CN103464169B - A kind of catalyst used for Fischer-Tropsch synthesis and Synthesis and applications thereof - Google Patents
A kind of catalyst used for Fischer-Tropsch synthesis and Synthesis and applications thereof Download PDFInfo
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Abstract
A kind of catalyst used for Fischer-Tropsch synthesis and Synthesis and applications thereof, this catalyst contains carrier, load iron on this carrier and/or cobalt metal component, take catalyst as benchmark, with the content of the iron of oxide basis and/or cobalt for 5-60 % by weight, in the content of the carrier of aluminium oxide for 40-95 % by weight, wherein, described carrier is the article shaped of alumina hydrate-containing.Compared with existing technical method, carbon monoxide-olefin polymeric provided by the invention not only has excellent F-T synthesis performance, and in addition, the preparation method of this catalyst is simple, production cost is starkly lower than catalyst prepared by existing method.
Description
Technical field
The present invention relates to a kind of catalyst used for Fischer-Tropsch synthesis and Synthesis and applications thereof.
Background technology
20th century the '30s, Fischer-Tropsch (FT or F-T) synthesis is at first in German Industrial, the U.S., France, the former Soviet Union and China etc. also establish similar artificial oil factory subsequently, after World War II because this route artificial oil cost is relatively high, benefit can not with oil competition and closing one after another, only have South Africa according to the F-T synthesis technology (fischer-tropsch synthesis process of Sasol company) of the national conditions Development of Coal liquefaction of national rich coal resources at present still at not development and improvement.Twentieth century seventies, Shell company of Holland started the research of F-T synthesis, and the Co catalysts of their development to be founded the factory operation in 1993 in Malaysia.In recent years; along with being becoming tight the day of petroleum resources, soaring, the continuous increase to the progressively harsh of demanded fuel and coal and natural gas proved reserves of crude oil price; make FT synthesize the research in this field very active, many companies research and develop on F-T synthesis.
Carrier is very complicated on the impact of Co catalysts in Fischer-Tropsch synthesis, and offshore company also differs from one another in the selection of catalyst carrier and the preparation of catalyst.SiO
2surface area is high, is conventional carrier, researches and develops as main also industrialization in the world with Shell company.Al
2o
3wearability good, mechanical strength is high, be applicable to slurry bed system operation, in the world based on the research and development of Sasol, Gulf/Chevron and Statoil company.TiO
2often need other oxide (as SiO as carrier
2, Al
2o
3and ZrO
2) carry out modification, in the world based on the research and development of Exxon-Mobil company.Also researcher is had in conventional molecular sieve (Appl.Catal.A, 1999,186,145-168), mesoporous molecular sieve (J.Catal., 2002,206,230-241) and activated carbon (Chinese patent CN01136889) carrier aspect work.
In iron-based FT synthetic catalyst, there is loading type iron (ZL01134919.0-activated carbon at present, CN200710172862.2-silica gel, CN200610165099.6-aluminium oxide), the catalyst such as precipitated iron (CN201110268041.5) and molten iron skeleton iron (ZL98119955.0).
Prior art shows, the difference of support, and the performance of FT synthetic catalyst is very large by difference.
Summary of the invention
That the technical problem to be solved in the present invention is to provide a kind of new FT catalyst for synthesizing and Synthesis and applications.
The content that the present invention relates to comprises:
1, a kind of catalyst used for Fischer-Tropsch synthesis, containing carrier, load iron on this carrier and/or cobalt metal component, take catalyst as benchmark, with the content of the iron of oxide basis and/or cobalt for 5-60 % by weight, in the content of the carrier of aluminium oxide for 40-95 % by weight, wherein, described carrier is the article shaped of alumina hydrate-containing.
2, the catalyst according to 1, is characterized in that, take catalyst as benchmark, with the content of the iron of oxide basis and/or cobalt for 10-50 % by weight, in the content of the carrier of aluminium oxide for 50-90 % by weight, wherein, described carrier is the article shaped of alumina hydrate-containing.
3, the catalyst according to 1, is characterized in that, the article shaped of described alumina hydrate-containing contains hydrated alumina and cellulose ether, and the radial crushing strength of described article shaped is more than or equal to 12N/mm, and water absorption rate is that 0.4-1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
4, the catalyst according to 3, is characterized in that, the radial crushing strength of described article shaped is 15-30N/mm, and water absorption rate is that 0.6-1, δ are less than or equal to 5%.
5, the catalyst according to 3, is characterized in that, with described article shaped for benchmark, the content of described cellulose ether is 0.5-8 % by weight.
6, the catalyst according to 5, is characterized in that, with described article shaped for benchmark, the content of described cellulose ether is 1-6 % by weight.
7, the catalyst according to 6, is characterized in that, with described article shaped for benchmark, the content of described cellulose ether is 2-5 % by weight.
8, the catalyst according to 3, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
9, the catalyst according to 8, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
10, the catalyst according to 1, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
11, the catalyst according to 10, is characterized in that, described hydrated alumina is boehmite.
12, the catalyst according to 1, it is characterized in that, described catalyst, also containing one or more adjuvant components be selected from La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd, is benchmark in element and with catalyst, and the content of described auxiliary agent is 0.001-25 % by weight.
13, the catalyst according to 12, is characterized in that, is benchmark in element and with catalyst, and the introduction volume of described adjuvant component is 0.01-10 % by weight.
14, a kind of preparation method of catalyst used for Fischer-Tropsch synthesis, comprise and prepare carrier and load iron and/or cobalt metal component also drying on this carrier, wherein, described carrier is the article shaped of alumina hydrate-containing, take catalyst as benchmark, the consumption of each component to make in described catalyst with the content of the iron of oxide basis and/or cobalt for 5-60 % by weight, in the content of the carrier of aluminium oxide for 40-95 % by weight, the condition of described drying comprises: temperature is 80-250 DEG C, and the time is 1-15 hour.
15, the method according to 14, it is characterized in that, take catalyst as benchmark, the consumption of each component to make in described catalyst with the content of the iron of oxide basis and/or cobalt as 10-50 % by weight, in the content of the carrier of aluminium oxide for 50-90 % by weight, the condition of described drying comprises: temperature 100-180 DEG C, and drying time is 2-6 hour.
16, the method according to 14, is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina.
17, the method according to 16, is characterized in that, described hydrated alumina is boehmite.
18, the method according to 14, it is characterized in that, described moisture and preparation method that is aluminium oxide article shaped comprises hydrated alumina and cellulose ether mixing, shaping and dry, the consumption of each component and shaping and drying condition make the radial crushing strength of described article shaped be more than or equal to 12N/mm, water absorption rate is that 0.4-1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
19, the method according to 18, is characterized in that, the consumption of each component and shaping and drying condition make the radial crushing strength of described article shaped be 15-30N/mm, and water absorption rate is that 0.6-1, δ are less than or equal to 5%.
20, the method according to 18, is characterized in that, with described article shaped for benchmark, the consumption of described cellulose ether is 0.5-8 % by weight, and described drying condition comprises: temperature 60 C to being less than 350 DEG C, drying time 1-48 hour.
21, the method according to 20, is characterized in that, with described article shaped for benchmark, the consumption of described cellulose ether is 1%-6 % by weight, and described drying condition comprises: temperature 80-150 DEG C, drying time 2-14 hour.
22, the method according to 21, is characterized in that, with described article shaped for benchmark, the consumption of described cellulose ether is 2%-5 % by weight, and described drying condition comprises: temperature 100-130 DEG C, drying time 3-10 hour.
23, the method according to 18, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
24, the method according to 23, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
25, the method according to 14, it is characterized in that, also comprise the step introducing one or more adjuvant components be selected from La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd in carrier, be benchmark in element and with catalyst, the introduction volume of described adjuvant component is no more than 25 % by weight.
26, the method according to 26, is characterized in that, is benchmark in element and with catalyst, and the introduction volume of described adjuvant component is 0.01-10 % by weight.
27, a Fischer-Tropsch synthesis method, under being included in Fischer-Tropsch synthesis condition, by the gas containing hydrogen and carbon monoxide and catalyst exposure, wherein, the catalyst that described catalyst provides for 1-13 any one claim.
According to the article shaped of alumina hydrate-containing provided by the invention, the radial crushing strength of preferred described article shaped is 15-30N/mm, and water absorption rate is that 0.6-1, δ are less than or equal to 5%.Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of hydrated alumina forming matter, and Q2 is hydrated alumina forming matter through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
The size of δ value represents hydrated alumina forming matter through the change (or be called loss of strength rate) of water soaking anteroposterior diameter to crushing strength.In the present invention, the measuring method of the radial crushing strength of described article shaped is carried out according to RIPP25-90 catalyst compressive resistance determination method, and the concrete steps measured about the radial crushing strength of article shaped have detailed introduction at RIPP25-90, do not repeat here.
Described water absorption rate adopts following concrete grammar to measure: first dried 4 hours by testing sample 120 DEG C.Take out sample, be positioned in desiccator and be cooled to room temperature, with 40 mesh standard sieve screenings, take oversize 20g (numbering: w1) testing sample, add 50g deionized water, soak 30min, filter, solid phase drains 5min, weigh solid phase weight (numbering: w2), solid phase be transferred in baking oven, 120 DEG C of heating, dryings 4 hours, are positioned in desiccator and are cooled to room temperature.Water absorption rate=(w2-w1)/w1
Be enough under the prerequisite that the radial crushing strength of described article shaped, water absorption rate and loss of strength rate are met the demands, the content of the present invention to cellulose ether is not particularly limited, in a particular embodiment, with hydrated alumina forming matter total amount for benchmark, the content of cellulose ether is preferably 0.5-8 % by weight, more preferably 1-6 % by weight, is more preferably 2-5 % by weight.Described cellulose ether preferably in methylcellulose, HEMC, hydroxypropyl methylcellulose one or more, further preferably methylcellulose, HEMC and their mixture wherein.
According to hydrated alumina forming matter provided by the invention, wherein can containing the adjuvant component not affecting or be of value to radial crushing strength, water absorption rate and the δ value of improving described article shaped.Such as, containing starch addO-on therapy, described starch can be the powder obtained through pulverizing by vegetable seeds arbitrarily, as sesbania powder.
Described hydrated alumina is selected from the hydrated alumina that any one can be used as adsorbent and catalyst carrier precursor, such as, can be boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, preferred boehmite.
According to the preparation method of hydrated alumina forming matter provided by the invention, described forming method can be arbitrary prior art.Such as, described forming method can be the forming method of extrusion, round as a ball, compressing tablet and their combination.For ensureing shaping carrying out smoothly, auxiliary agent and water etc. can be introduced herein in material (being the mixture of hydrated alumina and cellulose ether) when shaping, such as, when adopting extrusion method shaping, comprise by described hydrated alumina and cellulose ether and water, containing or do not mix containing extrusion aid, then extrusion molding, obtains wet bar, then drying obtains article shaped of the present invention.Described auxiliary agent is selected from starch, and described starch can be the powder obtained through pulverizing by vegetable seeds arbitrarily, as sesbania powder.Preferred forming method is the method for extruded moulding.Described drying condition comprises: temperature 60 C to being less than 350 DEG C, drying time 1-48 hour, preferable temperature is 80-150 DEG C, and drying time is 1-15h, and further preferable temperature is 100-130 DEG C, and drying time is 2-10h.
The method of described load iron and/or cobalt on shaping water and alumina support is preferably the method for dipping, and described dipping method is conventional method, such as hole saturation dipping, excessive immersion stain and spray impregnating.Wherein, comprise preparation dipping solution, such as, with the compound preparation dipping solution containing described iron and/or cobalt, afterwards by the method for this dipping solution difference impregnated carrier.Described drying means is the method for conventional method, such as heating, drying, and described drying condition condition comprises: baking temperature 80-250 DEG C, preferred 100-180 DEG C, and drying time, 1-15 hour, was preferably 2-6 hour.
The compound of described iron content and/or cobalt is selected from one or more in their soluble compound, such as, can be one or more in the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.Wherein, the preferred ferric nitrate of iron containing compounds, the preferred cobalt nitrate of cobalt compound.
Prior art shows, introduces one or more adjuvant components be selected from La, Zr, Ce, W, Cu, Mn or K in fischer-tropsch synthetic catalyst; Introduce one or more adjuvant components be selected from Ru, Re, Pt and Pd, favourable to the serviceability improving catalyst.Optionally, the present invention preferably quotes these promoter metal components in the catalyst.Be benchmark in element and with catalyst, the introduction volume of above-mentioned auxiliary agent is 0.001-25 % by weight, is preferably 0.01-10 % by weight.
When in described catalyst containing one or more adjuvant components be selected from La, Zr, Ce, W, Cu, Mn or K, and when being selected from one or more adjuvant components in the components such as Ru, Re, Pt and Pd, the present invention is not particularly limited its introducing method.Such as, can be adopt the method for dipping to introduce described carrier and drying after the compound containing described adjuvant component and the compound containing active metal component are mixed with hybrid infusion solution; Can also be adopt the method for dipping to introduce described carrier drying by after independent for the compound containing described auxiliary agent obtain solution.Described drying condition comprises: temperature is 80-250 DEG C, and be preferably 100-180 DEG C, drying time is 1-15 hour, is preferably 2-6 hour.
The FT synthetic method also provided according to the present invention, wherein said FT synthetic reaction condition is the popular response condition of FT synthetic reaction.Such as, according to the conventional method in this area, first by catalyst reduction, suitable reducing condition comprises: reduction temperature is 100 DEG C to 800 DEG C, is preferably 200 DEG C to 600 DEG C, more preferably 300 DEG C to 450 DEG C; Recovery time is 0.5-72 hour, be preferably 1-24 hour, more preferably 2-8 hour, described reduction can be carried out in pure hydrogen, also can carry out in the gaseous mixture of hydrogen and inert gas, as carried out in the gaseous mixture of hydrogen and nitrogen and/or argon gas, Hydrogen Vapor Pressure is 0.1-4MPa, is preferably 0.1-2MPa.
According to FT synthetic method provided by the invention, the described condition that the mixture of carbon monoxide and hydrogen and described catalyst exposure are reacted: preferable temperature is 160 ~ 280 DEG C, more preferably 190 ~ 250 DEG C, pressure is preferably 1 ~ 8MPa, more preferably 1-5MPa, the mol ratio of hydrogen and carbon monoxide is 0.4 ~ 2.5, is preferably 1.5 ~ 2.5, more preferably 1.8 ~ 2.2, the space-time speed of gas is 200 ~ 10000h
-1, be preferably 500 ~ 4000h
-1.
Described contact can be carried out in the reactor of any one type, such as fixed bed reactors, slurry bed system tank reactor, fluidized-bed reactor or bubbling bed reactor and corresponding scheme.Obviously, the reaction scheme that adopts according to them of the granular size of catalyst and changing.Select most suitable catalyst granules granularity to given reaction scheme, relate to reactant and the diffusion problem of product in catalyst granules, beds and reaction medium, this belongs to the general knowledge of those skilled in the art.
Compared with existing technical method, carbon monoxide-olefin polymeric provided by the invention not only has excellent F-T synthesis performance, determined by its preparation method, the preparation method of fischer-tropsch synthetic catalyst provided by the invention is simple, production cost is starkly lower than catalyst prepared by existing method.
Detailed description of the invention
The present invention will be further illustrated below by embodiment.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Embodiment 1-6 illustrates and can be used for preparing the shaping carrier and preparation thereof that the invention provides catalyst.
Embodiment 1
Get the boehmite powder 500g that catalyst Chang Ling branch company produces, add 20.0g methylcellulose, 15.0g sesbania powder and 475mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped to be positioned in baking oven 150 DEG C of dryings 12 hours.Obtain carrier Z1.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value (loss of strength rate), the results are shown in table 1.
Embodiment 2
Get the boehmite powder 250g that catalyst Chang Ling branch company produces, self-control unformed aluminium hydroxide powder 250g, add 10.0g methylcellulose, 15.0g HEMC and 475mL deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped to be positioned in baking oven 220 DEG C of dryings 6 hours.Obtain carrier Z2.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 3
Get the boehmite powder 300g that catalyst Chang Ling branch company produces, three water-aluminum hydroxide 200g, add 5.0g methylcellulose, 10.0g hydroxypropyl methylcellulose, 15.0g sesbania powder and 475mL deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped to be positioned in baking oven 80 DEG C of dryings 12 hours.Obtain carrier Z3.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 4
Get the boehmite SB powder 500g that Sasol company produces, add 15.0g HEMC and 450mL deionized water, be fully uniformly mixed, after even by banded extruder kneading, extruded moulding obtains shaping bar.The shaping bar of aluminium hydroxide to be positioned in baking oven 150 DEG C of dryings 12 hours.Obtain carrier Z4.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 5
Get the boehmite SB powder 500g that Sasol company produces, add 15.0g HEMC, 10.0g hydroxypropyl methylcellulose, 15.0g sesbania powder and 450mL deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains shaping bar.The shaping bar of aluminium hydroxide to be positioned in baking oven 250 DEG C of dryings 4 hours.Obtain carrier Z5.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 6
Get the boehmite powder 500g that Yantai, Shandong Heng Hui Chemical Co., Ltd. produces, add 25.0g hydroxypropyl methylcellulose, 15.0g sesbania powder and 450mL deionized water, be fully uniformly mixed, after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 120 DEG C of dryings 4 hours.Obtain carrier Z6.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Comparative example 1-4 illustrates reference shaping carrier and preparation thereof.
Comparative example 1
Get the boehmite powder 500g that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 12.5mL, 15.0g sesbania powder and 475mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 80 DEG C of dryings 4 hours.Obtain shaping carrier DB1, measure the radial crushing strength of DB1, water absorption rate and δ value, the results are shown in table 1.
Comparative example 2
Get the boehmite SB powder 500g that Sasol company produces, add 100ml Alumina gel, 15.0g sesbania powder and 450mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 150 DEG C of dryings 4 hours.Obtain shaping carrier DB2, measure the radial crushing strength of DB2, water absorption rate and δ value, the results are shown in table 1.
Comparative example 3
Get the boehmite powder 500g that Yantai, Shandong Heng Hui Chemical Co., Ltd. produces, add 25.0mL acetic acid, 15.0g sesbania powder and 450mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 180 DEG C of dryings 4 hours.Obtain shaping carrier DB3, measure the radial crushing strength of DB3, water absorption rate and δ value, the results are shown in table 1.
Comparative example 4
Get the boehmite powder 500g that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 12.5mL, 15.0g sesbania powder and 475mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 80 DEG C of dryings 4 hours.Dried strip 600 DEG C of roastings 4 hours.Obtain comparison vehicle DB4, measure the radial crushing strength of DB4, water absorption rate and δ value, the results are shown in table 1.
Table 1
*butt: the 600 DEG C of roastings 4 hours in Muffle furnace of boehmite article shaped dried strip, afterwards, before calculating roasting aftershaping thing and roasting, % by weight of article shaped obtains.
Embodiment 7 ~ 12 illustrates by the iron-base fischer-tropsch synthesis catalyst that the invention provides boehmite article shaped carrier and prepare.
Embodiment 7
Take the carrier Z1 (water absorption rate is 0.84) of 56.0g, weigh the ferric nitrate (Fe (NO getting 38.0g
3)
39H
2o), be dissolved into 47.1 milliliters of maceration extracts with water, use impregnation fluid carrier, dry 5h at 150 DEG C respectively in baking oven, obtains catalyst Fe C1 afterwards.
Embodiment 8
Take the carrier Z2 (water absorption rate is 0.76) of 57.0g, take 5.0gZr (NO
3)
45H
2o is also dissolved into 43.3 milliliters of maceration extract a with water; Flood this Z2 carrier with maceration extract a, in baking oven, dry 3h at 160 DEG C afterwards, obtain the carrier of Zr modification.Weigh the ferric nitrate (Fe (NO getting 38.0g
3)
39H
2o), 2.1g manganese nitrate solution (concentration of manganese nitrate is 50%) and 0.90 gram of potassium nitrate, 43.3 milliliters of maceration extract b are dissolved into water, flood modified carrier with maceration extract b, dry 4h at 140 DEG C respectively in baking oven, obtains catalyst Fe C2 afterwards.
Embodiment 9
Take the carrier Z3 (water absorption rate is 0.91) of 58.0g, take 2.5g ammonium metatungstate (tungsten oxide content is 87%) and be dissolved into 52.7 milliliters of maceration extract a with water; Flood this Z3 carrier with maceration extract a, in baking oven, dry 3h at 140 DEG C afterwards, obtain the carrier of W modification.Weigh the ferric nitrate (Fe (NO getting 38.0g
3)
39H
2o), 2.5gCr (NO
3)
39H
2and 0.5gCu (NO O)
3)
23H
2o), be dissolved into 52.7 milliliters of maceration extract b with water, flood modified carrier with maceration extract b, dry 6h at 120 DEG C respectively in baking oven, obtains catalyst Fe C3 afterwards.
Embodiment 10
Take the carrier Z4 (water absorption rate is 0.73) of 59.0g, weigh and get 3.0gCr (NO
3)
39H
2o), the ferric nitrate (Fe (NO of 38.0g
3)
39H
2o), 1.32 grams of potassium nitrate and 0.75gCu (NO
3)
23H
2o), be dissolved into 43.0 milliliters of maceration extracts with water, with impregnation fluid Z4 carrier, dry 5h at 140 DEG C respectively in baking oven, obtains catalyst Fe C4 afterwards.
Embodiment 11
Take the carrier Z5 (water absorption rate is 0.68) of 51.0g, weigh the ferric nitrate (Fe (NO getting 37.4g
3)
39H
2o), 2.5g manganese nitrate solution (concentration of manganese nitrate is 50%), 1.0 grams of potassium nitrate and 1.2gCu (NO
3)
23H
2o), be dissolved into 35.0 milliliters of maceration extracts with water, with impregnation fluid Z5 carrier, dry 4h at 160 DEG C respectively in baking oven, obtains catalyst Fe C5 afterwards.
Embodiment 12
Take the carrier Z6 (water absorption rate is 0.80) of 61.0g, weigh and get 2.0 lanthanum nitrates (La (NO
3)
36H
2and 2.0g cerous nitrate (Ce (NO O)
3)
36H
2and be dissolved into 48.8 milliliters of maceration extract a with water O); Flood this Z6 carrier with maceration extract a, 120 DEG C of dry 6h in baking oven, obtain the carrier of Ce modification afterwards.Weigh the ferric nitrate (Fe (NO getting 37.4g
3)
39H
2o)), 1.0 grams of potassium nitrate and 5.30g palladium ammonium salt solution (concentration of Pd is 1.04%), 48.8 milliliters of maceration extract b are dissolved into water, flood modified carrier with maceration extract b, dry 3h at 150 DEG C respectively in baking oven, obtains catalyst Fe C6 afterwards.
Comparative example 5
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, the ferric nitrate (Fe (NO of 38.0g
3)
39H
2o) be dissolved into 38 milliliters of maceration extracts with water, with impregnation fluid DB4 carrier, afterwards in baking oven respectively at 120 DEG C dry 4h, at 400 DEG C of roasting 4h, obtain catalyst Fe CDB1.
Comparative example 6
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, take the Zr (NO of 7.0g
3)
45H
2o is also dissolved into 38.0 milliliters of maceration extract a with water; With maceration extract a impregnated carrier DB4, dry 3h at 120 DEG C in baking oven afterwards; After drying in Muffle furnace roasting 3h at 420 DEG C, obtain the carrier of Zr modification.Get the ferric nitrate (Fe (NO of 38.0g
3)
39H
2o), 0.56g nitrosyl nitrate ruthenium solution (concentration of Ru is 9.6%) and 1.20 grams of potassium nitrate; 38.0 milliliters of maceration extract b are dissolved into water; the carrier of Zr modification is flooded with maceration extract b; afterwards in baking oven respectively at 120 DEG C dry 4h, at 380 DEG C of roasting 4h, obtain catalyst Fe CDB2.
Embodiment 13-18 illustrates the application and the effect thereof that the invention provides catalyst.
The Fischer-Tropsch synthesis performance of difference evaluate catalysts FeC1, FeC2, FeC3, FeC4, FeC5 and FeC6 in fixed bed reactors.
Unstripped gas forms: H
2/ CO/N
2=64%/32%/4% (volume hundred number).Catalyst grain size: 40 ~ 60 orders.
Catalyst reduction reaction condition: pressure is normal pressure, heating rate is 5 DEG C/min, and hydrogen gas space velocity is 2000h
-1, reduction temperature is 400 DEG C, and the recovery time is 5 hours.
Reaction condition: pressure 2.5MPa, temperature 280 DEG C, synthesis gas (unstripped gas) air speed 2000h
-1.
Get gas sample after reaction carries out 24 hours and carry out chromatography, wherein, COization charcoal percent conversion, methane selectively and C5+ hydrocarbon selective list in table 2.
Comparative example 7-8 illustrates application and the effect thereof of reference catalyst FeCDB1 and FeCDB2.
Reference catalyst FeCDB1 and FeCDB2 is evaluated according to embodiment 13-18 same procedure.Wherein, COization charcoal percent conversion, methane selectively and C5+ hydrocarbon selective list in table 2.
Table 2
Embodiment 19 ~ 24 illustrates by the Co based Fischer-Tropsch synthesis catalyst that the invention provides boehmite article shaped carrier and prepare.
Embodiment 19
Take the carrier Z1 (water absorption rate is 0.84) of 56.0g, take the Zr (NO of 7.0g
3)
45H
2o is also dissolved into 47.1 milliliters of maceration extract a with water; With maceration extract a impregnated carrier Z1, dry 6h at 120 DEG C in baking oven, obtains the carrier of Zr modification afterwards.Weigh the cobalt nitrate (Co (NO getting 37.4g
3)
26H
2and 0.56g nitrosyl nitrate ruthenium solution (concentration of Ru is 9.6%) O), be dissolved into 27.3 milliliters of maceration extract b with water, flood the carrier of modification with maceration extract b, dry 3h at 150 DEG C respectively in baking oven, obtains CATALYST Co C1 afterwards.
Embodiment 20
Take the carrier Z2 (water absorption rate is 0.76) of 57.0g, take 5.0gZr (NO
3)
45H
2o is also dissolved into 43.3 milliliters of maceration extract a with water; Flood this Z2 carrier with maceration extract a, in baking oven, dry 4h at 130 DEG C afterwards, obtain the carrier of Zr modification.Weigh the cobalt nitrate (Co (NO getting 37.4g
3)
26H
2and 0.56g nitrosyl nitrate ruthenium solution (concentration of Ru is 9.6%) O), be dissolved into 25.4 milliliters of maceration extract b, flood modified carrier with maceration extract b with water, dry 4h at 130 DEG C respectively in baking oven, obtains CATALYST Co C2 afterwards.
Embodiment 21
Take the carrier Z3 (water absorption rate is 0.91) of 58.0g, take 2.5g ammonium metatungstate (tungsten oxide content is 87%) and be dissolved into 52.7 milliliters of maceration extract a with water; Flood this Z3 carrier with maceration extract a, 140 DEG C of dry 3h in baking oven, obtain the carrier of W modification afterwards.Weigh the cobalt nitrate (Co (NO getting 37.4g
3)
26H
2and 4.10g platinum ammonium salt solution (concentration of Pt is 1.36%) O), be dissolved into 30.1 milliliters of maceration extract b, flood modified carrier with maceration extract b with water, dry 4h at 120 DEG C respectively in baking oven, obtains CATALYST Co C3 afterwards.
Embodiment 22
Take the carrier Z4 (water absorption rate is 0.73) of 58.0g, weigh and get 2.5g ammonium metatungstate (tungsten oxide content is 87%), the cobalt nitrate (Co (NO of 37.4g
3)
26H
2and 4.10g platinum ammonium salt solution (concentration of Pt is 1.36%) O), be dissolved into 42.4 milliliters of maceration extracts with water, with impregnation fluid Z4 carrier, dry 4h at 150 DEG C respectively in baking oven, obtains CATALYST Co C4 afterwards.
Embodiment 23
Take the carrier Z5 (water absorption rate is 0.68) of 58.0g, weigh and get 4.50g perrhenic acid (rhenium content is 4.2%), the cobalt nitrate (Co (NO of 37.4g
3)
26H
2and 4.10g platinum ammonium salt solution (concentration of Pt is 1.36%) O), be dissolved into 39.6 milliliters of maceration extracts with water, with impregnation fluid Z5 carrier, dry 4h at 160 DEG C respectively in baking oven, obtains CATALYST Co C4 afterwards.
Embodiment 24
Take the carrier Z6 (water absorption rate is 0.80) of 58.0g, weigh and get 3.50g cerous nitrate (Ce (NO
3)
36H
2and be dissolved into 46.4 milliliters of maceration extract a with water O); Flood this Z6 carrier with maceration extract a, in baking oven, dry 3h at 150 DEG C afterwards, obtain the carrier of Ce modification.Weigh the cobalt nitrate (Co (NO getting 37.4g
3)
26H
2and 5.30g palladium ammonium salt solution (concentration of Pd is 1.04%) O), be dissolved into 26.4 milliliters of maceration extract b, flood modified carrier with maceration extract b with water, dry 3h at 150 DEG C respectively in baking oven, obtains CATALYST Co C6 afterwards.
Comparative example 9
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, the cobalt nitrate (Co (NO of 37.4g
3)
26H
2o), be dissolved into 38.0 milliliters of maceration extracts with water, with impregnation fluid DB4 carrier, afterwards in baking oven respectively at 120 DEG C dry 4h, at 400 DEG C of roasting 4h, obtain CATALYST Co CDB1.
Comparative example 10
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, take the Zr (NO of 7.0g
3)
45H
2o is also dissolved into 38.0 milliliters of maceration extract a with water; With maceration extract a impregnated carrier DB4, dry 3h at 120 DEG C in baking oven afterwards; After drying in Muffle furnace roasting 3h at 420 DEG C, obtain the carrier of Zr modification.Weigh the cobalt nitrate (Co (NO getting 37.4g
3)
26H
2and 0.56g nitrosyl nitrate ruthenium solution (concentration of Ru is 9.6%) O); 38.0 milliliters of maceration extract b are dissolved into water; flood the carrier of Zr modification with maceration extract b, afterwards in baking oven respectively at 120 DEG C dry 4h, at 380 DEG C of roasting 4h, obtain CATALYST Co CDB2.
Embodiment 19-24 illustrates the application and the effect thereof that the invention provides catalyst.
The Fischer-Tropsch synthesis performance of difference evaluate catalysts CoC1, CoC2, CoC3, CoC4, CoC5 and CoC6 in fixed bed reactors.
Unstripped gas forms: H
2/ CO/N
2=64%/32%/4% (volume hundred number).Catalyst grain size: 40 ~ 60 orders.
Catalyst reduction reaction condition: pressure is normal pressure, heating rate is 5 DEG C/min, and hydrogen gas space velocity is 2000h
-1, reduction temperature is 400 DEG C, and the recovery time is 5 hours.
Reaction condition: pressure 2.5MPa, temperature 200 DEG C, synthesis gas (unstripped gas) air speed 2000h
-1.
Get gas sample after reaction carries out 24 hours and carry out chromatography, wherein, COization charcoal percent conversion, methane selectively and C5+ hydrocarbon selective list in table 3.
Comparative example 11-12 illustrates application and the effect thereof of reference catalyst CoCDB1 and CoCDB2.
Reference catalyst CoCDB1 and CoCDB2 is evaluated according to embodiment 19-24 same procedure.Wherein, COization charcoal percent conversion, methane selectively and C5+ hydrocarbon selective list in table 3.
Table 3
As shown in Table 3, FT synthetic catalyst of the present invention has active high, and C5+ hydrocarbon selective is low, the feature that methane selectively is low, is better than prior art comparative example.
Claims (25)
1. a catalyst used for Fischer-Tropsch synthesis, containing carrier, load iron on this carrier and/or cobalt metal component, take catalyst as benchmark, with the content of the iron of oxide basis and/or cobalt for 5-60 % by weight, in the content of the carrier of aluminium oxide for 40-95 % by weight, wherein, described carrier is the article shaped of alumina hydrate-containing, the article shaped of described alumina hydrate-containing contains hydrated alumina and cellulose ether, the radial crushing strength of described article shaped is 12-30N/mm, water absorption rate is that 0.4-1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
2. catalyst according to claim 1, is characterized in that, take catalyst as benchmark, with the content of the iron of oxide basis and/or cobalt for 10-50 % by weight, in the content of the carrier of aluminium oxide for 50-90 % by weight.
3. catalyst according to claim 1, is characterized in that, the radial crushing strength of described article shaped is 15-30N/mm, and water absorption rate is that 0.6-1, δ are less than or equal to 5%.
4. catalyst according to claim 1, is characterized in that, with described article shaped for benchmark, the content of described cellulose ether is 0.5-8 % by weight.
5. catalyst according to claim 4, is characterized in that, with described article shaped for benchmark, the content of described cellulose ether is 1-6 % by weight.
6. catalyst according to claim 5, is characterized in that, with described article shaped for benchmark, the content of described cellulose ether is 2-5 % by weight.
7. catalyst according to claim 1, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
8. catalyst according to claim 7, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
9. catalyst according to claim 1, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
10. catalyst according to claim 9, is characterized in that, described hydrated alumina is boehmite.
11. catalyst according to claim 1, it is characterized in that, described catalyst contains one or more adjuvant components be selected from La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd, is benchmark in element and with catalyst, and the content of described auxiliary agent is 0.001-25 % by weight.
12. catalyst according to claim 11, is characterized in that, are benchmark in element and with catalyst, and the introduction volume of described adjuvant component is 0.01-10 % by weight.
The preparation method of 13. 1 kinds of catalyst used for Fischer-Tropsch synthesis, comprise and prepare carrier and load iron and/or cobalt metal component also drying on this carrier, wherein, described carrier is the article shaped of alumina hydrate-containing, take catalyst as benchmark, the consumption of each component to make in described catalyst with the content of the iron of oxide basis and/or cobalt as 5-60 % by weight, in the content of the carrier of aluminium oxide for 40-95 % by weight, the condition of described drying comprises: temperature is 80-250 DEG C, time is 1-15 hour, hydrated alumina and cellulose ether mix by described moisture comprising with preparation method that is aluminium oxide article shaped, shaping and dry, the consumption of each component and shaping and drying condition make the radial crushing strength of described article shaped be 12-30N/mm, water absorption rate is 0.4-1.5, δ value is for being less than or equal to 10%, wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
14. methods according to claim 13, it is characterized in that, take catalyst as benchmark, the consumption of each component to make in described catalyst with the content of the iron of oxide basis and/or cobalt as 10-50 % by weight, in the content of the carrier of aluminium oxide for 50-90 % by weight, the condition of described drying comprises: temperature 100-180 DEG C, and drying time is 2-6 hour.
15. methods according to claim 13, is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina.
16. methods according to claim 15, is characterized in that, described hydrated alumina is boehmite.
17. methods according to claim 13, is characterized in that, the consumption of each component and shaping and drying condition make the radial crushing strength of described article shaped be 15N/mm-30N/mm, and water absorption rate is that 0.6-1, δ are less than or equal to 5%.
18. methods according to claim 13, is characterized in that, with described article shaped for benchmark, the consumption of described cellulose ether is 0.5-8 % by weight, and described drying condition comprises: temperature 60 C to being less than 350 DEG C, drying time 1-48 hour.
19. methods according to claim 18, is characterized in that, with described article shaped for benchmark, the consumption of described cellulose ether is 1%-6 % by weight, and described drying condition comprises: temperature 80-150 DEG C, drying time 2-14 hour.
20. methods according to claim 19, is characterized in that, with described article shaped for benchmark, the consumption of described cellulose ether is 2%-5 % by weight, and described drying condition comprises: temperature 100-130 DEG C, drying time 3-10 hour.
21. methods according to claim 13, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
22. methods according to claim 21, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
23. methods according to claim 13, it is characterized in that, also comprise the step introducing one or more adjuvant components be selected from La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd in carrier, be benchmark in element and with catalyst, the introduction volume of described adjuvant component is no more than 25 % by weight.
24. methods according to claim 23, is characterized in that, are benchmark in element and with catalyst, and the introduction volume of described adjuvant component is 0.01-10 % by weight.
25. 1 kinds of Fischer-Tropsch synthesis methods, under being included in Fischer-Tropsch synthesis condition, by the gas containing hydrogen and carbon monoxide and catalyst exposure, wherein, the catalyst that described catalyst provides for 1-12 any one claim.
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