CN103464169A - Fischer-Tropsch synthesis catalyst, preparation and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a Fischer-Tropsch synthesis catalyst, preparation and an application thereof. The catalyst comprises a carrier and an iron and/or cobalt metal component loaded on the carrier, wherein the iron and/or cobalt content (calculated as oxide) is 5-60 wt% and the carrier content (calculated as alumina) is 40-95 wt% through adopting the catalyst as the reference, and the carrier is a forming composition containing hydrated alumina. Compared with the catalyst prepared by using the method in the prior art, the catalyst composition of the present invention has excellent Fischer-Tropsch synthesis performances. In addition, the preparation method is simple, and a production cost of the catalyst of the present invention is significantly lower than a production cost of the catalyst prepared through the existing method.
Description
Technical field
The present invention relates to a kind of used for Fischer-Tropsch synthesis catalyst and preparation and application.
Background technology
20th century the '30s, Fischer-Tropsch (FT or F-T) is synthetic at first in German Industrial, the U.S., France, the former Soviet Union and China etc. have also set up similar artificial oil factory subsequently, relatively high because of this route artificial oil cost after World War II, benefit can not be closed one after another with oil competition, only have South Africa according to the Fischer-Tropsch synthetic 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 development and improvement not.Twentieth century seventies, Holland Shell company started the synthetic research of Fischer-Tropsch, the Co catalysts of their development in 1993 in Malaysia's operation of founding the factory.In recent years; along with day being becoming tight of petroleum resources, crude oil price soaring, to the continuous increase of progressively harshness and coal and the natural gas proved reserves of demanded fuel; make the research in synthetic this field of FT very active, many companies research and develop on Fischer-Tropsch is synthetic.
Carrier on Co catalysts the impact in the Fischer-Tropsch building-up process very complicated, offshore company also differs from one another in the preparation of the selection of catalyst carrier and catalyst.SiO
2surface area is high, is carrier commonly used, take in the world the research and development of Shell company as main and industrialization.Al
2o
3wearability good, mechanical strength is high, is applicable to starch state bed operation, take in the world the research and development of Sasol, Gulf/Chevron and Statoil company as main.TiO
2the oxide that often needs other as carrier is (as SiO
2, Al
2o
3and ZrO
2) carry out modification, take in the world the research and development of Exxon-Mobil company as main.Also have the researcher 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.
Aspect iron-based FT synthetic catalyst, loading type iron (ZL01134919.0-activated carbon is arranged 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 preparation and application.
The content the present invention relates to comprises:
1, a kind of used for Fischer-Tropsch synthesis catalyst, contain carrier, load on iron and/or cobalt metal component on this carrier, take catalyst as benchmark, take the iron of oxide and/or the content of cobalt is the 5-60 % by weight, the content of carrier of aluminium oxide of take is the 40-95 % by weight, wherein, the article shaped that described carrier is alumina hydrate-containing.
2, according to 1 described catalyst, it is characterized in that, take catalyst as benchmark, take the iron of oxide and/or the content of cobalt is the 10-50 % by weight, the content of carrier of aluminium oxide of take is the 50-90 % by weight, wherein, and the article shaped that described carrier is alumina hydrate-containing.
3, according to 1 described catalyst, it is characterized in that, the article shaped of described alumina hydrate-containing contains hydrated alumina and cellulose ether, and the radially crushing strength of described article shaped is more than or equal to 12N/mm, and water absorption rate is 0.4-1.5, and the δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, the radially crushing strength that Q1 is article shaped, Q2 is article shaped through water soaking 30 minutes, radially crushing strength through 120 ℃ of heating, dryings after 4 hours.
4, according to 3 described catalyst, it is characterized in that, the radially crushing strength of described article shaped is 15-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.
5, according to 3 described catalyst, it is characterized in that, take described article shaped as benchmark, the content of described cellulose ether is the 0.5-8 % by weight.
6, according to 5 described catalyst, it is characterized in that, take described article shaped as benchmark, the content of described cellulose ether is the 1-6 % by weight.
7, according to 6 described catalyst, it is characterized in that, take described article shaped as benchmark, the content of described cellulose ether is the 2-5 % by weight.
8, according to 3 described catalyst, it is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
9, according to 8 described catalyst, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
10, according to 1 described catalyst, it is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
11, according to 10 described catalyst, it is characterized in that, described hydrated alumina is boehmite.
12, according to 1 described catalyst, it is characterized in that, described catalyst also contains one or more adjuvant components that are selected from La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd, and in element and take catalyst as benchmark, the content of described auxiliary agent is the 0.001-25 % by weight.
13, according to 12 described catalyst, it is characterized in that, in element and take catalyst as benchmark, the introduction volume of described adjuvant component is the 0.01-10 % by weight.
14, a kind of preparation method of used for Fischer-Tropsch synthesis catalyst, comprise and prepare carrier and load iron and/or cobalt metal component dry on this carrier, wherein, the article shaped that described carrier is alumina hydrate-containing, take catalyst as benchmark, and it is the 5-60 % by weight that the consumption of each component makes in described catalyst take the iron of oxide and/or the content of cobalt, and the content of carrier of aluminium oxide of take is the 40-95 % by weight, the condition of described drying comprises: temperature is 80-250 ℃, and the time is 1-15 hour.
15, according to 14 described methods, it is characterized in that, take catalyst as benchmark, it is the 10-50 % by weight that the consumption of each component makes in described catalyst take the iron of oxide and/or the content of cobalt, the content of carrier of aluminium oxide of take is the 50-90 % by weight, the condition of described drying comprises: temperature 100-180 ℃, be 2-6 hour drying time.
16, according to 14 described methods, it is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina.
17, according to 16 described methods, it is characterized in that, described hydrated alumina is boehmite.
18, according to 14 described methods, it is characterized in that, the described moisture and preparation method aluminium oxide article shaped comprise by hydrated alumina and cellulose ether mix, moulding dry, the consumption of each component and moulding and drying condition make the radially crushing strength of described article shaped be more than or equal to 12N/mm, water absorption rate is 0.4-1.5, and the δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, the radially crushing strength that Q1 is article shaped, Q2 is article shaped through water soaking 30 minutes, radially crushing strength through 120 ℃ of heating, dryings after 4 hours.
19, according to 18 described methods, it is characterized in that, it is 15-30N/mm that the consumption of each component and moulding and drying condition make the radially crushing strength of described article shaped, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.
20, according to 18 described methods, it is characterized in that, take described article shaped as benchmark, the consumption of described cellulose ether is the 0.5-8 % by weight, and described drying condition comprises: temperature 60 C is to being less than 350 ℃, drying time 1-48 hour.
21, according to 20 described methods, it is characterized in that, take described article shaped as benchmark, the consumption of described cellulose ether is the 1%-6 % by weight, and described drying condition comprises: temperature 80-150 ℃, drying time 2-14 hour.
22, according to 21 described methods, it is characterized in that, take described article shaped as benchmark, the consumption of described cellulose ether is the 2%-5 % by weight, and described drying condition comprises: temperature 100-130 ℃, drying time 3-10 hour.
23, according to 18 described methods, it is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
24, according to 23 described methods, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
25, according to 14 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components in La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd, in element and take catalyst as benchmark, the introduction volume of described adjuvant component is no more than 25 % by weight.
26, according to 26 described methods, it is characterized in that, in element and take catalyst as benchmark, the introduction volume of described adjuvant component is the 0.01-10 % by weight.
27, a kind of Fischer-Tropsch synthesis method, be included under the Fischer-Tropsch synthesis condition, and the gas that will contain hydrogen and carbon monoxide contacts with catalyst, wherein, and 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 radially crushing strength of preferred described article shaped is 15-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.Wherein, δ=((Q1-Q2)/Q1) * 100%, Q1 is radially crushing strength of hydrated alumina forming matter, Q2 is hydrated alumina forming matter through water soaking 30 minutes, the radially crushing strength through 120 ℃ of heating, dryings after 4 hours.
The size of δ value is representing hydrated alumina forming matter variation (or being called the loss of strength rate) to crushing strength through the water soaking anteroposterior diameter.In the present invention, the described article shaped radially measuring method of crushing strength is carried out according to RIPP 25-90 catalyst compressive resistance determination method, about the article shaped concrete steps that radially crushing strength is measured, at RIPP 25-90, detailed introduction is arranged, and does not repeat here.
Described water absorption rate adopts following concrete grammar to measure: first 120 ℃ of testing samples are dried 4 hours.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 the 50g deionized water, soak 30min, filter, solid phase drains 5min, weighing solid phase weight (numbering: w2), solid phase is transferred in baking oven, and 120 ℃ of heating, dryings 4 hours, be positioned in desiccator and be cooled to room temperature.Water absorption rate=(w2-w1)/w1
Under the prerequisite met the demands in the radially crushing strength that is enough to make described article shaped, water absorption rate and loss of strength rate, the present invention is not particularly limited the content of cellulose ether, in concrete embodiment, take the hydrated alumina forming matter total amount as benchmark, the content of cellulose ether is preferably the 0.5-8 % by weight, more preferably the 1-6 % by weight, more be preferably the 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 contain the adjuvant component that does not affect or be of value to radially crushing strength, water absorption rate and the δ value of improving described article shaped.For example, contain starch and add component, described starch can be the powder obtained through pulverizing by vegetable seeds arbitrarily, as the sesbania powder.
Described hydrated alumina is selected from any hydrated alumina that can be used as adsorbent and catalyst carrier precursor, for example, can be boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, preferably boehmite.
According to the preparation method of hydrated alumina forming matter provided by the invention, described forming method can be prior art arbitrarily.For example, described forming method can be the forming method of extrusion, round as a ball, compressing tablet and their combination.For guaranteeing carrying out smoothly of moulding, can in material (being the mixture of hydrated alumina and cellulose ether), introduce auxiliary agent and water etc. herein when moulding, for example, when adopting the moulding of extrusion method, comprise by described hydrated alumina and cellulose ether and water, containing or containing extrusion aid, do not mix, then extrusion molding, obtain 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 the sesbania powder.The method that preferred forming method is extruded moulding.Described drying condition comprises: temperature 60 C is to being less than 350 ℃, drying time 1-48 hour, preferably temperature is 80-150 ℃, be 1-15h drying time, further preferably temperature is 100-130 ℃, be 2-10h drying time.
On the described water in moulding and alumina support, the method for load iron and/or cobalt is preferably the method for dipping, and described dipping method is conventional method, for example hole saturation dipping, excessive immersion stain and spray impregnating.Wherein, comprise the preparation dipping solution, for example, use, containing the compound preparation dipping solution of described iron and/or cobalt, is distinguished the method for impregnated carrier afterwards with this dipping solution.Described drying means is conventional method, the method for heating, drying for example, and described drying condition condition comprises: baking temperature 80-250 ℃, preferred 100-180 ℃, drying time, 1-15 hour, be preferably 2-6 hour.
The compound of described iron content and/or cobalt is selected from one or more in their soluble compound, for example, can be one or more in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals.Wherein, the preferred ferric nitrate of iron containing compounds, the preferred cobalt nitrate of cobalt compound.
Prior art shows, in fischer-tropsch synthetic catalyst, introduces and is selected from one or more adjuvant components in La, Zr, Ce, W, Cu, Mn or K; Introducing is selected from one or more adjuvant components in Ru, Re, Pt and Pd, favourable to the serviceability of improving catalyst.Optionally, the present invention preferably quotes these promoter metal components in catalyst.In element and take catalyst as benchmark, the introduction volume of above-mentioned auxiliary agent is the 0.001-25 % by weight, is preferably the 0.01-10 % by weight.
Contain one or more adjuvant components that are selected from La, Zr, Ce, W, Cu, Mn or K in described catalyst, and while 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 to its introducing method.For example, can be the compound that will contain described adjuvant component adopts the method for dipping to introduce described carrier dry with containing after compound containing active metal component is mixed with hybrid infusion solution; Can also be after the independent obtain solution of the compound that contains described auxiliary agent, to adopt the method for dipping to introduce described carrier drying.Described drying condition comprises: temperature is 80-250 ℃, is preferably 100-180 ℃, and be 1-15 hour drying time, is preferably 2-6 hour.
The FT synthetic method also provided according to the present invention, the popular response condition that wherein said FT synthetic reaction condition is the FT synthetic reaction.For example, according to the conventional method in this area, at first by catalyst reduction, suitable reducing condition comprises: reduction temperature is 100 ℃ to 800 ℃, is preferably 200 ℃ to 600 ℃, more preferably 300 ℃ to 450 ℃; Recovery time is 0.5-72 hour, be preferably 1-24 hour, 2-8 hour more preferably, described reduction can be carried out in pure hydrogen, also can in the gaseous mixture of hydrogen and inert gas, carry out, as carried out in the gaseous mixture at 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, described by the mixture of carbon monoxide and hydrogen and the catalytic condition of described catalyst: preferably temperature is 160～280 ℃, more preferably 190～250 ℃, pressure is preferably 1～8MPa, 1-5MPa more preferably, 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 type, for example fixed bed reactors, slurry state bed tank reactor, fluidized-bed reactor or bubbling bed reactor and corresponding scheme.Obviously, the reaction scheme that the granular size of catalyst adopts according to them changes.Given reaction scheme is selected to most suitable catalyst granules granularity, relate to reactant and the product diffusion problem in catalyst granules, beds and reaction medium, this belongs to those skilled in the art's general knowledge.
With existing technical method, compare, carbon monoxide-olefin polymeric provided by the invention not only has the synthetic performance of excellent Fischer-Tropsch, by its preparation method, determined, 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.
The specific embodiment
Below will further illustrate the present invention by embodiment.
Agents useful for same in example, except special instruction, be chemically pure reagent.
Embodiment 1-6 explanation can be used for shaping carrier and the preparation thereof that preparation the invention provides catalyst.
Embodiment 1
Get the boehmite powder 500g that catalyst Chang Ling branch company produces, add the 20.0g methylcellulose, 15.0g sesbania powder and 475mL deionized water, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped is positioned in baking oven to 150 ℃ of dryings 12 hours.Obtain carrier Z1.Measure radially crushing strength, water absorption rate and the δ value (loss of strength rate) of dry aftershaping carrier, 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 the 10.0g methylcellulose, 15.0g HEMC and 475mL deionized water, fully be uniformly mixed, after even by the banded extruder kneading, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped is positioned in baking oven to 220 ℃ of dryings 6 hours.Obtain carrier Z2.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, 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 the 5.0g methylcellulose, 10.0g hydroxypropyl methylcellulose, 15.0g sesbania powder and 475mL deionized water, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped is positioned in baking oven to 80 ℃ of dryings 12 hours.Obtain carrier Z3.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, 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, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.Aluminium hydroxide moulding bar is positioned in baking oven 150 ℃ of dryings 12 hours.Obtain carrier Z4.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 5
Get the boehmite SB powder 500g that Sasol company produces, add the 15.0g HEMC, the 10.0g hydroxypropyl methylcellulose, 15.0g sesbania powder and 450mL deionized water, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.Aluminium hydroxide moulding bar is positioned in baking oven 250 ℃ of dryings 4 hours.Obtain carrier Z5.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 6
Get the boehmite powder 500g that Yantai, Shandong permanent brightness chemical industry Co., Ltd produces, add the 25.0g hydroxypropyl methylcellulose, 15.0g sesbania powder and 450mL deionized water, fully be uniformly mixed, after even by the banded extruder kneading, extruded moulding obtains the moulding bar.The moulding bar is positioned in baking oven 120 ℃ of dryings 4 hours.Obtain carrier Z6.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Comparative Examples 1-4 explanation reference shaping carrier and preparation thereof.
Comparative Examples 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, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in baking oven 80 ℃ of dryings 4 hours.Obtain shaping carrier DB1, measure radially crushing strength, water absorption rate and the δ value of DB1, the results are shown in table 1.
Comparative Examples 2
Get the boehmite SB powder 500g that Sasol company produces, add 100ml aluminium colloidal sol, 15.0g sesbania powder and 450mL deionized water, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in baking oven 150 ℃ of dryings 4 hours.Obtain shaping carrier DB2, measure radially crushing strength, water absorption rate and the δ value of DB2, the results are shown in table 1.
Comparative Examples 3
Get the boehmite powder 500g that Yantai, Shandong permanent brightness chemical industry Co., Ltd produces, add 25.0mL acetic acid, 15.0g sesbania powder and 450mL deionized water, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in baking oven 180 ℃ of dryings 4 hours.Obtain shaping carrier DB3, measure radially crushing strength, water absorption rate and the δ value of DB3, the results are shown in table 1.
Comparative Examples 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, fully be uniformly mixed, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in baking oven 80 ℃ of dryings 4 hours.600 ℃ of roastings of dried strip 4 hours.Obtain comparison vehicle DB4, measure radially crushing strength, water absorption rate and the δ value of DB4, the results are shown in table 1.
Table 1
*butt: the 600 ℃ of roastings 4 hours in Muffle furnace of boehmite article shaped dried strip, afterwards, calculate roasting aftershaping thing and obtain with the % by weight of the front article shaped of roasting.
Embodiment 7～12 illustrates the iron-base fischer-tropsch synthesis catalyst prepared by the invention provides boehmite article shaped carrier.
Embodiment 7
Take the carrier Z1 (water absorption rate is 0.84) of 56.0g, the ferric nitrate (Fe (NO of 38.0g is got in weighing
3)
39H
2o), water is dissolved into 47.1 milliliters of maceration extracts, uses the maceration extract impregnated carrier, and dry 5h under 150 ℃ respectively in baking oven, obtain catalyst Fe C1 afterwards.
Embodiment 8
Take the carrier Z2 (water absorption rate is 0.76) of 57.0g, take 5.0g Zr (NO
3)
45H
2o water are dissolved into 43.3 milliliters of maceration extract a; Flood this Z2 carrier with maceration extract a, dry 3h under 160 ℃ afterwards in baking oven, obtain the carrier of Zr modification.Ferric nitrate (Fe (the NO of 38.0g is got in weighing
3)
39H
2o), 2.1g manganese nitrate solution (concentration of manganese nitrate is 50%) and 0.90 gram potassium nitrate, water is dissolved into 43.3 milliliters of maceration extract b, with the carrier after the modification of maceration extract b dipping, dry 4h under 140 ℃ respectively in baking oven, obtain 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%) water and be dissolved into 52.7 milliliters of maceration extract a; Flood this Z3 carrier with maceration extract a, dry 3h under 140 ℃ afterwards in baking oven, obtain the carrier of W modification.Ferric nitrate (Fe (the NO of 38.0g is got in weighing
3)
39H
2o), 2.5g Cr (NO
3)
39H
2o) and 0.5g Cu (NO
3)
23H
2o), water is dissolved into 52.7 milliliters of maceration extract b, and with the carrier after the modification of maceration extract b dipping, dry 6h under 120 ℃ respectively in baking oven, obtain catalyst Fe C3 afterwards.
Embodiment 10
Take the carrier Z4 (water absorption rate is 0.73) of 59.0g, 3.0g Cr (NO is got in weighing
3)
39H
2o), the ferric nitrate of 38.0g (Fe (NO
3)
39H
2o), 1.32 gram potassium nitrate and 0.75g Cu (NO
3)
23H
2o), water is dissolved into 43.0 milliliters of maceration extracts, and with maceration extract dipping Z4 carrier, dry 5h under 140 ℃ respectively in baking oven, obtain catalyst Fe C4 afterwards.
Embodiment 11
Take the carrier Z5 (water absorption rate is 0.68) of 51.0g, the ferric nitrate (Fe (NO of 37.4g is got in weighing
3)
39H
2o), 2.5g manganese nitrate solution (concentration of manganese nitrate is 50%), 1.0 gram potassium nitrate and 1.2g Cu (NO
3)
23H
2o), water is dissolved into 35.0 milliliters of maceration extracts, and with maceration extract dipping Z5 carrier, dry 4h under 160 ℃ respectively in baking oven, obtain catalyst Fe C5 afterwards.
Embodiment 12
Take the carrier Z6 (water absorption rate is 0.80) of 61.0g, 2.0 lanthanum nitrates (La (NO is got in weighing
3)
36H
2o) and 2.0g cerous nitrate (Ce (NO
3)
36H
2o), and water be dissolved into 48.8 milliliters of maceration extract a; Flood this Z6 carrier with maceration extract a, 120 ℃ of dry 6h in baking oven afterwards, obtain the carrier of Ce modification.Ferric nitrate (Fe (the NO of 37.4g is got in weighing
3)
39H
2o)), 1.0 gram potassium nitrate and 5.30g palladium ammonium salt solution (concentration of Pd is 1.04%), water is dissolved into 48.8 milliliters of maceration extract b, with the carrier after the modification of maceration extract b dipping, dry 3h under 150 ℃ respectively in baking oven, obtain catalyst Fe C6 afterwards.
Comparative Examples 5
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, the ferric nitrate of 38.0g (Fe (NO
3)
39H
2o) water is dissolved into 38 milliliters of maceration extracts, with maceration extract dipping DB4 carrier, afterwards in baking oven respectively under 120 ℃ dry 4h, at 400 ℃ of roasting 4h, obtain catalyst Fe CDB1.
Comparative Examples 6
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, take the Zr (NO of 7.0g
3)
45H
2o water are dissolved into 38.0 milliliters of maceration extract a; With maceration extract a impregnated carrier DB4, dry 3h under 120 ℃ in baking oven afterwards; After drying in Muffle furnace 420 ℃ of lower roasting 3h, obtain the carrier of Zr modification.Get the ferric nitrate (Fe (NO of 38.0g
3)
39H
2o), 0.56g nitrosyl radical nitric acid ruthenium solution (concentration of Ru is 9.6%) and 1.20 gram potassium nitrate; water is dissolved into 38.0 milliliters of maceration extract b; carrier with maceration extract b dipping Zr modification; afterwards in baking oven respectively under 120 ℃ dry 4h, at 380 ℃ of roasting 4h, obtain catalyst Fe CDB2.
Embodiment 13-18 explanation the invention provides application and the effect thereof of 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 umbers).Catalyst grain size: 40～60 orders.
The catalyst reduction reaction condition: pressure is normal pressure, and heating rate is 5 ℃/minute, and hydrogen gas space velocity is 2000h
-1, reduction temperature is 400 ℃, the recovery time is 5 hours.
Reaction condition: pressure 2.5MPa, 280 ℃ of temperature, synthesis gas (unstripped gas) air speed 2000h
-1.
Reaction is carried out getting the gas sample after 24 hours and is carried out chromatography, and wherein, the conversion ratio of COization carbon, methane selectively and C5+ hydrocarbon selective are listed in table 2.
Application and the effect thereof of Comparative Examples 7-8 explanation reference catalyst FeCDB1 and FeCDB2.
Estimate reference catalyst FeCDB1 and FeCDB2 according to embodiment 13-18 same procedure.Wherein, the conversion ratio of COization carbon, methane selectively and C5+ hydrocarbon selective are listed in table 2.
Table 2
Embodiment 19～24 illustrates the Co based Fischer-Tropsch synthesis catalyst prepared by the invention provides boehmite article shaped carrier.
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 water are dissolved into 47.1 milliliters of maceration extract a; With maceration extract a impregnated carrier Z1, dry 6h under 120 ℃ in baking oven afterwards, obtain the carrier of Zr modification.Cobalt nitrate (Co (the NO of 37.4g is got in weighing
3)
26H
2o) and 0.56g nitrosyl radical nitric acid ruthenium solution (concentration of Ru is 9.6%), water is dissolved into 27.3 milliliters of maceration extract b, and with the carrier of maceration extract b dipping modification, dry 3h under 150 ℃ respectively in baking oven, obtain CATALYST Co C1 afterwards.
Embodiment 20
Take the carrier Z2 (water absorption rate is 0.76) of 57.0g, take 5.0g Zr (NO
3)
45H
2o water are dissolved into 43.3 milliliters of maceration extract a; Flood this Z2 carrier with maceration extract a, dry 4h under 130 ℃ afterwards in baking oven, obtain the carrier of Zr modification.Cobalt nitrate (Co (the NO of 37.4g is got in weighing
3)
26H
2o) and 0.56g nitrosyl radical nitric acid ruthenium solution (concentration of Ru is 9.6%), water is dissolved into 25.4 milliliters of maceration extract b, and with the carrier after the modification of maceration extract b dipping, dry 4h under 130 ℃ respectively in baking oven, obtain 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%) water and be dissolved into 52.7 milliliters of maceration extract a; Flood this Z3 carrier with maceration extract a, 140 ℃ of dry 3h in baking oven afterwards, obtain the carrier of W modification.Cobalt nitrate (Co (the NO of 37.4g is got in weighing
3)
26H
2o) and 4.10g platinum ammonium salt solution (concentration of Pt is 1.36%), water is dissolved into 30.1 milliliters of maceration extract b, and with the carrier after the modification of maceration extract b dipping, dry 4h under 120 ℃ respectively in baking oven, obtain CATALYST Co C3 afterwards.
Embodiment 22
Take the carrier Z4 (water absorption rate is 0.73) of 58.0g, 2.5g ammonium metatungstate (tungsten oxide content is 87%), the cobalt nitrate of 37.4g (Co (NO are got in weighing
3)
26H
2o) and 4.10g platinum ammonium salt solution (concentration of Pt is 1.36%), water is dissolved into 42.4 milliliters of maceration extracts, and with maceration extract dipping Z4 carrier, dry 4h under 150 ℃ respectively in baking oven, obtain CATALYST Co C4 afterwards.
Embodiment 23
Take the carrier Z5 (water absorption rate is 0.68) of 58.0g, 4.50g perrhenic acid (rhenium content is 4.2%), the cobalt nitrate of 37.4g (Co (NO are got in weighing
3)
26H
2o) and 4.10g platinum ammonium salt solution (concentration of Pt is 1.36%), water is dissolved into 39.6 milliliters of maceration extracts, and with maceration extract dipping Z5 carrier, dry 4h under 160 ℃ respectively in baking oven, obtain CATALYST Co C4 afterwards.
Embodiment 24
Take the carrier Z6 (water absorption rate is 0.80) of 58.0g, 3.50g cerous nitrate (Ce (NO is got in weighing
3)
36H
2o), and water be dissolved into 46.4 milliliters of maceration extract a; Flood this Z6 carrier with maceration extract a, dry 3h under 150 ℃ afterwards in baking oven, obtain the carrier of Ce modification.Cobalt nitrate (Co (the NO of 37.4g is got in weighing
3)
26H
2o) and 5.30g palladium ammonium salt solution (concentration of Pd is 1.04%), water is dissolved into 26.4 milliliters of maceration extract b, and with the carrier after the modification of maceration extract b dipping, dry 3h under 150 ℃ respectively in baking oven, obtain CATALYST Co C6 afterwards.
Comparative Examples 9
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, the cobalt nitrate of 37.4g (Co (NO
3)
26H
2o), water is dissolved into 38.0 milliliters of maceration extracts, with maceration extract dipping DB4 carrier, afterwards in baking oven respectively under 120 ℃ dry 4h, at 400 ℃ of roasting 4h, obtain CATALYST Co CDB1.
Comparative Examples 10
Take the carrier DB4 (water absorption rate is 0.95) of 40.0g, take the Zr (NO of 7.0g
3)
45H
2o water are dissolved into 38.0 milliliters of maceration extract a; With maceration extract a impregnated carrier DB4, dry 3h under 120 ℃ in baking oven afterwards; After drying in Muffle furnace 420 ℃ of lower roasting 3h, obtain the carrier of Zr modification.Cobalt nitrate (Co (the NO of 37.4g is got in weighing
3)
26H
2o) and 0.56g nitrosyl radical nitric acid ruthenium solution (concentration of Ru is 9.6%); water is dissolved into 38.0 milliliters of maceration extract b; with the carrier of maceration extract b dipping Zr modification, afterwards in baking oven respectively under 120 ℃ dry 4h, at 380 ℃ of roasting 4h, obtain CATALYST Co CDB2.
Embodiment 19-24 explanation the invention provides application and the effect thereof of 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 umbers).Catalyst grain size: 40～60 orders.
The catalyst reduction reaction condition: pressure is normal pressure, and heating rate is 5 ℃/minute, and hydrogen gas space velocity is 2000h
-1, reduction temperature is 400 ℃, the recovery time is 5 hours.
Reaction condition: pressure 2.5MPa, 200 ℃ of temperature, synthesis gas (unstripped gas) air speed 2000h
-1.
Reaction is carried out getting the gas sample after 24 hours and is carried out chromatography, and wherein, the conversion ratio of COization carbon, methane selectively and C5+ hydrocarbon selective are listed in table 3.
Application and the effect thereof of Comparative Examples 11-12 explanation reference catalyst CoCDB1 and CoCDB2.
Estimate reference catalyst CoCDB1 and CoCDB2 according to embodiment 19-24 same procedure.Wherein, the conversion ratio of COization carbon, methane selectively and C5+ hydrocarbon selective are listed in table 3.
Table 3
As shown in Table 3, FT synthetic catalyst of the present invention has active high, and the C5+ hydrocarbon selective is low, and the characteristics that methane selectively is low are better than the prior art Comparative Examples.
Claims (27)
1. a used for Fischer-Tropsch synthesis catalyst, contain carrier, load on iron and/or cobalt metal component on this carrier, take catalyst as benchmark, take the iron of oxide and/or the content of cobalt is the 5-60 % by weight, the content of carrier of aluminium oxide of take is the 40-95 % by weight, wherein, the article shaped that described carrier is alumina hydrate-containing.
2. according to 1 described catalyst, it is characterized in that, take catalyst as benchmark, take the iron of oxide and/or the content of cobalt is the 10-50 % by weight, and the content of carrier of aluminium oxide of take is the 50-90 % by weight.
3. according to 1 described catalyst, it is characterized in that, the article shaped of described alumina hydrate-containing contains hydrated alumina and cellulose ether, and the radially crushing strength of described article shaped is more than or equal to 12N/mm, and water absorption rate is 0.4-1.5, and the δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, the radially crushing strength that Q1 is article shaped, Q2 is article shaped through water soaking 30 minutes, radially crushing strength through 120 ℃ of heating, dryings after 4 hours.
4. according to 3 described catalyst, it is characterized in that, the radially crushing strength of described article shaped is 15-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.
5. according to 3 described catalyst, it is characterized in that, take described article shaped as benchmark, the content of described cellulose ether is the 0.5-8 % by weight.
6. according to 5 described catalyst, it is characterized in that, take described article shaped as benchmark, the content of described cellulose ether is the 1-6 % by weight.
7. according to 6 described catalyst, it is characterized in that, take described article shaped as benchmark, the content of described cellulose ether is the 2-5 % by weight.
8. according to 3 described catalyst, it is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
9. according to 8 described catalyst, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
10. according to 1 described catalyst, it is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
11. according to 10 described catalyst, it is characterized in that, described hydrated alumina is boehmite.
12. according to 1 described catalyst, it is characterized in that, described catalyst contains one or more adjuvant components that are selected from La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd, and in element and take catalyst as benchmark, the content of described auxiliary agent is the 0.001-25 % by weight.
13. according to 12 described catalyst, it is characterized in that, in element and take catalyst as benchmark, the introduction volume of described adjuvant component is the 0.01-10 % by weight.
14. the preparation method of a used for Fischer-Tropsch synthesis catalyst, comprise and prepare carrier and load iron and/or cobalt metal component dry on this carrier, wherein, the article shaped that described carrier is alumina hydrate-containing, take catalyst as benchmark, and it is the 5-60 % by weight that the consumption of each component makes in described catalyst take the iron of oxide and/or the content of cobalt, and the content of carrier of aluminium oxide of take is the 40-95 % by weight, the condition of described drying comprises: temperature is 80-250 ℃, and the time is 1-15 hour.
15. according to 14 described methods, it is characterized in that, take catalyst as benchmark, it is the 10-50 % by weight that the consumption of each component makes in described catalyst take the iron of oxide and/or the content of cobalt, the content of carrier of aluminium oxide of take is the 50-90 % by weight, the condition of described drying comprises: temperature 100-180 ℃, be 2-6 hour drying time.
16. according to 14 described methods, it is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina.
17. according to 16 described methods, it is characterized in that, described hydrated alumina is boehmite.
18. according to 14 described methods, it is characterized in that, the described moisture and preparation method aluminium oxide article shaped comprise by hydrated alumina and cellulose ether mix, moulding dry, the consumption of each component and moulding and drying condition make the radially crushing strength of described article shaped be more than or equal to 12N/mm, water absorption rate is 0.4-1.5, and the δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, the radially crushing strength that Q1 is article shaped, Q2 is article shaped through water soaking 30 minutes, radially crushing strength through 120 ℃ of heating, dryings after 4 hours.
19. according to 18 described methods, it is characterized in that, it is 15N/mm-30N/mm that the consumption of each component and moulding and drying condition make the radially crushing strength of described article shaped, water absorption rate is 0.6-1, and δ is less than or equal to 5%.
20. according to 18 described methods, it is characterized in that, take described article shaped as benchmark, the consumption of described cellulose ether is the 0.5-8 % by weight, described drying condition comprises: temperature 60 C is to being less than 350 ℃, drying time 1-48 hour.
21. according to 20 described methods, it is characterized in that, take described article shaped as benchmark, the consumption of described cellulose ether is the 1%-6 % by weight, described drying condition comprises: temperature 80-150 ℃, drying time 2-14 hour.
22. according to 21 described methods, it is characterized in that, take described article shaped as benchmark, the consumption of described cellulose ether is the 2%-5 % by weight, described drying condition comprises: temperature 100-130 ℃, drying time 3-10 hour.
23. according to 18 described methods, it is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose.
24. according to 23 described methods, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
25. according to 14 described methods, it is characterized in that, also comprise in carrier and introduce the step that is selected from one or more adjuvant components in La, Zr, Ce, W, Cu, Mn, K, Ru, Re, Pt and Pd, in element and take catalyst as benchmark, the introduction volume of described adjuvant component is no more than 25 % by weight.
26. according to 25 described methods, it is characterized in that, in element and take catalyst as benchmark, the introduction volume of described adjuvant component is the 0.01-10 % by weight.
27. a Fischer-Tropsch synthesis method, be included under the Fischer-Tropsch synthesis condition, the gas that will contain hydrogen and carbon monoxide contacts with catalyst, wherein, and the catalyst that described catalyst provides for 1-13 any one claim.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104926619A (en) * | 2015-05-21 | 2015-09-23 | 石家庄鼎盈化工股份有限公司 | Synthesis method for petrochemical methyl tertiary butyl ether |
| CN111036233A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Wide-temperature methanol synthesis catalyst and preparation method and application thereof |
| CN111068691A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN113751017A (en) * | 2020-06-05 | 2021-12-07 | 国家能源投资集团有限责任公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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| CN102247895A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Preparation methods for catalyst carrier and Fischer-Tropsch synthesis catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104926619A (en) * | 2015-05-21 | 2015-09-23 | 石家庄鼎盈化工股份有限公司 | Synthesis method for petrochemical methyl tertiary butyl ether |
| CN111036233A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Wide-temperature methanol synthesis catalyst and preparation method and application thereof |
| CN111036233B (en) * | 2018-10-12 | 2022-11-29 | 中国石油化工股份有限公司 | Wide-temperature methanol synthesis catalyst and preparation method and application thereof |
| CN111068691A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN111068691B (en) * | 2018-10-18 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN113751017A (en) * | 2020-06-05 | 2021-12-07 | 国家能源投资集团有限责任公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN113751017B (en) * | 2020-06-05 | 2024-01-19 | 北京低碳清洁能源研究院 | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
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