method for spin.It is 50-300 DEG C that the condition of described drying comprises baking temperature, is preferably 100-250 DEG C; Drying time is 1-48 hour, is preferably 1-12 hour.In the powder obtained, add water makes in the step of wet-milling, and the amount adding water can calculate according to " saturated water absorption ", and those skilled in the art understands how to determine saturated water absorption and to calculate the amount needing the water added, therefore not to repeat here.
Described kernel and outer field thickness can be that the routine of this area is selected, but in order to make cleanser and catalytically-active metals component play better mating reaction, the average diameter of described kernel is preferably 1-6mm, is more preferably 1.5-4mm; Described outer field average thickness is preferably 0.05-3mm, is more preferably 0.1-1.5mm.In the concrete preparation process of described catalyst, can by regulate extrusion time orifice plate size and regulate the rotating speed of nodulizer to control the average diameter of kernel, then control outer field average thickness by the weight ratio of the second catalyst support powder and/or the second catalyst carrier precursor powder in the first catalyst support powder in kernel and/or the first catalyst carrier precursor powder and skin.Described rolling ball method is conventionally known to one of skill in the art, and therefore not to repeat here.
The kind of described cleanser can be selected according to needing in raw material the impurity purified, and such as, can be desulfurizing agent and/or deoxidier.In addition, the kind of described catalytically-active metals component also can be selected in reaction as required.Such as, when described catalyst is fischer-tropsch synthetic catalyst, described cleanser can be desulfurizing agent, and the desulphurizing activated metal component of described desulfurizing agent is selected from least one in zinc, iron, manganese molybdenum, cobalt molybdenum, iron molybdenum and cobalt nickel molybdenum, and described catalytically-active metals component is iron and/or cobalt.Correspondingly, the compound of described catalytically-active metals component can for the conventional compound that can form active metal component for Fischer-Tropsch synthesis catalyst, such as, it can be the compound of iron and/or cobalt, wherein, the compound of iron can be ferric nitrate and/or ironic citrate, and the compound of cobalt can be selected from one or more in cobalt nitrate, cobalt acetate, citric acid cobalt etc.
For fischer-tropsch synthetic catalyst, described load has the first catalyst support powder of the compound of cleanser (i.e. the compound of desulphurizing activated metal component) and/or the first catalyst carrier precursor powder and described load to have the consumption of the second catalyst support powder of catalytically-active metals component and/or the second catalyst carrier precursor powder to make with oxide basis and with the gross weight of described catalyst for benchmark, the total content of described desulphurizing activated metal component and catalytically-active metals component can be 1-80 % by weight, be preferably 1-60 % by weight, be more preferably 5-50 % by weight, most preferably be 10-40 % by weight.In addition, the weight ratio of described desulphurizing activated metal component and described catalytically-active metals component is particularly preferably 0.2-0.8:1, and described desulphurizing activated metal component and catalytically-active metals component can be made like this to play better mating reaction, thus obtains C
5+the fischer-tropsch synthetic catalyst that hydrocarbon selective is higher.
On described second catalyst support powder and/or the second catalyst precursor powder, also load has catalyst promoter, and the skin of the catalyst obtained can be made so also containing catalyst promoter.Those skilled in the art can according to the type of reaction and the suitable catalyst promoter of the type selecting of catalytically-active metals component.Such as, when described catalyst is fischer-tropsch synthetic catalyst, and described catalytically-active metals component is when being iron, described catalyst promoter can be at least one in the compound of IA race metal and the compound of I B-group metal, the consumption of described catalyst promoter makes with oxide basis and with the gross weight of catalyst for benchmark, the content of the compound of IA race metal is 0-4 % by weight, the content of the compound of I B-group metal is 0-6 % by weight, is zero when the content of compound of IA race metal is different with the content of the compound of I B-group metal, or, when described catalyst is fischer-tropsch synthetic catalyst, and described catalytically-active metals component is when being cobalt, described catalyst promoter can be at least one in the compound of group VIII metal beyond the compound of group VIB metal and deironing and cobalt, the consumption of described catalyst promoter makes with oxide basis and with the gross weight of catalyst for benchmark, the content of the compound of group VIB metal is 0-30 % by weight, the content of the compound of the group VIII metal beyond deironing and cobalt is 0-5 % by weight, the content of the compound of group VIB metal and deironing different with the content of the compound of the group VIII metal beyond cobalt time be zero.Particularly, the example of catalyst promoter comprises at least one in the compound of the metals such as palladium, ruthenium and tungsten.
Described first catalyst support powder and the first catalyst carrier precursor powder and the second catalyst support powder and the second catalyst carrier precursor powder can be the conventional powder for the preparation of catalyst, are preferably selected from one or more in boehmite, silica-alumina colloid, alumina silicate, silica, titanium oxide, zirconia and active carbon.Above-mentioned particle diameters can be 0.1-150 μm.Above-mentioned first catalyst support powder, the first catalyst carrier precursor powder, the second catalyst support powder and the second catalyst carrier precursor powder can by commercially available, as SB powder, C1 powder that Sasol company (former German condea company) produces, the CL powder that Chang Ling catalyst plant is produced, the aluminum silicon powder SA40 etc. of Research Institute of Petro-Chemical Engineering.
Fischer-Tropsch synthesis method provided by the invention comprises synthesis gas is synthesized liquid fuel under above-mentioned catalyst existent condition.
The resistance to SO_2 method for expressing of described catalyst: when synthesis gas continuous feed, the duration of runs of different catalysts when to investigate CO conversion ratio be 10%, the length of this time can be used for the difference of visual representation catalyst resistance to SO_2 under the situation of sulfur-bearing synthesis gas.Simultaneously according to the length in this reaction time, also can calculate the sulfur content entering reaction system, utilize the size into sulfur content also can compare the appearance sulphur ability of different catalysts, compare the resistance to SO_2 of different catalysts with this.
Before above-mentioned catalyst provided by the invention is used for Fischer-Tropsch synthesis, preferably in presence of hydrogen, first the active metal component of oxidation state is carried out reduction activation.Wherein, the condition of described reduction activation can comprise: reduction temperature is 200-1000 DEG C, is preferably 200-800 DEG C; Recovery time is 1-96 hour, is preferably 2-24 hour.In addition, described reduction activation can be carried out in pure hydrogen, and also can carry out in the mist of hydrogen and inert gas, as carried out in the gaseous mixture of hydrogen and nitrogen, wherein, Hydrogen Vapor Pressure can be 0.1-4MPa, is preferably 0.1-2MPa.What described inert gas was known to the skilled person does not variously participate in the gas of chemical reaction, as nitrogen and/or zero group gas under above-mentioned reduction activation condition.
In addition, the improvements of Fischer-Tropsch synthesis method provided by the invention are only to employ a kind of new catalyst, and the raw material of F-T synthesis and reaction condition can be all the selection of this area routine, and therefore not to repeat here.
Below will be described the present invention by embodiment.
Preparation example 1
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
Be that the sesbania powder of the boehmite powder (the SB powder purchased from Sasol company) of 10-120 micron and 6 grams is (purchased from Henan Lankao County natural plant gum factory by the particle diameter of 200 grams, lower same) mixing, then the concentration added containing 2 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, and add 27 grams of zinc nitrates, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, then at screw extruder (purchased from South China Science & Engineering University's science and technology industry head factory, model is F-26, the cylindrical bar of 1.5 millimeters is extruded into down together), get part again and extrude bar (being equivalent to spend totally 90 grams, SB powder) balling-up in nodulizer, obtain kernel.Through measuring, the average diameter of kernel is 3mm.28 grams of unfired boehmites being immersed in 26 ml concns is in the cobalt nitrate solution of 4.9mol/L and drying, the ratio of 1 gram of water is added according to every 3 grams of boehmites, have to load in the boehmite powder of cobalt nitrate and add water, and then the product obtained is sprayed to above-mentioned kernel is housed nodulizer in.Afterwards, by the sample that obtains prior to 140 DEG C of dryings 4 hours, again in 300 DEG C of roastings 4 hours, obtain comprising kernel and outer field catalyst A 1, wherein, with oxide basis and with the gross weight of catalyst A 1 for benchmark, the content of desulphurizing activated metal component is 2.81 % by weight, and the content of catalyst activity metal component is 10.07 % by weight.In addition, the average diameter of the kernel of catalyst A 1 is 3mm, and outer field average thickness is 0.14mm.
Preparation example 2
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
Be the boehmite (Chang Ling catalyst plant CL powder) of 10-120 micron and the sesbania powder mixing of 6 grams by the particle diameter of 200 grams, then the concentration added containing 3 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, and add 35 grams of zinc nitrates, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, on screw extruder, is then extruded into the cylindrical bar of 1.5 millimeters, then get part extrude bar (being equivalent to spend totally 125 grams, CL powder) balling-up in nodulizer, obtain kernel.Through measuring, the average diameter of kernel is 3mm.56 grams of unfired boehmites being immersed in 30 milliliters of mass concentrations is in the cobalt nitrate solution of 4mol/L and drying, the ratio of 1 gram of water is added according to every 2 grams of boehmites, have to load in the boehmite powder of cobalt nitrate and add water, and then the product obtained is sprayed to above-mentioned kernel is housed nodulizer in.Afterwards, by the sample that obtains prior to 140 DEG C of dryings 4 hours, again in 410 DEG C of roastings 4 hours, obtain comprising kernel and outer field catalyst A 2, wherein, with oxide basis and with the gross weight of catalyst A 2 for benchmark, the content of desulphurizing activated metal component is 3.42 % by weight, and the content of catalyst activity metal component is 6.41 % by weight.In addition, the average diameter of the kernel of catalyst A 2 is 3mm, and outer field average thickness is 0.2mm.
Preparation example 3
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
Be the boehmite powder (the SB powder purchased from Sasol company) of 10-120 micron and the sesbania powder mixing of 6 grams by the particle diameter of 200 grams, then the concentration added containing 3 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, and add 10 grams of zinc hydroxides, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, on screw extruder, is then extruded into the cylindrical bar of 1.5 millimeters, then get part extrude bar (being equivalent to spend totally 125 grams, SB powder) balling-up in nodulizer, obtain kernel.Through measuring, the average diameter of kernel is 3mm.56 grams of unfired boehmites being immersed in 42 ml concns is in the cobalt nitrate solution of 5mol/L and drying, the ratio of 0.8 gram of water is added according to every 3 grams of boehmites, have to load in the boehmite powder of cobalt nitrate and add water, and then the product obtained is sprayed to above-mentioned kernel is housed nodulizer in.Afterwards, by the sample that obtains prior to 140 DEG C of dryings 4 hours, again in 350 DEG C of roastings 4 hours, obtain comprising kernel and outer field catalyst A 3, wherein, with oxide basis and with the gross weight of catalyst A 3 for benchmark, the content of desulphurizing activated metal component is 2.80 % by weight, and the content of catalyst activity metal component is 10.75 % by weight.In addition, the average diameter of the kernel of catalyst A 3 is 3mm, and outer field average thickness is 0.21mm.
Preparation example 4
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
Be the boehmite (Sasol company C1 powder) of 10-120 micron and the sesbania powder mixing of 6 grams by the particle diameter of 200 grams, then the concentration added containing 3 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, and add 20 grams of ferric nitrates, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, on screw extruder, is then extruded into the cylindrical bar of 1.5 millimeters, then get part and extrude bar (being equivalent to spend totally 125 grams, C1 powder) after balling-up, obtain kernel in nodulizer.Through measuring, the average diameter of kernel is 3mm.By 60 grams of boehmite powder 600 DEG C of roastings after 4 hours, being immersed in 23 ml concns is in the cobalt nitrate solution of 5mol/L and drying, the ratio of 0.8 gram of water is added according to every 3 grams of boehmites, have to load in the boehmite powder of cobalt nitrate and add water, and then the product obtained is sprayed to above-mentioned kernel is housed nodulizer in.Afterwards, by the sample that obtains prior to 140 DEG C of dryings 4 hours, again in 410 DEG C of roastings 4 hours, obtain comprising kernel and outer field catalyst A 4, wherein, with oxide basis and with the gross weight of catalyst A 4 for benchmark, the content of desulphurizing activated metal component is 1.59 % by weight, and the content of catalyst activity metal component is 6.15 % by weight.In addition, the average diameter of the kernel of catalyst A 4 is 3mm, and outer field average thickness is 0.2mm.
Preparation example 5
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
Be the aluminum silicon powder (Research Institute of Petro-Chemical Engineering SA40) of 10-120 micron and the sesbania powder mixing of 6 grams by the particle diameter of 200 grams, then the concentration added containing 3 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, and add 20 grams of zinc oxide, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, on screw extruder, is then extruded into the cylindrical bar of 1.5 millimeters, then get part and extrude bar (being equivalent to spend totally 125 grams, SA40 powder) after balling-up, obtain kernel in nodulizer.Through measuring, the average diameter of kernel is 3mm.It is in the cobalt nitrate solution of 5.5mol/L that 70 grams of aluminum silicon powders without roasting are immersed in 40 ml concns, then not drying directly by powder spray in the nodulizer that above-mentioned kernel is housed.Afterwards, by the sample that obtains prior to 180 DEG C of dryings 4 hours, again in 410 DEG C of roastings 4 hours, obtain comprising kernel and outer field catalyst A 5, wherein, with oxide basis and with the gross weight of catalyst A 5 for benchmark, the content of desulphurizing activated metal component is 7.58 % by weight, and the content of catalyst activity metal component is 10 % by weight.In addition, the average diameter of the kernel of catalyst A 5 is 3mm, and outer field average thickness is 0.23mm.
Preparation example 6
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
According to the method Kaolinite Preparation of Catalyst of preparation example 1, unlike, in outer field process preparation, the iron nitrate solution of to be cobalt nitrate solution 26 ml concns of 4.9mol/L by 26 ml concns be 4.9mol/L substitutes, obtain comprising kernel and outer field catalyst A 6, wherein, with oxide basis and with the gross weight of catalyst A 6 for benchmark, the content of desulphurizing activated metal component is 2.83 % by weight, and the content of catalyst activity metal component is 9.71 % by weight.In addition, the average diameter of the kernel of catalyst A 6 is 3mm, and outer field average thickness is 0.15mm.
Preparation example 7
This preparation example is for illustration of Catalysts and its preparation method provided by the invention.
According to the method Kaolinite Preparation of Catalyst of preparation example 1, unlike, in outer field preparation process, also add ammonium metatungstate, making to go back load in the outer core obtained has catalyst promoter tungsten, and detailed process is as follows:
Be the boehmite powder (the SB powder purchased from Sasol company) of 10-120 micron and the sesbania powder mixing of 6 grams by the particle diameter of 200 grams, then the concentration added containing 2 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, and add 27 grams of zinc nitrates, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, on screw extruder, is then extruded into the cylindrical bar of 1.5 millimeters, then get part extrude bar (being equivalent to spend totally 90 grams, SB powder) balling-up in nodulizer, obtain kernel.Through measuring, the average diameter of kernel is 3mm.28 grams of unfired boehmites being immersed in 26 milliliters contains in the aqueous solution of the ammonium metatungstate of 4.9mol/L cobalt nitrate and 0.02mol/L also dry, the ratio of 1 gram of water is added according to every 3 grams of boehmites, have to load in the boehmite powder of cobalt nitrate and ammonium metatungstate and add water, and then the product obtained is sprayed to above-mentioned kernel is housed nodulizer in.Afterwards, by the sample that obtains prior to 140 DEG C of dryings 4 hours, again in 300 DEG C of roastings 4 hours, obtain comprising kernel and outer field catalyst A 7, wherein, with oxide basis and with the gross weight of catalyst A 7 for benchmark, the content of desulphurizing activated metal component is 3.43 % by weight, the content of catalyst activity metal component is 9.86 % by weight, and the content of catalyst promoter is 1.50 % by weight.In addition, the average diameter of the kernel of catalyst A 7 is 3mm, and outer field average thickness is 0.14mm.
Contrast preparation example 1
This contrast preparation example is for illustration of the Catalysts and its preparation method of reference.
According to the method Kaolinite Preparation of Catalyst of preparation example 1, unlike, in the preparation process of kernel, do not add zinc nitrate in solution, make non-load in the kernel obtained have desulphurizing activated metal component, detailed process is as follows:
Be the boehmite powder (the SB powder purchased from Sasol company) of 10-120 micron and the sesbania powder mixing of 6 grams by the particle diameter of 200 grams, then the concentration added containing 2 grams of nitric acid is the aqueous solution of nitric acid of 1.6 mol/L, add water wherein afterwards, to control the weight ratio of the water in mixture and described boehmite powder 0.8.Said mixture is mixed, on screw extruder, is then extruded into the cylindrical bar of 1.5 millimeters, then get part extrude bar (being equivalent to spend totally 90 grams, SB powder) balling-up in nodulizer, obtain kernel.Through measuring, the average diameter of kernel is 3mm.28 grams of unfired boehmites being immersed in 26 ml concns is in the cobalt nitrate solution of 4.9mol/L and drying, the ratio of 1 gram of water is added according to every 3 grams of boehmites, have to load in the boehmite powder of cobalt nitrate and add water, and then the product obtained is sprayed to above-mentioned kernel is housed nodulizer in.Afterwards, by the sample that obtains prior to 140 DEG C of dryings 4 hours, then in 300 DEG C of roastings 4 hours, obtain comprising kernel and outer field reference catalyst DA1, wherein, with oxide basis and with the gross weight of reference catalyst DA1 for benchmark, the content of catalyst activity metal component is 10.37 % by weight.In addition, the average diameter of the kernel of reference catalyst DA1 is 3mm, and outer field average thickness is 0.14mm.
Embodiment 1-7
Embodiment 1-7 is for illustration of Fischer-Tropsch synthesis provided by the invention.
Be filled in fixed bed reactors by the catalyst A 1-A7 that preparation example 1-7 prepares respectively, the amount of fill of catalyst is 2 grams.Then, inject hydrogen with the flow of 1000NL/g-cat/h (representing that relative to every gram of catalyst flow hourly be 1000 standard liters), and be warming up to 400 DEG C with the heating rate of 4 DEG C/min, and keep 5 hours at such a temperature.
Then, 210 DEG C, under 2.5MPa, with 2000h
-1gas hourly space velocity (GHSV) in described fixed bed reactors, pass into H
2, CO mist (H
2/ CO mol ratio is 2), thus carry out Fischer-Tropsch synthesis.React after 12 hours, switch the H being mixed with hydrogen sulfide that the concentration passed into containing sulphur is 6.37 μ g/L
2, CO mist (H
2/ CO mol ratio is 2), the conversion ratio (X of CO is evaluated by the product in described fixed bed reactors
cO), C
5(C above
5+) hydro carbons selective
cH
4selective
and CO
2selective
obtain different catalysts CO conversion ratio to 10% time, different catalysts hold sulfur content, its result is as shown in table 1 below.Particularly, X
cO, C
5+,
with
calculate respectively by following formula:
Wherein, V
1, V
2under being illustrated respectively in the status of criterion, entering the volume of the unstripped gas of reaction system in certain time period and flow out the exhaust gas volumes of reaction system; c
1, CO, c
2, COrepresent the content of CO in unstripped gas and tail gas respectively.N
confor being participated in the molal quantity of the CO of reaction in certain time period by reaction bed,
for generating CO
2the molal quantity of CO,
for generating CH
4the molal quantity of CO,
for generating CH
4, C
2hydrocarbon, C
3hydrocarbon and C
4the molal quantity sum of the CO of hydrocarbon, result is as shown in table 1.
Comparative example 1
This comparative example is for illustration of the Fischer-Tropsch synthesis of reference.
Carry out reduction activation according to the method for embodiment 1 and carry out Fischer-Tropsch synthesis, unlike, substituted by the reference catalyst DA1 of catalyst A 1 with identical weight part, result is as shown in table 1.
Table 1
As can be seen from contrast with comparative example 1 of embodiment 1, kernel-outer layer catalyst provided by the invention has catalytic activity and the C of raising in Fischer-Tropsch synthesis
5+hydrocarbon selective, and carbon dioxide and the selective of methane also significantly reduce; Meanwhile, in kernel load after cleanser, when reaching certain conversion ratio, catalyst can hold more sulphur, illustrates that its resistance to SO_2 enhances.In addition, the preparation method of catalyst involved in the present invention compared with the preparation method of traditional catalyst, have simple to operation, repeatability is strong, kernel and skin in conjunction with the advantage such as firm, have 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 detailed description of the invention, 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 combination.
In addition, also can be combined 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 (17)
1. a catalyst, it is characterized in that, described catalyst comprises kernel and is coated on the skin on described kernel, described kernel comprises the first catalyst carrier and the cleanser of load in described first catalyst carrier, described skin comprises the second catalyst carrier and the catalytically-active metals component of load in described second catalyst carrier, and described first catalyst carrier is identical with the material of the second catalyst carrier.
2. catalyst according to claim 1, wherein, the average diameter of described kernel is 1-6mm, and described outer field average thickness is 0.05-3mm.
3. catalyst according to claim 1, wherein, described cleanser is desulfurizing agent and/or deoxidier.
4. according to the catalyst in claim 1-3 described in any one, wherein, described catalyst is fischer-tropsch synthetic catalyst, described cleanser is desulfurizing agent, and the desulphurizing activated metal component of described desulfurizing agent is selected from least one in zinc, iron, manganese molybdenum, cobalt molybdenum, iron molybdenum and cobalt nickel molybdenum, described catalytically-active metals component is iron and/or cobalt.
5. catalyst according to claim 4, wherein, with oxide basis and with the gross weight of described catalyst for benchmark, the total content of described desulphurizing activated metal component and catalytically-active metals component is 1-80 % by weight.
6. catalyst according to claim 5, wherein, the weight ratio of described desulphurizing activated metal component and described catalytically-active metals component is 0.2-0.8:1.
7. catalyst according to claim 4, wherein, described skin is also containing catalyst promoter; Described catalytically-active metals component is iron, described catalyst promoter is at least one in the compound of IA race metal and the compound of I B-group metal, with oxide basis and with the gross weight of catalyst for benchmark, the content of the compound of IA race metal is 0-4 % by weight, the content of the compound of I B-group metal is 0-6 % by weight, is zero when the content of compound of IA race metal is different with the content of the compound of I B-group metal; Or, described catalytically-active metals component is cobalt, described catalyst promoter is at least one in the compound of group VIII metal beyond the compound of group VIB metal and deironing and cobalt, with oxide basis and with the gross weight of catalyst for benchmark, the content of the compound of group VIB metal is 0-30 % by weight, the content of the compound of the group VIII metal beyond deironing and cobalt is 0-5 % by weight, is zero when the content of the compound of group VIB metal is different from the content of the compound of the group VIII metal beyond deironing and cobalt.
8. catalyst according to claim 4, wherein, the first catalyst carrier and described second catalyst carrier are selected from least one in aluminium oxide, silica, alumina silicate, titanium oxide, zirconia and active carbon.
9. the preparation method of a catalyst, the method comprises employing load has the first catalyst support powder of the compound of cleanser and/or the first catalyst carrier precursor powder to prepare kernel, and load had the second catalyst support powder of the compound of catalytically-active metals component and/or the second catalyst carrier precursor powder to be coated on described kernel, then drying and roasting is carried out, obtain the outer field catalyst comprising kernel and be coated on described kernel, described first catalyst support powder is identical with the second catalyst carrier precursor powder with the second catalyst support powder with the first catalyst carrier precursor powder.
10. preparation method according to claim 9, wherein, method load being had the second catalyst support powder of the compound of catalytically-active metals component and/or the second catalyst carrier precursor powder to be coated on described kernel is:
Second catalyst support powder and/or the second catalyst carrier precursor powder are immersed in the solution of the compound containing catalytically-active metals component and make wet-milling, then be coated on described kernel with rolling ball method; Or,
Second catalyst support powder and/or the second catalyst carrier precursor powder are immersed in the solution of the compound containing catalytically-active metals component also dry, again dried powder is carried out roasting or not roasting, then in the powder obtained, add water and make wet-milling, then be coated on described kernel with rolling ball method.
11. preparation methods according to claim 9, wherein, the average diameter of described kernel is 1-6mm, and described outer field average thickness is 0.05-3mm.
12. preparation methods according to claim 9, wherein, described cleanser is desulfurizing agent and/or deoxidier.
13. according to the preparation method in claim 9-12 described in any one, wherein, described catalyst is fischer-tropsch synthetic catalyst, described cleanser is desulfurizing agent, and the desulphurizing activated metal component of described desulfurizing agent is selected from least one in zinc, iron, manganese molybdenum, cobalt molybdenum, iron molybdenum and cobalt nickel molybdenum, described catalytically-active metals component is iron and/or cobalt.
14. preparation methods according to claim 13, wherein, described load has the first catalyst support powder of the compound of cleanser and/or the first catalyst carrier precursor powder and described load to have the consumption of the second catalyst support powder of the compound of catalytically-active metals component and/or the second catalyst carrier precursor powder to make with oxide basis and with the gross weight of the catalyst obtained for benchmark, the total content of described desulphurizing activated metal component and catalytically-active metals component is 1-80 % by weight; The weight ratio of described desulphurizing activated metal component and described catalytically-active metals component is 0.2-0.8:1.
15. preparation methods according to claim 13, wherein, on described second catalyst support powder and/or the second catalyst carrier precursor powder, also load has catalyst promoter, described catalytically-active metals component is iron, described catalyst promoter is at least one in the compound of IA race metal and the compound of I B-group metal, the consumption of described catalyst promoter makes with oxide basis and with the gross weight of the catalyst obtained for benchmark, the content of the compound of IA race metal is 0-4 % by weight, the content of the compound of I B-group metal is 0-6 % by weight, is zero when the content of compound of IA race metal is different with the content of the compound of I B-group metal, or, described catalytically-active metals component is cobalt, described catalyst promoter is at least one in the compound of group VIII metal beyond the compound of group VIB metal and deironing and cobalt, the consumption of described catalyst promoter makes with oxide basis and with the gross weight of the catalyst obtained for benchmark, the content of the compound of group VIB metal is 0-30 % by weight, the content of the compound of the group VIII metal beyond deironing and cobalt is 0-5 % by weight, the content of the compound of group VIB metal is zero time different from the content of the compound of the group VIII metal beyond deironing and cobalt.
16. preparation methods according to claim 13, wherein, described first catalyst support powder and the first catalyst carrier precursor powder and the second catalyst support powder and the second catalyst carrier precursor powder are selected from one or more in boehmite, silica-alumina colloid, alumina silicate, silica, titanium oxide, zirconia and active carbon.
17. 1 kinds of Fischer-Tropsch synthesis methods, the method comprises synthesis gas is synthesized liquid fuel under catalyst existent condition, and it is characterized in that, described catalyst is the catalyst in claim 1-8 described in any one.
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| CN110773176A (en) * | 2019-11-08 | 2020-02-11 | 中国石油化工股份有限公司 | Catalyst for reducing sulfur content of petroleum coke, preparation method and application thereof |
| CN114950430A (en) * | 2022-05-16 | 2022-08-30 | 东莞理工学院 | Yolk-eggshell structure Fe @ ZrO 2 Preparation method and application of Fischer-Tropsch synthesis catalyst |
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| CN101757952A (en) * | 2008-12-23 | 2010-06-30 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and Fischer-Tropsch method |
| CN103272603A (en) * | 2013-05-21 | 2013-09-04 | 神华集团有限责任公司 | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof |
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| CN101602000A (en) * | 2009-07-15 | 2009-12-16 | 神华集团有限责任公司 | A kind of Fischer-Tropsch synthesis contain cobalt auxiliary agent iron catalyst and preparation method thereof |
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| CN110773176A (en) * | 2019-11-08 | 2020-02-11 | 中国石油化工股份有限公司 | Catalyst for reducing sulfur content of petroleum coke, preparation method and application thereof |
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| CN114950430A (en) * | 2022-05-16 | 2022-08-30 | 东莞理工学院 | Yolk-eggshell structure Fe @ ZrO 2 Preparation method and application of Fischer-Tropsch synthesis catalyst |
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