CN104815663A - Cobalt-based synthesis catalyst, preparation method and application thereof - Google Patents

Cobalt-based synthesis catalyst, preparation method and application thereof Download PDF

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CN104815663A
CN104815663A CN201510167126.2A CN201510167126A CN104815663A CN 104815663 A CN104815663 A CN 104815663A CN 201510167126 A CN201510167126 A CN 201510167126A CN 104815663 A CN104815663 A CN 104815663A
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cobalt
catalyst
acid
mol
aluminate
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CN104815663B (en
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李德宝
侯博
贾丽涛
刘岩
张国权
刘亚纯
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Zhongke Lu'an Energy Technology Co., Ltd.
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention relates to a cobalt-based synthesis catalyst, a preparation method and an application thereof. The cobalt-based synthesis catalyst is composed of cobaltosic oxide and aluminate modified alumina, wherein, cobaltosic oxide accounts for 15-45% of final catalyst by weight composition, and mol ratio of the aluminate to alumina in the modified alumina is 1: 5-20. Compared with prior art, cobalt effective load capacity is increased, cobalt dispersiveness and reduction degree can be increased, and activity and stability of a ft synthesis reaction can be increased.

Description

A kind of cobalt-based synthetic catalyst and its preparation method and application
Technical field
The present invention relates to a kind of cobalt-based synthetic catalyst and its preparation method and application.
Background technology
Co based Fischer-Tropsch synthesis catalyst adopts dipping method to prepare usually, and infusion process adopts the specific area of carrier, Acidity of Aikalinity, pore structure, intensity and carrier and intermetallic interaction etc. to be all the key factors affecting catalyst activity and stability.SiO 2, Al 2o 3, TiO 2, molecular sieve and active carbon etc. all can be used as the carrier of Co based Fischer-Tropsch synthesis catalyst.Wherein, Al 2o 3there is larger duct and higher specific area, effectively can solve the diffusion of heavy constituent in catalyst duct in fischer-tropsch reaction product, can effectively prevent carbon deposit and the problem such as the catalyst activity reduction caused or inactivation.In addition, Al 2o 3there is resistant to elevated temperatures inertia, hardness be high, good stability of the dimension, being excellent heat conductor, can accelerating the transfer of fischer-tropsch reaction heat, is a kind of good carrier for exothermic reaction.But under certain reaction condition, metallic cobalt and carrying alumina are known from experience and are interacted, generate not easily reduction and do not have activated cobalt aluminate, and cause specific surface area of catalyst to decline, pore volume reduces, duct diminishes, and causes effective active metallic cobalt content to reduce simultaneously, and directly causes the reduction of fischer-tropsch reaction activity and stability.
Summary of the invention
Cobalt-based synthetic catalyst that the object of the present invention is to provide a kind of high activity and high stability and its preparation method and application.
First the present invention makes metal M (M is active metal Co or other metal, as Mg, Cu, Ni, Zn etc.) occupy the coordination of alumina tetrahedra vacancy and generates aluminate MAl 2o 4modified aluminas, and then flood Co, thus avoid the cobalt that flooded afterwards and carrier coordination generates cobalt aluminate, the pay(useful) load amount of cobalt can be improved like this, weaken the interaction of metallic cobalt and carrier, and increase decentralization and the reduction degree of cobalt.
Catalyst of the present invention is made up of cobaltosic oxide and aluminate modified aluminas, and wherein, the weight that cobaltosic oxide accounts for final catalyst consists of 15%-45%, and in modified aluminas, the mol ratio of aluminate and aluminium oxide is 1:5-20.
Aluminate as above is the aluminate of cobalt, copper, zinc, magnesium or nickel.
The preparation method of catalyst of the present invention is as follows:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take soluble metallic salt and aluminum soluble salt and carboxylic acid miscible in distilled water, by mixed solution after 50-90 DEG C of stirred in water bath evaporation, incipient impregnation, in aluminium oxide, obtains support precursor; By support precursor after 90-150 DEG C of dry 6-24h, obtain modified aluminas MAl in 600-900 DEG C of roasting 2-12h 2o 4-Al 2o 3; By the weight ratio of cobaltosic oxide and modified aluminas, take soluble cobalt, obtain solution, incipient impregnation is in above-mentioned modified aluminas, and 60-120 DEG C of dry 6-24h, in 250-400 DEG C of roasting 2-8h, obtains final CATALYST Co 3o 4/ MAl 2o 4-Al 2o 3.
Soluble metallic salt (M as above 2+), aluminum soluble salt (Al 3+), the molar composition ratio of carboxylic acid and aluminium oxide is M 2+: Al 3+: carboxylic acid: aluminium oxide=1:2:(0.5-2.0): (5-20).
Soluble metallic salt described above is the one in cobalt nitrate, cobalt acetate, copper nitrate, zinc nitrate, magnesium nitrate, zinc oxalate, nickel nitrate, copper carbonate, Schweinfurt green; Aluminum soluble salt is the one in aluminum nitrate, aluminium chloride, aluminum sulfate.
Carboxylic acid described above is the one of citric acid, malic acid, tartaric acid, lactic acid, salicylic acid, aspartic acid, gallic acid, malonic acid, succinic acid etc.
Aluminium oxide described above is self-control or buying business activated alumina, and its specific area is 120-500m 2g -1, pore volume is 0.2-1.2cm 3g -1, average pore size is 3.0-20nm.
Catalyst described above reduces in fixed bed, and reducing condition is: 300 ~ 450 DEG C, 0.5 ~ 1.5MPa, volume space velocity 500 ~ 1500h -1, constant temperature 6 ~ 24h, H 2: N 2=(0.05-0.95): 1 (mol/mol).
Catalyst as above carries out Fischer-Tropsch synthesis in fixed bed reactors, and reaction condition is: 190-240 DEG C, 1.0 ~ 3.0MPa, volume space velocity 500 ~ 3000h -1, H 2: CO=(0.1.5-2.5): 1 (mol/mol).
The present invention compared with prior art, can improve the pay(useful) load amount of cobalt, improves decentralization and the reduction degree of cobalt, improves Co based Fischer-Tropsch synthesis catalyst activity and stability.
Detailed description of the invention
The present invention will be further described for embodiment below, and protection scope of the present invention is not by the restriction of these embodiments.
Embodiment 1:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Cu (NO 3) 23H 2o, Al (NO 3) 39H 2o and citric acid are dissolved in distilled water, and by mixed solution after 60 DEG C of stirred in water bath are evaporated to certain volume, in a certain amount of aluminium oxide, (specific area is 300m to incipient impregnation for Shandong Aluminum Co., Ltd., activated alumina 2g -1, pore volume 0.4cm 3g -1, average pore size 10nm), wherein Cu 2+: Al 3+: citric acid: Al 2o 3=1:2:1.5:20 (mol/mol), obtains support precursor; By support precursor after 110 DEG C of dry 12h, be transferred in Muffle furnace, obtain modified aluminas CuAl in 750 DEG C of roasting 4h 2o 4-Al 2o 3; By Co 3o 4account for 30 (wt.) % of final catalyst, take Co (NO 3) 26H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 100 DEG C of dry 8h, is transferred in Muffle furnace, obtains final CATALYST Co in 350 DEG C of roasting 6h 3o 4/ CuAl 2o 4-Al 2o 3, wherein CuAl 2o 4: Al 2o 3=1:20 (mol/mol), Co 3o 4/ (Co 3o 4+ CuAl 2o 4+ Al 2o 3)=30 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 400 DEG C, 1.0MPa, constant temperature 8h, 1500h -1(V/V), H 2: N 2=0.05:1 (mol/mol).Reaction condition is: 235 DEG C, 2.0MPa, 2500h -1(V/V), H 2/ CO (mol)=1.8.Evaluation result: in CO conversion ratio 63%, 720h, inactivation rate is 0.02%.
Embodiment 2:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Zn (NO 3) 26H 2o, Al 2(SO 4) 318H 2o and tartaric acid are dissolved in distilled water, by mixed solution after 70 DEG C of stirred in water bath are evaporated to certain volume, incipient impregnation is in a certain amount of aluminium oxide (self-control activated alumina, 1mol/L aluminum nitrate and the co-precipitation of 1mol/L ammoniacal liquor, precipitation temperature 50 DEG C, aging temperature 70 DEG C, ageing time 2h, 110 DEG C of dry 12h, 600 DEG C of roasting 4h, specific area is 270m 2g -1, pore volume 0.7cm 3g -1, average pore size 14nm), wherein Zn 2+: Al 3+: tartaric acid: Al 2o 3=1:2:0.8:15 (mol/mol), obtains support precursor; By support precursor after 150 DEG C of dry 10h, be transferred in Muffle furnace, obtain modified aluminas ZnAl in 650 DEG C of roasting 6h 2o 4-Al 2o 3.By Co 3o 4account for 25 (wt.) % of final catalyst, take Co (NO 3) 26H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 90 DEG C of dry 18h, is transferred in Muffle furnace, obtains final CATALYST Co in 250 DEG C of roasting 10h 3o 4/ ZnAl 2o 4-Al 2o 3, wherein ZnAl 2o 4: Al 2o 3=1:15 (mol/mol), Co 3o 4/ (Co 3o 4+ ZnAl 2o 4+ Al 2o 3)=25 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 450 DEG C, 0.2MPa, constant temperature 4h, 1000h -1(V/V), H 2: N 2=0.2:1 (mol/mol).Reaction condition is: 230 DEG C, 2.0MPa, 2000h -1(V/V), H 2/ CO (mol)=2.0.Evaluation result: in CO conversion ratio 69.6%, 720h, inactivation rate is 0.04%.
Embodiment 3:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Ni (NO 3) 26H 2o, Al (NO 3) 39H 2o and malic acid are dissolved in distilled water, and by mixed solution after 80 DEG C of stirred in water bath are evaporated to certain volume, in a certain amount of aluminium oxide, (specific area is 500m to incipient impregnation for Sa Suoer company, activated alumina 2g -1, pore volume 1.1cm 3g -1, average pore size 6nm), wherein Ni 2+: Al 3+: malic acid: Al 2o 3=1:2:0.5:5 (mol/mol), obtains support precursor; By support precursor after 80 DEG C of dry 24h, be transferred in Muffle furnace, obtain modified aluminas NiAl in 700 DEG C of roasting 10h 2o 4-Al 2o 3.By Co 3o 4account for 18 (wt.) % of final catalyst, take C 4h 6o 4co4H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 120 DEG C of dry 2h, is transferred in Muffle furnace, obtains final CATALYST Co in 300 DEG C of roasting 8h 3o 4/ NiAl 2o 4-Al 2o 3, wherein NiAl 2o 4: Al 2o 3=1:5 (mol/mol), Co 3o 4/ (Co 3o 4+ NiAl 2o 4+ Al 2o 3)=18 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 360 DEG C, 0.5MPa, constant temperature 2h, 700h -1(V/V), H 2: N 2=0.4:1 (mol/mol).Reaction condition is: 225 DEG C, 2.2MPa, 1800h -1(V/V), H 2/ CO (mol)=2.1.Evaluation result: in CO conversion ratio 75.2%, 720h, inactivation rate is 0.01%.
Embodiment 4:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Mg (NO 3) 26H 2o, Al 2(SO 4) 318H 2o and salicylic acid are dissolved in distilled water, by mixed solution after 90 DEG C of stirred in water bath are evaporated to certain volume, incipient impregnation is in a certain amount of aluminium oxide (self-control activated alumina, the sodium aluminate of 2mol/L and the co-precipitation of 2mol/L red fuming nitric acid (RFNA), precipitation temperature 80 DEG C, aging temperature 85 DEG C, ageing time 2h, 120 DEG C of dry 24h, 650 DEG C of roasting 6h, specific area is 280m 2g -1, pore volume 0.8cm 3g -1, average pore size 12nm), wherein Mg 2+: Al 3+: salicylic acid: Al 2o 3=1:2:2:12 (mol/mol), obtains support precursor; By support precursor after 80 DEG C of dry 16h, be transferred in Muffle furnace, obtain modified aluminas MgAl in 600 DEG C of roasting 5h 2o 4-Al 2o 3.By Co 3o 4account for 45 (wt.) % of final catalyst, take Co (NO 3) 26H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 90 DEG C of dry 12h, is transferred in Muffle furnace, obtains final CATALYST Co in 360 DEG C of roasting 5h 3o 4/ MgAl 2o 4-Al 2o 3, wherein MgAl 2o 4: Al 2o 3=1:12 (mol/mol), Co 3o 4/ (Co 3o 4+ CuAl 2o 4+ Al 2o 3)=45 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 390 DEG C, 0.6MPa, constant temperature 12h, 500h -1(V/V), H 2: N 2=0.95:1 (mol/mol).Reaction condition is: 215 DEG C, 2.5MPa, 500h -1(V/V), H 2/ CO (mol)=2.0.Evaluation result: in CO conversion ratio 91.5%, 720h, inactivation rate is 0.0%.
Embodiment 5:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Co (NO 3) 26H 2o, Al (NO 3) 39H 2o and lactic acid are dissolved in distilled water, and by mixed solution after 60 DEG C of stirred in water bath are evaporated to certain volume, in a certain amount of aluminium oxide, (Gongyi, Henan honest feedwater material factory, activated alumina, specific area is 320m to incipient impregnation 2g -1, pore volume 0.5cm 3g -1, average pore size 9nm), wherein Co 2+: Al 3+: lactic acid: Al 2o 3=1:2:0.75:8 (mol/mol), obtains support precursor; By support precursor after 100 DEG C of dry 12h, be transferred in Muffle furnace, obtain modified aluminas CoAl in 800 DEG C of roasting 2h 2o 4-Al 2o 3.By Co 3o 4account for 35 (wt.) % of final catalyst, take C 4h 6o 4co4H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 60 DEG C of dry 12h, is transferred in Muffle furnace, obtains final CATALYST Co in 400 DEG C of roasting 2h 3o 4/ CoAl 2o 4-Al 2o 3, wherein CoAl 2o 4: Al 2o 3=1:8 (mol/mol), Co 3o 4/ (Co 3o 4+ CoAl 2o 4+ Al 2o 3)=35 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 450 DEG C, 0.3MPa, constant temperature 6h, 800h -1(V/V), H 2: N 2=0.75:1 (mol/mol).Reaction condition is: 220 DEG C, 2.0MPa, 3000h -1(V/V), H 2/ CO (mol)=1.95.Evaluation result: in CO conversion ratio 55.1%, 720h, inactivation rate is 0.05%.
Embodiment 6:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Cu (NO 3) 23H 2o, Al 2(SO 4) 318H 2o and aspartic acid are dissolved in distilled water, and by mixed solution after 90 DEG C of stirred in water bath are evaporated to certain volume, in a certain amount of aluminium oxide, (specific area is 350m to incipient impregnation for Shandong Aluminum Co., Ltd., activated alumina 2g -1, pore volume 0.6cm 3g -1, average pore size 15nm), wherein Cu 2+: Al 3+: aspartic acid: Al 2o 3=1:2:1.25:18 (mol/mol), obtains support precursor; By support precursor after 150 DEG C of dry 6h, be transferred in Muffle furnace, obtain modified aluminas CuAl in 850 DEG C of roasting 8h 2o 4-Al 2o 3.By Co 3o 4account for 15 (wt.) % of final catalyst, take Co (NO 3) 26H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 100 DEG C of dry 8h, is transferred in Muffle furnace, obtains final CATALYST Co in 250 DEG C of roasting 10h 3o 4/ CuAl 2o 4-Al 2o 3, wherein CuAl 2o 4: Al 2o 3=1:18 (mol/mol), Co 3o 4/ (Co 3o 4+ CuAl 2o 4+ Al 2o 3)=15 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 420 DEG C, 1.2MPa, constant temperature 18h, 750h -1(V/V), H 2: N 2=0.8:1 (mol/mol).Reaction condition is: 210 DEG C, 1.8MPa, 1800h -1(V/V), H 2/ CO (mol)=2.0.Evaluation result: in CO conversion ratio 85.5%, 720h, inactivation rate is 0.03%.
Embodiment 7:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take a certain amount of Ni (NO 3) 26H 2o, Al (NO 3) 39H 2o and citric acid are dissolved in distilled water, and by mixed solution after 85 DEG C of stirred in water bath are evaporated to certain volume, in a certain amount of aluminium oxide, (specific area is 380m to incipient impregnation for Shanxi Aluminum, activated alumina 2g -1, pore volume 0.4cm 3g -1, average pore size 7.5nm), wherein Ni 2+: Al 3+: citric acid: Al 2o 3=1:2:1.1:8 (mol/mol), obtains support precursor; By support precursor after 100 DEG C of dry 15h, be transferred in Muffle furnace, obtain modified aluminas NiAl in 900 DEG C of roasting 8h 2o 4-Al 2o 3.By Co 3o 4account for 27 (wt.) % of final catalyst, take Co (NO 3) 26H 2o, obtain solution, incipient impregnation, in above-mentioned modified aluminas, after 120 DEG C of dry 12h, is transferred in Muffle furnace, obtains final CATALYST Co in 300 DEG C of roasting 5h 3o 4/ NiAl 2o 4-Al 2o 3, wherein NiAl 2o 4: Al 2o 3=1:8 (mol/mol), Co 3o 4/ (Co 3o 4+ CuAl 2o 4+ Al 2o 3)=27 (wt.) %.
In fixed bed reactors, (Ф 10 × 500mm) does not dilute the above-mentioned catalyst of filling 5ml, and reducing condition is: 390 DEG C, 0.3MPa, constant temperature 10h, 900h -1(V/V), H 2: N 2=0.9:1 (mol/mol).Reaction condition is: 205 DEG C, 2.4MPa, 2200h -1(V/V), H 2/ CO (mol)=2.0.Evaluation result: in CO conversion ratio 76.7%, 720h, inactivation rate is 0.024%.

Claims (8)

1. a cobalt-based synthetic catalyst, it is characterized in that catalyst is made up of cobaltosic oxide and aluminate modified aluminas, wherein, the weight that cobaltosic oxide accounts for final catalyst consists of 15%-45%, and in modified aluminas, the mol ratio of aluminate and aluminium oxide is 1:5-20.
2. a kind of cobalt-based synthetic catalyst as claimed in claim 1, is characterized in that described aluminate is the aluminate of cobalt, copper, zinc, magnesium or nickel.
3. the preparation method of a kind of cobalt-based synthetic catalyst as claimed in claim 1 or 2, is characterized in that comprising the steps:
According to the mol ratio of aluminate in modified aluminas and aluminium oxide, take soluble metallic salt and aluminum soluble salt and carboxylic acid miscible in distilled water, by mixed solution after 50-90 DEG C of stirred in water bath evaporation, incipient impregnation, in aluminium oxide, obtains support precursor; By support precursor after 90-150 DEG C of dry 6-24h, obtain modified aluminas MAl in 600-900 DEG C of roasting 2-12h 2o 4-Al 2o 3; By the weight ratio of cobaltosic oxide and modified aluminas, take soluble cobalt, obtain solution, incipient impregnation is in above-mentioned modified aluminas, and 60-120 DEG C of dry 6-24h, in 250-400 DEG C of roasting 2-8h, obtains final CATALYST Co 3o 4/ MAl 2o 4-Al 2o 3;
Wherein soluble metallic salt M 2+, aluminum soluble salt Al 3+, carboxylic acid and aluminium oxide molar composition ratio be M 2+: Al 3+: carboxylic acid: aluminium oxide=1:2:0.5-2.0:5-20.
4. the preparation method of a kind of cobalt-based synthetic catalyst as claimed in claim 3, is characterized in that described soluble metallic salt is the one in cobalt nitrate, cobalt acetate, copper nitrate, zinc nitrate, magnesium nitrate, zinc oxalate, nickel nitrate, copper carbonate, Schweinfurt green.
5. the preparation method of a kind of cobalt-based synthetic catalyst as claimed in claim 3, is characterized in that described aluminum soluble salt is the one in aluminum nitrate, aluminium chloride, aluminum sulfate.
6. the preparation method of a kind of cobalt-based synthetic catalyst as claimed in claim 3, is characterized in that described carboxylic acid is the one in citric acid, malic acid, tartaric acid, lactic acid, salicylic acid, aspartic acid, gallic acid, malonic acid, succinic acid.
7. the preparation method of a kind of cobalt-based synthetic catalyst as claimed in claim 3, it is characterized in that described aluminium oxide is for self-control or buying business activated alumina, its specific area is 120-500 m 2g -1, pore volume is 0.2-1.2 cm 3g -1, average pore size is 3.0-20 nm.
8. the application of a kind of cobalt-based synthetic catalyst as claimed in claim 1 or 2, it is characterized in that catalyst reduces in fixed bed, reducing condition is: 300 ~ 450 DEG C, 0.5 ~ 1.5MPa, volume space velocity 500 ~ 1500h -1, constant temperature 6 ~ 24 h, H 2: N 2mol ratio=(0.05-0.95): 1;
Catalyst carries out Fischer-Tropsch synthesis in fixed bed reactors, and reaction condition is: 190-240 DEG C, 1.0 ~ 3.0MPa, volume space velocity 500 ~ 3000h -1, H 2: CO mol ratio=(0.1.5-2.5): 1.
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