CN101269329A - Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof - Google Patents
Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof Download PDFInfo
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- CN101269329A CN101269329A CNA2008100551047A CN200810055104A CN101269329A CN 101269329 A CN101269329 A CN 101269329A CN A2008100551047 A CNA2008100551047 A CN A2008100551047A CN 200810055104 A CN200810055104 A CN 200810055104A CN 101269329 A CN101269329 A CN 101269329A
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Abstract
The invention relates to a fischer-tropsch cobalt-based catalyst composed of an active component and a carrier, wherein, the metal cobalt accounts for 5-35 percent, and the carrier accounts for 65-95 percent of the catalyst which is made by a method of impregnation. The fischer-tropsch cobalt-based catalyst has the advantages of improving the reactivity of the catalyst and optimizing the distribution of products as well as increasing the selectivity for C5<+>; besides, the fischer-tropsch cobalt-based catalyst has simple process and is suitable for mass industrial production.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and preparation method and application, relate to a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method and application specifically.
Background technology
Fischer-Tropsch synthesis refers to that carbon monoxide and hydrogen (synthesis gas) are converted into the reaction of hydro carbons under metal catalytic effects such as iron, cobalt, ruthenium, is that coal, natural gas indirect reformer are the core process of clean chemicals (gasoline, diesel oil, alcohols etc.).Because petroleum resources is exhausted day by day, and resources such as coal, natural gas, living beings are abundant relatively, contain carbon resource production synthesis gas from coal, natural gas, living beings etc., pass through the Fischer-Tropsch synthetic liquid fuel by synthesis gas again, can alleviate dependence to a certain extent, national security and social benefit are had significance petroleum resources.In recent years, along with international oil price rises steadily and the enhancing of people's environmental consciousness, the research in this field was very active.Yet the efficient core that transforms of synthesis gas remains and the relevant catalysis problem of fischer-tropsch synthetic catalyst research.
Simple substance cobalt is the active phase of Fischer-Tropsch synthesis cobalt-based catalyst.In general, catalyst adopts pure hydrogen reduction to obtain active specy.A large amount of research work think Co based Fischer-Tropsch synthesis catalyst active with its reduction degree and decentralization direct correlation.In order to improve catalyst activity, a large amount of research work are devoted to how to improve catalyst reduction degree and decentralization.At present, main approach can be divided into two: the one, change Preparation of Catalyst condition (comprise and change carrier, cobalt source, interpolation auxiliary agent, roasting condition etc.).The selection of method for preparing catalyst and preparation condition has determined the generation of active component at state, distribution and the surface compound of catalyst surface, and the bonding state of cobalt species finally can influence the reduction act and the reactivity of catalyst.In these influence factor documents and the patent comparatively detailed argumentation is arranged.(Top.Catal.2003, the air velocity when 26:121) discovering by the roasting of raising catalyst can improve the decentralization of cobalt and then improve the catalyst reaction activity Van der Loosdrecht etc.Jelle R.A.Si etsma etc. (Stud.Surf.Sci.Catal., 2007,172:55) discover that catalyst precarsor roasting in 1%NO/He can improve catalyst activity.
The 2nd, adopt different reduction treatment process to improve the reduction degree and the decentralization of catalyst to catalyst.USP 5585316 has reported with CO can improve catalyst activity and C to cobalt-base catalyst
5 +Selectivity.By research trace oxygen, CO and CO/H
2Atmosphere is to going back ortho states Co-Ru/ γ-Al
2O
3Passivating process, and Soina Hammache etc. (Catal.Today, 2002,71:361) find a series of significant conclusions.At first, CO/H
2Passivating process can prevent to go back the heat release in air time of ortho states catalyst exposure efficiently; Secondly, micro-O
2And CO/H
2It is active that the catalyst exposure of Passivation Treatment secondary reduction behind air can recover, and the sample after the CO passivation then part recovers active, and reason may be that carbon distribution has covered the activity of such catalysts position; At last, expose the carbon distribution that produces when air helps removing the carbon-containing atmosphere passivation.USP5292705 also shows employing CO and CO/H
2It is effective and feasible that atmosphere is carried out the catalyst structure protection.
Above patent and document can improve the reactivity of catalyst to the processing of catalyst, distribute but can not optimize product, improve C
5 +Selectivity.
Summary of the invention
The object of the present invention is to provide a kind of preparation simple, reactivity height, C
5 +Fischer-Tropsch synthesis cobalt-based catalyst that selectivity is good and preparation method and application.
Catalyst of the present invention is made up of active component and carrier, and its percentage by weight consists of: metallic cobalt: 5-35%, carrier 65-95%.The preferred 10-20% of metallic cobalt, the preferred 80-90% of carrier.
The preparation method of cobalt-base catalyst provided by the present invention is as follows:
(1) it is as follows to adopt reduction-deactivation method to prepare the catalyst step:
Form cobalt salt added according to catalyst and be made into the solution that mass percentage concentration is 2-5wt% in deionized water or the alcohol, according to the catalyst composition carrier is joined in the solution that has configured, after stirring, at room temperature leave standstill 12h-90h, dry 12h-100h between 50 ℃-120 ℃ then, pulverize after dry and obtain powder, with powder roasting 3h-24h between 300 ℃-600 ℃, pressed powder after the roasting is ground the back to be warming up to 300 ℃-500 ℃ and to reduce and handle 3h-60h in reducing atmosphere, switch to passivating gas passivation 2h-48h after naturally cooling to 20 ℃-250 ℃, pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains catalyst.
(2) it is as follows to adopt direct-reduction process to prepare the catalyst step:
Form by catalyst and cobalt salt to be added the preparation mass percentage concentration is the solution of 2-5wt% in deionized water or the alcohol, by the catalyst composition carrier is joined in the solution that has configured, after stirring, room temperature leaves standstill 12h-90h, dry 12h-100h between 50 ℃-120 ℃ then, pulverize after dry and obtain powder, then powder is placed reducing atmosphere to handle 3h-60h for following 300 ℃-500 ℃, naturally switch to passivating gas passivation 2h-48h after cooling is reduced to 20 ℃-250 ℃, with the pressed powder compression molding after handling, sieve is got 40-80 order component, obtains catalyst.
Described cobalt salt is cobalt nitrate, cobalt acetate or acetylacetone cobalt etc.
Described carrier can be the poromerics of aperture less than 2nm, also can be the mesoporous material of aperture between 2nm and 50nm, can also be the large pore material of aperture greater than 50nm, and poromerics, mesoporous material or large pore material can be silica, aluminium oxide, titanium oxide or zirconia etc.
Described alcohol can be one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the butanols.
Reducing gases among the described preparation method can be H
2, CO or CO percentage by volume be CO and the H of 1-99%
2The gaseous mixture of forming.
Reduction mode among the described preparation method can be H
2Reduction, the CO reduction, the CO percentage by volume is CO and the H of 1-99%
2The gaseous mixture reduction of forming, first H
2The CO reduction of reduction back, first CO reduction back H
2Reduction, first H
2Reduction back CO percentage by volume is CO and the H of 1-99%
2The gaseous mixture reduction of forming, first CO reduction back CO percentage by volume is CO and the H of 1-99%
2The gaseous mixture reduction of forming.
Reducing condition among the described preparation method is: 300 ℃-500 ℃ of reduction temperatures, recovery time 3h-60h, reduction pressure 0-0.8MPa, reduction volume space velocity 100-5000h
-1
Passivating gas among the described preparation method can be O
2Percentage by volume is the O of 1-20%
2With N
2The gaseous mixture of forming, CO and the N that the CO percentage by volume is 10-90%
2The gaseous mixture of forming, CO and the H that the CO percentage by volume is 10-90%
2The gaseous mixture or the CO that form.
Described preparation method's passivation condition is: 20 ℃-250 ℃ of passivation temperatures, passivation time 2h-48h, passivation pressure 0-0.8MPa, passivation volume space velocity 100-5000h
-1
Catalyst of the present invention is applied to the reducing condition of Fischer-Tropsch when synthetic: 300 ℃-500 ℃ of reduction temperatures, recovery time 3h-60h, reduction pressure 0-0.8MPa, reduction volume space velocity 100-5000h
-1, reducing atmosphere is pure hydrogen.
Catalyst of the present invention is applied to the reaction condition of Fischer-Tropsch when synthetic: reaction pressure 1.0-3.0MPa, preferred 1.5-2.5MPa, 180 ℃-250 ℃ of reaction temperatures, reaction volume air speed 500-3000h
-1, unstripped gas is a hydrogen-carbon ratio at 1.6-3.5: the synthesis gas between 1.
The present invention has the following advantages:
1. adopt the preparation method of the cobalt-base catalyst that the present invention relates to, can improve reactivity and C
5 +Selectivity.
2. the cobalt-base catalyst preparation that the present invention relates to is simple with activating process, and the prospect of large-scale industrial production is arranged.
The specific embodiment
The following examples will the present invention is further illustrated, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1:
Taking by weighing cabaltous nitrate hexahydrate 7.4 grams, be dissolved in the 20mL deionized water, obtain homogeneous solution, is carrier (specific area 176m with commercial silica gel
2/ g, average pore size 11.32nm), according to 15%Co/SiO
2The catalyst composition joins the commercial silica gel of 8.49 grams in the solution that has configured, the back room temperature that stirs leaves standstill 90h, 50 ℃ of dry 100h in vacuum drying chamber then, after dried solid fully ground, 600 ℃ of roasting 3h in air, pressed powder after the roasting slowly is warming up to 300 ℃ of reduction handles 60h in hydrogen atmosphere, 0.8MPa is pressed in reduction, reduction air speed 100h
-1(V/V), reduction finishes the back cools off naturally, switches to CO passivating gas passivation 10h after waiting to reduce to 250 ℃.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains 15%Co/SiO
2Catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing 1mL15%Co/SiO in pressurization static bed reactor
2Catalyst, in the reaction tube of packing into, reducing condition is 420 ℃, 0.4MPa, 800h
-1(V/V), 12h.Program is warming up to cooling naturally after 420 ℃ of reduction in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjusting synthesis gas pressure is 1.5MPa.Reaction condition is: 180 ℃, and 1.5MPa, 500h
-1(V/V), H
2/ CO=1.6/1.For guaranteeing that Fischer-Tropsch synthesis enters stable state, need the above blending operation of operation 24h to think that just reaction system enters steady-state operation.Product C O, CO
2, CH
4And H
2Detect with carbon molecular sieve post and TCD, gaseous hydrocarbon detects with Porapak-Q post and FID, and oil sample and wax sample detect with OV-101 capillary column and FID.The catalytic perfomance evaluation is listed in the subordinate list.
Embodiment 2:
Take by weighing cobalt nitrate hexahydrate 4.94 grams, be dissolved in the 20mL absolute ethyl alcohol, obtain homogeneous solution, with the ZSM-5 molecular sieve is carrier (aperture is 0.51*0.55nm), according to 10%Co/ZSM-5 catalyst composition 9.03 gram ZSM-5 molecular sieves are joined in the solution that has configured, the back room temperature that stirs leaves standstill 12h, 50 ℃ of dry 100h in vacuum drying chamber, after dried solid fully ground, 300 ℃ of roasting 24h in air, pressed powder after the roasting slowly is warming up to 400 ℃ in hydrogen atmosphere, reduction pressure 0.3MPa, reduction air speed 5000h
-1(V/V) reduce under the condition and handle 3h, switch to the CO percentage by volume and be 99% CO and H
2The gaseous mixture of forming is at 400 ℃, reduction pressure 0.3MPa, reduction air speed 5000h
-1(V/V) 3h is handled in reduction under the condition, cools off naturally then, switches to O after waiting to reduce to 20 ℃
2Percentage by volume is 20% O
2With N
2The gaseous mixture passivation 2h that forms.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains the 10%Co/ZSM-5 catalyst.。
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing the 1mL10%Co/ZSM-5 catalyst, and in the reaction tube of packing into, reducing condition is 300 ℃, 0.0MPa, 5000h in pressurization static bed reactor
-1(V/V).Program is warming up to cooling naturally behind 300 ℃ of reduction 60h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 2.5MPa.Reaction condition is: 250 ℃, and 2.5MPa, 3000h
-1(V/V), H
2/ CO=3.5/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 3:
Take by weighing cobalt nitrate hexahydrate 2.47 grams, be dissolved in the mixed solution of 20mL methyl alcohol and ethanol, obtain homogeneous solution, the Y zeolite that obtains with ion-exchange is carrier (average pore size is 0.74nm), according to 5%Co/HY catalyst composition 9.50 gram HY are joined in the solution that has configured, the back room temperature that stirs leaves standstill 90h, 120 ℃ of dry 12h in drying box, after dried solid fully ground, 600 ℃ of roasting 3h in air, pressed powder after the roasting slowly is being warming up to 300 ℃ in CO atmosphere, reduction pressure 0.0MPa, reduction air speed 1000h
-1(V/V) reduce under the condition and handle 30h, after to switch to the CO percentage by volume be 1% CO and H
2The gaseous mixture of forming is at 300 ℃, reduction pressure 0.0MPa, reduction air speed 1000h
-1(V/V) 30h is handled in reduction under the condition, cools off naturally to wait to reduce to that to switch to the CO percentage by volume after 100 ℃ be 10% CO and N
2The gaseous mixture passivation 4h that forms.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains the 5%Co/HY catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing the 1mL5%Co/HY catalyst, and in the reaction tube of packing into, reducing condition is 350 ℃, 0.2MPa, 2500h in pressurization static bed reactor
-1(V/V).Program is warming up to cooling naturally behind 350 ℃ of reduction 30h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 1.5MPa.Reaction condition is: 220 ℃, and 1.5MPa, 500h
-1(V/V), H
2/ CO=2.3/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 4:
Take by weighing cobalt acetate 7.4 grams, be dissolved in the mixed solution of 30mL butanols and ethanol (volume ratio of butanols and ethanol is 1: 1) configuration, obtain homogeneous solution, with SBA-15 molecular sieve (average pore size is 8.0nm) is carrier, according to 15%Co/SBA-15 catalyst composition 17.9 gram SBA-15 molecular sieves are joined in the solution that has prepared, the back room temperature that stirs leaves standstill 18h, 80 ℃ of dry 60h in vacuum drying chamber, after dried solid fully ground, 450 ℃ of roasting 6h in air, pressed powder after the roasting slowly is warming up to 500 ℃ in CO atmosphere reduce and handle 3h, reduction pressure 0.8MPa, reduction air speed 100h
-1(V/V), cool off naturally the back, switches to 60%CO/N after waiting to reduce to 45 ℃
2(volume fraction of CO is 60%) passivating gas passivation 48h.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains the 15%Co/SBA-15 catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing the 1mL15%Co/SBA-15 catalyst, and in the reaction tube of packing into, reducing condition is 350 ℃, 0.5MPa, 100h in pressurization static bed reactor
-1(V/V).Program is warming up to cooling naturally behind 350 ℃ of reduction 18h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 2.0MPa.Reaction condition is: 220 ℃, and 2.0MPa, 3000h
-1(V/V), H
2/ CO=2.5/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 5:
Take by weighing cobalt nitrate hexahydrate 7.4 grams, be dissolved in the 30mL deionized water, obtain homogeneous solution, with mesoporous TiO
2For carrier (average pore size is 23.5nm), according to 15%Co/TiO
2Catalyst is formed the mesoporous TiO of 8.49 grams
2Join in the solution that has prepared, the back room temperature that stirs leaves standstill 18h, 70 ℃ of dry 12h in vacuum drying chamber, after dried solid fully ground, 350 ℃ of roasting 6h in air, pressed powder after the roasting slowly is warming up to 450 ℃ in hydrogen atmosphere reduce and handle 4h, reduction pressure 0.5MPa, reduction air speed 2500h
-1(V/V), cool off naturally the back, switches to 3%O after waiting to reduce to 35 ℃
2/ N
2(O
2Volume fraction is 3%) passivating gas passivation 24h.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains 15%Co/TiO
2Catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing 1mL15%Co/TiO in pressurization static bed reactor
2Catalyst, in the reaction tube of packing into, reducing condition is 450 ℃, 0.5MPa, 2000h
-1(V/V).Program is warming up to cooling naturally behind 450 ℃ of reduction 16h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 2.8MPa.Reaction condition is: 190 ℃, and 2.8MPa, 800h
-1(V/V), H
2/ CO=2/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 6:
Take by weighing cobalt nitrate hexahydrate 4.94 grams, be dissolved in the 80mL deionization, obtain homogeneous solution, with commercial CNT (CNT) is carrier (average pore size is 15nm), according to 10%Co/CNT catalyst composition the commercial CNT of 9.03 grams is joined in the solution that has prepared, the back room temperature that stirs leaves standstill 90h, 60 ℃ of dry 16h in vacuum drying chamber, after dried solid fully ground, 350 ℃ of roasting 4h in air, pressed powder after the roasting slowly is warming up to 500 ℃ reduces and handle 2h in CO atmosphere, after switch to H
2500 ℃ are reduced and handle 1h, reduction pressure 0.5MPa, reduction air speed 500h
-1(V/V), switch to CO passivating gas passivation 15h after cooling waits to reduce to 80 ℃ naturally.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains the 1mL10%Co/CNT catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing the 1mL10%Co/CNT catalyst, and in the reaction tube of packing into, reducing condition is 500 ℃, 0.5MPa, 2000h in pressurization static bed reactor
-1(V/V).Program is warming up to cooling naturally behind 500 ℃ of reduction 3h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 1.9MPa.Reaction condition is: 220 ℃, and 1.9MPa, 1000h
-1(V/V), H
2/ CO=3/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 7:
Taking by weighing acetylacetone cobalt 2.47 grams, be dissolved in the 60mL deionization, obtain homogeneous solution, is carrier (average pore size is 80nm) with commercial macro porous silica gel, according to 5%Co/SiO
2The catalyst composition joins the commercial macro porous silica gel of 7.76 grams in the solution that has prepared, the back room temperature that stirs leaves standstill 10h, 60 ℃ of dry 12h in drying box, after dried solid fully ground, 350 ℃ of roasting 8h in air, pressed powder after the roasting slowly is warming up to 350 ℃ in synthesis gas (volume fraction of CO is 50%) atmosphere reduce and handle 8h, reduction pressure 0.3MPa, reduction air speed 2500h
-1(V/V), naturally cooling to reduce to and switch to the CO percentage by volume after 60 ℃ be 10% CO and H
2The gaseous mixture passivation 10h that forms.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains 5%Co/SiO
2Catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing 1mL5%Co/SiO in pressurization static bed reactor
2Catalyst, in the reaction tube of packing into, reducing condition is 500 ℃, 0.5MPa, 2000h
-1(V/V).Program is warming up to cooling naturally behind 500 ℃ of reduction 3h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 2.1MPa.Reaction condition is: 240 ℃, and 2.1MPa, 1000h
-1(V/V), H
2/ CO=2/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 8:
Taking by weighing cobalt nitrate hexahydrate 4.94 grams, be dissolved in the 100mL ethanol, obtain homogeneous solution, is carrier with mesoporous zircite (method that adopts publication number CN 1631796 to provide is prepared, and the aperture is 10.6nm), according to 10%Co/ZrO
2The catalyst composition joins 9.03 gram mesoporous zircites in the solution that has prepared, the back room temperature that stirs leaves standstill 32h, 80 ℃ of dry 12h in vacuum drying chamber, after dried solid fully ground, 550 ℃ of roasting 2h in air, with the pressed powder after the roasting in hydrogen atmosphere, slowly be warming up to 350 ℃ reduce handle 2h after, switch to CO and continue to reduce and handle 6h at 350 ℃, reduction pressure 0.25MPa, reduction air speed 1200h
-1(V/V), switch to CO passivating gas passivation 36h after cooling is reduced to 30 ℃ naturally.Passivation pressure is identical with air speed and reduction process.Pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains 10%Co/ZrO
2Catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing 1mL10%Co/ZrO in pressurization static bed reactor
2Catalyst, in the reaction tube of packing into, reducing condition is 300 ℃, 0.8MPa, 2000h
-1(V/V).Program is warming up to cooling naturally behind 300 ℃ of reduction 60h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 2.2MPa.Reaction condition is: 180 ℃, and 2.2MPa, 1800h
-1(V/V), H
2/ CO=1.9/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 9:
Take by weighing cobalt nitrate hexahydrate 2.47 grams, be dissolved in the 20mL deionized water, obtain homogeneous solution, the Y zeolite that obtains with ion-exchange is carrier (average pore size is 0.74nm), forms according to the 5%Co/HY catalyst 9.50 gram HY molecular sieves are joined in the solution that has prepared, the back room temperature that stirs leaves standstill 18h, 80 ℃ of dry 12h in vacuum drying chamber are after dried solid fully ground, in the following 450 ℃ of reduction 4h of CO atmosphere, reduction pressure 0.3MPa, reduction air speed 2500h
-1(V/V), switch to CO passivating gas passivation 36h after cooling is reduced to 30 ℃ naturally.Passivation pressure is identical with air speed and reduction process.With the pressed powder moulding after handling, sieve is got 40-80 order component, obtains the 5%Co/HY catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing the 1mL5%Co/HY catalyst, and in the reaction tube of packing into, reducing condition is 500 ℃, 0.0MPa, 5000h in pressurization static bed reactor
-1(V/V).Program is warming up to cooling naturally behind 500 ℃ of reduction 3h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 3.0MPa.Reaction condition is: 180 ℃, and 3.0MPa, 500h
-1(V/V), H
2/ CO=3.5/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Embodiment 10:
Take by weighing cobalt nitrate hexahydrate 22.2 grams, be dissolved in the 100mL deionized water, obtain homogeneous solution, with mesoporous TiO
2For carrier (average pore size is 23.5nm), according to 35%Co/TiO
2Catalyst is formed the mesoporous TiO of 8.35 grams
2Join in the solution that has prepared, the back room temperature that stirs leaves standstill 18h, and 70 ℃ of dry 12h in vacuum drying chamber are after dried solid fully ground, in the following 400 ℃ of reduction 8h of hydrogen atmosphere, reduction pressure 0.5MPa, reduction air speed 1500h
-1(V/V), naturally cooling to reduce to and switch to the CO percentage by volume after 50 ℃ be 20% CO and H
2The gaseous mixture passivation 16h that forms.Passivation pressure is identical with air speed and reduction process.With the pressed powder moulding after handling, sieve is got 40-80 order component, obtains 35%Co/TiO
2Catalyst.
(Φ 10 * 500mm) carries out catalytic reaction, takes by weighing 1mL35%Co/TiO in pressurization static bed reactor
2Catalyst, in the reaction tube of packing into, reducing condition is 300 ℃, 0.8MPa, 100h
-1(V/V).Program is warming up to cooling naturally behind 300 ℃ of reduction 60h in hydrogen atmosphere, switches to synthesis gas after waiting to reduce to room temperature, and adjustment synthesis gas pressure is 1.0MPa.Reaction condition is: 250 ℃, and 1.0MPa, 3000h
-1(V/V), H
2/ CO=1.6/1.The catalytic perfomance evaluation result is listed in the subordinate list.
Subordinate list: the Fischer-Tropsch synthesis result of catalyst
Claims (16)
1, a kind of Fischer-Tropsch synthesis cobalt-based catalyst is characterized in that catalyst is made up of active component and carrier, and its percentage by weight consists of: metallic cobalt: 5-35%, carrier 65-95%.
2, a kind of Fischer-Tropsch synthesis cobalt-based catalyst as claimed in claim 1, it is characterized in that described catalyst weight percentage consists of: metallic cobalt selects 10-20%, carrier 80-90%.
3, a kind of Fischer-Tropsch synthesis cobalt-based catalyst as claimed in claim 1, it is characterized in that described carrier be the aperture less than the poromerics of 2nm, aperture between 2nm and 50nm mesoporous material or the aperture greater than the large pore material of 50nm.
4, the described a kind of Fischer-Tropsch synthesis cobalt-based catalyst of claim 3 is characterized in that described poromerics, mesoporous material or large pore material are silica, aluminium oxide, titanium oxide or zirconia.
5,, it is characterized in that comprising the steps: as the preparation method of each described a kind of Fischer-Tropsch synthesis cobalt-based catalyst of claim 1-4
Form cobalt salt added according to catalyst and be made into the solution that mass percentage concentration is 2-5wt% in deionized water or the alcohol, according to the catalyst composition carrier is joined in the solution that has configured, after stirring, at room temperature leave standstill 12h-90h, dry 12h-100h between 50 ℃-120 ℃ then, pulverize after dry and obtain powder, with powder roasting 3h-24h between 300 ℃-600 ℃, pressed powder after the roasting is ground the back to be warming up to 300 ℃-500 ℃ and to reduce and handle 3h-60h in reducing atmosphere, switch to passivating gas passivation 2h-48h after naturally cooling to 20 ℃-250 ℃, pressed powder compression molding after the processing, sieve is got 40-80 order component, obtains catalyst.
6,, it is characterized in that comprising the steps: as the preparation method of each described a kind of Fischer-Tropsch synthesis cobalt-based catalyst of claim 1-4
Form by catalyst and cobalt salt to be added the preparation mass percentage concentration is the solution of 2-5wt% in deionized water or the alcohol, by the catalyst composition carrier is joined in the solution that has configured, after stirring, room temperature leaves standstill 12h-90h, dry 12h-100h between 50 ℃-120 ℃ then, pulverize after dry and obtain powder, then powder is placed reducing atmosphere to handle 3h-60h for following 300 ℃-500 ℃, naturally switch to passivating gas passivation 2h-48h after cooling is reduced to 20 ℃-250 ℃, with the pressed powder compression molding after handling, sieve is got 40-80 order component, obtains catalyst.
7,, it is characterized in that described cobalt salt is cobalt nitrate, cobalt acetate or acetylacetone cobalt as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts.
8,, it is characterized in that described alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the butanols as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts.
9,, it is characterized in that described reducing gases can be H as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts
2, CO or CO percentage by volume be CO and the H of 1-99%
2The gaseous mixture of forming.
10,, it is characterized in that described reduction mode is first H as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts
2The CO reduction of reduction back, first CO reduction back H
2Reduction, first H
2Reduction back CO percentage by volume is CO and the H of 1-99%
2Gaseous mixture reduction of forming or first CO reduction back CO percentage by volume are CO and the H of 1-99%
2The gaseous mixture reduction of forming.
11, as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts, it is characterized in that described reducing condition is: 300 ℃-500 ℃ of reduction temperatures, recovery time 3h-60h, reduction pressure 0-0.8MPa, reduction volume space velocity 100-5000h
-1
12,, it is characterized in that described passivating gas is O as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts
2Percentage by volume is the O of 1-20%
2With N
2The gaseous mixture of forming, CO and the N that the CO percentage by volume is 10-90%
2The gaseous mixture of forming, CO and the H that the CO percentage by volume is 10-90%
2Gaseous mixture or the CO gas formed.
13, as the preparation method of claim 5 or 6 described a kind of Fischer-Tropsch synthesis cobalt-based catalysts, it is characterized in that described passivation condition is: 20 ℃-250 ℃ of passivation temperatures, passivation time 2h-48h, passivation pressure 0-0.8MPa, passivation volume space velocity 100-5000h
-1
14, as the application of each described a kind of Fischer-Tropsch synthesis cobalt-based catalyst of claim 1-4, it is characterized in that the reducing condition when being applied to Fischer-Tropsch synthesizes is: 300 ℃-500 ℃ of reduction temperatures, recovery time 3h-60h, reduction pressure 0-0.8MPa, reduction volume space velocity 100-5000h
-1, reducing atmosphere is pure hydrogen.
15,, it is characterized in that the reaction condition when being applied to Fischer-Tropsch synthesizes is: reaction pressure 1.0-3.0MPa, 180 ℃-250 ℃ of reaction temperatures, reaction volume air speed 500-3000h as the application of each described a kind of Fischer-Tropsch synthesis cobalt-based catalyst of claim 1-4
-1, unstripped gas is a hydrogen-carbon ratio at 1.6-3.5: the synthesis gas between 1.
16,, it is characterized in that described reaction pressure is 1.5-2.5MPa as the application of each described a kind of Fischer-Tropsch synthesis cobalt-based catalyst of claim 1-4.
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