CN105344356A - Alumina loaded cobalt catalyst and preparation method and uses in Fischer-Tropsch synthesis - Google Patents

Alumina loaded cobalt catalyst and preparation method and uses in Fischer-Tropsch synthesis Download PDF

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CN105344356A
CN105344356A CN201510799054.3A CN201510799054A CN105344356A CN 105344356 A CN105344356 A CN 105344356A CN 201510799054 A CN201510799054 A CN 201510799054A CN 105344356 A CN105344356 A CN 105344356A
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alumina
oxide
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catalyst
slurries
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CN105344356B (en
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李德宝
刘岩
贾丽涛
侯博
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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

An alumina loaded cobalt catalyst is composed of cobaltosic oxide, metal adjuvant oxide and alumina with weight proportion of 40-80: 0.5-5: 100. The alumina loaded cobalt catalyst can be used in slurry reactor and fixed bed Fischer-Tropsch synthesis reactions with high activity and stability.

Description

A kind of alumina load Co catalysts and method for making and the application at F-T synthesis
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and preparation method and application thereof, specifically a kind of alumina load Co based Fischer-Tropsch synthesis catalyst and preparation method and the application at F-T synthesis.
Background technology
Along with the development of World Economics, the demand of petroleum resources and reserves, distribute between contradiction, obtaining liquid product oil fuel by new method is the significant problem that China and even the whole world face.Fischer-Tropsch synthesis can produce clean fuel and other high valuable chemicals of high-quality on a large scale, and its unstripped gas) wide material sources, can be obtained through gasification by coal, natural gas, living beings, be applicable to the Energy Situation that the rich coal of China is oil-poor.
Cobalt-base catalyst for F-T synthesis adopts coprecipitation or infusion process to prepare usually.Wherein the catalyst for preparing of coprecipitation is assembled due to its active component, and the activity for Fischer-Tropsch synthesis is high, also causing catalyst to be easy to " temperature runaway " when reacting simultaneously, have impact on its commercial Application; And the catalyst that infusion process prepares is uniformly dispersed due to active component, carrier thermal conductivity and heat resistance good, so catalyst reaction process is steady.Silica, aluminium oxide, titanium oxide, magnesia, zinc oxide, zirconia, molecular sieve and active carbon etc. all can be used as the carrier of impregnating metal cobalt, and wherein aluminium oxide is the modal carrier of industrial applications.The specific area of aluminium oxide, Acidity of Aikalinity, pore structure, intensity and and metallic cobalt between interaction etc. be all affect the catalytic activity of its load cobalt catalyst and the key factor of stability, having the greatest impact of its central hole structure, obtains and has suitable pore size and the narrow aluminium oxide of pore size distribution range is the final goal that this area researcher pursues.
Summary of the invention
For solving the problem, the object of the present invention is to provide a kind of there is high activity and stability the alumina load Co catalysts for slurry bed system and fixed bed Fischer-Tropsch synthesis and method for making and the application at F-T synthesis.
The present invention introduces organic carbon source as aluminium oxide expanding agent, and under microwave, guide the distribution of aluminum precursor in organic carbon source, finally realize the orderly pore size distribution of Woelm Alumina after roasting, greatly can improve the mass-and heat-transfer efficiency of load cobalt catalyst, and then improve F-T synthesis catalytic performance.
Catalyst of the present invention is made up of cobaltosic oxide, metal promoter oxide and aluminium oxide, and its weight consists of cobaltosic oxide: metal promoter oxide: aluminium oxide=(40-80): (0.5-5): 100.
As mentioned above, metal promoter oxide is strontium oxide strontia, yittrium oxide, niobium oxide, molybdenum oxide.
Concrete preparation method is as follows for catalyst of the present invention: form according to final catalyst, take alumina precursor, and be mixed with the molten slurry of alumina precursor that solid content is 10-30wt%, agitating heating 0.5-2h at 40-70 DEG C, obtains slurries A; Account for the 10-200wt% of alumina precursor according to organic carbon source, take organic carbon source, be mixed with the molten slurry of organic carbon source that solid content is 10-30wt%, gelatinization 1-6h at 50-90 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 0.5-3.0h, then micro-wave oven is placed in, take out after microwave 5-60min under power is 200-800W, at 60-90 DEG C, obtain carbon containing alumina precursor after vacuum drying 12-36h, then at 450-800 DEG C, obtain alumina support after roasting 4-12h; Again by soluble cobalt and the water-soluble incipient impregnation of solubility promoter metal salt on above-mentioned alumina support, at 60-90 DEG C, roasting 2-6h at dry 12-24h, 300-400 DEG C, obtains final catalyst.
As mentioned above, alumina precursor is the one of aluminium carbonate ammonia, aluminium hydroxide or boehmite.
As mentioned above, organic carbon source is the one of starch, cellulose, hemicellulose, plant glycogen, agar-agar or pectin etc.
As mentioned above, soluble cobalt is cobalt nitrate or cobalt acetate.
As mentioned above, solubility promoter metal salt is strontium nitrate, yttrium nitrate, niobium oxalate or ammonium dimolybdate.
Fischer-Tropsch synthesis cobalt-based catalyst as above, can carry out reducing, reacting in fixed bed reactors; Reducing condition is: 350-450 DEG C, 0.3-1.5MPa, GHSV=500-1000h -1, constant temperature 12-36h, adopts hydrogen reduction gas in nitrogen, H 2content is 15%-85% (v/v); Reaction condition is: 170-230 DEG C, 2.0-3.0Mpa, GHSV=700-2500h -1, H 2/ CO (v/v)=2.0-2.5.
Fischer-Tropsch synthesis cobalt-based catalyst as above, can carry out reducing, reacting in paste state bed reactor; Reducing condition is: 270-320 DEG C, 0.2-1.2MPa, GHSV=500-800h -1, constant temperature 12-36h, adopts hydrogen reduction gas in nitrogen, H 2content is 15%-85% (v/v), and rotating speed is 400-800rpm; Reaction condition is: 170-230 DEG C, 2.0-3.0MPa, GHSV=700-2500h -1, H 2/ CO (v/v)=2.0-3.0, rotating speed is 400-800rpm.
Catalyst of the present invention has the advantages that specific area is large, pore passage structure enriches, mass-and heat-transfer performance is good, can accelerate reaction rate for Fischer-Tropsch synthesis, improves C 5+ selective and reduce methane selectively.
Detailed description of the invention
Embodiment 1
Form according to final catalyst, take 117.65g boehmite, be mixed with the molten slurry of boehmite that solid content is 10 (wt.) %, agitating heating 2.0h at 40 DEG C, obtains slurries A; Account for 100 (wt.) % of boehmite according to plant glycogen, take 117.65g plant glycogen, be mixed with the molten slurry of plant glycogen that solid content is 10 (wt.) %, gelatinization 3h at 70 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 3.0h, be then placed in micro-wave oven, take out after microwave 15min under power is 400W, at 60 DEG C, obtain carbon containing alumina precursor after vacuum drying 36h, then in Muffle furnace, obtain alumina catalyst support after roasting 4h at 800 DEG C; Again by 144.95g cobalt acetate and the water-soluble incipient impregnation of 2.02g niobium oxalate in above-mentioned alumina support, dry 12h at 90 DEG C, roasting 6h at 300 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: Nb 2o 5: Al 2o 3=40:0.5:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 450 DEG C, 0.3MPa, constant temperature 12h, 1000h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 15% (v/v).Reaction condition is: 180 DEG C, 3.0MPa, 700h -1(v/v), H 2/ CO (mol)=2.0.Evaluation result: CO conversion ratio 90.6%, CH 4selective is 2.3%, C 5 +selective is 93.3%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 320 DEG C, 0.2MPa, 700h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 15% (v/v), constant temperature 30h, 750rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 230 DEG C, 2.0MPa, 2500h -1(v/v), H 2/ CO (v/v)=3.0,700rpm.Evaluation result: CO conversion ratio 41.2%, CH 4selective is 15.6%, C 5 +selective is 72.2%.
Embodiment 2
Form according to final catalyst, take 273.55g aluminium carbonate ammonia, be mixed with the molten slurry of aluminium carbonate ammonia that solid content is 15 (wt.) %, agitating heating 1.8h at 50 DEG C, obtains slurries A; Account for 50 (wt.) % of aluminium carbonate ammonia according to starch, take 136.78g starch, be mixed with the molten slurry of starch that solid content is 15 (wt.) %, gelatinization 6h at 50 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 2.5h, be then placed in micro-wave oven, take out after microwave 60min under power is 200W, at 65 DEG C, obtain carbon containing alumina precursor after vacuum drying 32h, then in Muffle furnace, obtain alumina catalyst support after roasting 6h at 700 DEG C; Again by 155.04g cobalt nitrate and the water-soluble incipient impregnation of 2.32g ammonium dimolybdate in above-mentioned alumina support, dry 14h at 85 DEG C, roasting 6h at 320 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: MoO 3: Al 2o 3=50:1:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 425 DEG C, 0.5MPa, constant temperature 16h, 900h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 25% (v/v).Reaction condition is: 190 DEG C, 2.8MPa, 1000h -1(v/v), H 2/ CO (mol)=2.0.Evaluation result: CO conversion ratio 80.5%, CH 4selective is 3.8%, C 5 +selective is 88.9%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 310 DEG C, 0.4MPa, 500h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 85% (v/v), constant temperature 36h, 450rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 220 DEG C, 2.2MPa, 2200h -1(v/v), H 2/ CO (v/v)=2.8,800rpm.Evaluation result: CO conversion ratio 54.4%, CH 4selective is 11.7%, C 5 +selective is 78.5%.
Embodiment 3
Form according to final catalyst, take 152.94g aluminium hydroxide, be mixed with the molten slurry of aluminium hydroxide that solid content is 20 (wt.) %, agitating heating 1.5h at 55 DEG C, obtains slurries A; Account for 10 (wt.) % of aluminium hydroxide according to cellulose, take 15.29g cellulose, be mixed with the molten slurry of cellulose that solid content is 17.5 (wt.) %, gelatinization 5h at 60 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 2.0h, be then placed in micro-wave oven, take out after microwave 50min under power is 300W, at 70 DEG C, obtain carbon containing alumina precursor after vacuum drying 28h, then in Muffle furnace, obtain alumina catalyst support after roasting 6h at 650 DEG C; Again by 199.3g cobalt acetate and the water-soluble incipient impregnation of 5.09g yttrium nitrate in above-mentioned alumina support, dry 16h at 80 DEG C, roasting 5h at 340 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: Y 2o 3: Al 2o 3=55:1.5:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 400 DEG C, 0.7MPa, constant temperature 20h, 800h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 35% (v/v).Reaction condition is: 200 DEG C, 2.6MPa, 1500h -1(v/v), H 2/ CO (mol)=2.2.Evaluation result: CO conversion ratio 70.7%, CH 4selective is 7.6%, C 5 +selective is 84.6%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 300 DEG C, 0.5MPa, 600h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 75% (v/v), constant temperature 32h, 550rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 210 DEG C, 2.2MPa, 2000h -1(v/v), H 2/ CO (v/v)=2.6,600rpm.Evaluation result: CO conversion ratio 58.6%, CH 4selective is 7.9%, C 5 +selective is 85.5%.
Embodiment 4
Form according to final catalyst, take 117.65g boehmite, be mixed with the molten slurry of boehmite that solid content is 25 (wt.) %, agitating heating 1.5h at 60 DEG C, obtains slurries A; Account for 20 (wt.) % of boehmite according to hemicellulose, take 23.53g hemicellulose, be mixed with the molten slurry of hemicellulose that solid content is 20 (wt.) %, gelatinization 4h at 65 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 1.5h, be then placed in micro-wave oven, take out after microwave 40min under power is 400W, at 75 DEG C, obtain carbon containing alumina precursor after vacuum drying 24h, then in Muffle furnace, obtain alumina catalyst support after roasting 8h at 600 DEG C; Again by 186.05g cobalt nitrate and the water-soluble incipient impregnation of 4.08g strontium nitrate in above-mentioned alumina support, dry 18h at 80 DEG C, roasting 4h at 350 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: SrO:Al 2o 3=60:2:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 375 DEG C, 0.8MPa, constant temperature 24h, 750h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 45% (v/v).Reaction condition is: 210 DEG C, 2.5MPa, 1800h -1(v/v), H 2/ CO (mol)=2.2.Evaluation result: CO conversion ratio 56.7%, CH 4selective is 9.4%, C 5 +selective is 84.7%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 290 DEG C, 0.6MPa, 750h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 65% (v/v), constant temperature 24h, 650rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 200 DEG C, 2.3MPa, 1000h -1(v/v), H 2/ CO (v/v)=2.2,500rpm.Evaluation result: CO conversion ratio 70.0%, CH 4selective is 11.1%, C 5 +selective is 80.0%.
Embodiment 5
Form according to final catalyst, take 273.55g aluminium carbonate ammonia, be mixed with the molten slurry of aluminium carbonate ammonia that solid content is 30 (wt.) %, agitating heating 1.2h at 60 DEG C, obtains slurries A; Account for 150 (wt.) % of aluminium carbonate ammonia according to agar-agar, take 410.33g agar-agar, be mixed with the molten slurry of agar-agar that solid content is 22.5 (wt.) %, gelatinization 3.5h at 70 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 1.5h, be then placed in micro-wave oven, take out after microwave 30min under power is 500W, at 80 DEG C, obtain carbon containing alumina precursor after vacuum drying 20h, then in Muffle furnace, obtain alumina catalyst support after roasting 10h at 550 DEG C; Again by 235.54g cobalt acetate and the water-soluble incipient impregnation of 10.17g yttrium nitrate in above-mentioned alumina support, dry 20h at 85 DEG C, roasting 4h at 370 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: Y 2o 3: Al 2o 3=65:3:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 350 DEG C, 1.0MPa, constant temperature 28h, 600h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 55% (v/v).Reaction condition is: 220 DEG C, 2.4MPa, 2000h -1(v/v), H 2/ CO (mol)=2.3.Evaluation result: CO conversion ratio 42.3%, CH 4selective is 12.9%, C 5 +selective is 80.1%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 280 DEG C, 0.8MPa, 800h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 55% (v/v), constant temperature 12h, 750rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 200 DEG C, 2.5MPa, 1500h -1(v/v), H 2/ CO (v/v)=2.5,400rpm.Evaluation result: CO conversion ratio 80.6%, CH 4selective is 15.6%, C 5 +selective is 72.6%.
Embodiment 6
Form according to final catalyst, take 152.94g aluminium hydroxide, be mixed with the molten slurry of aluminium hydroxide that solid content is 17.5 (wt.) %, agitating heating 1.0h at 65 DEG C, obtains slurries A; Account for 200 (wt.) % of aluminium hydroxide according to pectin, take 305.88g pectin, be mixed with the molten slurry of pectin that solid content is 25 (wt.) %, gelatinization 2h at 80 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 1.0h, be then placed in micro-wave oven, take out after microwave 20min under power is 600W, at 85 DEG C, obtain carbon containing alumina precursor after vacuum drying 16h, then in Muffle furnace, obtain alumina catalyst support after roasting 10h at 500 DEG C; Again by 217.06g cobalt nitrate and the water-soluble incipient impregnation of 13.56g yttrium nitrate in above-mentioned alumina support, dry 22h at 85 DEG C, roasting 3h at 380 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: Y 2o 3: Al 2o 3=70:4:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 325 DEG C, 1.2MPa, constant temperature 32h, 550h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 70% (v/v).Reaction condition is: 225 DEG C, 2.2MPa, 2200h -1(v/v), H 2/ CO (mol)=2.4.Evaluation result: CO conversion ratio 51.0%, CH 4selective is 13.2%, C 5 +selective is 77.7%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 280 DEG C, 1.0MPa, 650h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 45% (v/v), constant temperature 20h, 800rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 185 DEG C, 2.8MPa, 1000h -1(v/v), H 2/ CO (v/v)=2.2,550rpm.Evaluation result: CO conversion ratio 83.0%, CH 4selective is 13.0%, C 5 +selective is 75.9%.
Embodiment 7
Form according to final catalyst, take 117.65g boehmite, be mixed with the molten slurry of boehmite that solid content is 22.5 (wt.) %, agitating heating 0.5h at 70 DEG C, obtains slurries A; Account for 30 (wt.) % of boehmite according to starch, take 35.3g starch, be mixed with the molten slurry of starch that solid content is 30 (wt.) %, gelatinization 1h at 90 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 0.5h, be then placed in micro-wave oven, take out after microwave 10min under power is 800W, at 90 DEG C, obtain carbon containing alumina precursor after vacuum drying 12h, then in Muffle furnace, obtain alumina catalyst support after roasting 12h at 450 DEG C; Again by 248.07g cobalt nitrate and the water-soluble incipient impregnation of 11.6g ammonium dimolybdate in above-mentioned alumina support, dry 24h at 90 DEG C, roasting 2h at 400 DEG C, obtains final catalyst, and final catalyst weight consists of Co 3o 4: Mo 3o:Al 2o 3=80:5:100.
Get above-mentioned catalyst 5ml not dilute and fill in (Ф 10 × 500mm) in fixed bed reactors, reducing condition is: 300 DEG C, 1.5MPa, constant temperature 36h, 500h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 85% (v/v).Reaction condition is: 230 DEG C, 2.0MPa, 2500h -1(v/v), H 2/ CO (mol)=2.5.Evaluation result: CO conversion ratio 41.5%, CH 4selective is 14.8%, C 5 +selective is 71.2%.
Get above-mentioned catalyst 10ml to evaluate in 1L paste state bed reactor, reducing condition is, 270 DEG C, 1.2MPa, 550h -1(v/v), hydrogen in nitrogen is adopted, H 2content is 30% (v/v), constant temperature 16h, 700rpm.Be down to room temperature after reduction to switch to synthesis gas and react, reaction condition is 170 DEG C, 3.0MPa, 700h -1(v/v), H 2/ CO (v/v)=2.0,650rpm.Evaluation result: CO conversion ratio 88.8%, CH 4selective is 3.2%, C 5 +selective is 91.1%.

Claims (9)

1. an alumina load Co catalysts, it is characterized in that catalyst is made up of cobaltosic oxide, metal promoter oxide and aluminium oxide, its weight consists of cobaltosic oxide: metal promoter oxide: aluminium oxide=40-80:0.5-5:100.
2. a kind of alumina load Co catalysts as claimed in claim 1, is characterized in that described metal promoter oxide is strontium oxide strontia, yittrium oxide, niobium oxide or molybdenum oxide.
3. the preparation method of a kind of alumina load Co catalysts as claimed in claim 1 or 2, is characterized in that comprising the steps:
Form according to final catalyst, take alumina precursor, be mixed with the molten slurry of alumina precursor that solid content is 10-30wt%, agitating heating 0.5-2h at 40-70 DEG C, obtains slurries A; Account for the 10-200wt% of alumina precursor according to organic carbon source, take organic carbon source, be mixed with the molten slurry of organic carbon source that solid content is 10-30wt%, gelatinization 1-6h at 50-90 DEG C, obtains slurries B; Slurries A and slurries B is mixed, use ultrasonic oscillation 0.5-3.0h, then micro-wave oven is placed in, take out after microwave 5-60min under power is 200-800W, at 60-90 DEG C, obtain carbon containing alumina precursor after vacuum drying 12-36h, then at 450-800 DEG C, obtain alumina support after roasting 4-12h; Again by soluble cobalt and the water-soluble incipient impregnation of solubility promoter metal salt on above-mentioned alumina support, at 60-90 DEG C, roasting 2-6h at dry 12-24h, 300-400 DEG C, obtains final catalyst.
4. the preparation method of a kind of alumina load Co catalysts as claimed in claim 3, is characterized in that described alumina precursor is the one of aluminium carbonate ammonia, aluminium hydroxide or boehmite.
5. the preparation method of a kind of alumina load Co catalysts as claimed in claim 3, is characterized in that described organic carbon source is the one in starch, cellulose, hemicellulose, plant glycogen, agar-agar or pectin.
6. the preparation method of a kind of alumina load Co catalysts as claimed in claim 3, is characterized in that described soluble cobalt is cobalt nitrate or cobalt acetate.
7. the preparation method of a kind of alumina load Co catalysts as claimed in claim 3, is characterized in that described solubility promoter metal salt is strontium nitrate, yttrium nitrate, niobium oxalate or ammonium dimolybdate.
8. the application at F-T synthesis of a kind of alumina load Co catalysts as claimed in claim 1 or 2, is characterized in that carrying out reducing, reacting in fixed bed reactors; Reducing condition is: 350-450 DEG C, 0.3-1.5MPa, GHSV=500-1000h -1, constant temperature 12-36h, adopts hydrogen reduction gas in nitrogen, H 2volume content is 15%-85%; Reaction condition is: 170-230 DEG C, 2.0-3.0Mpa, GHSV=700-2500h -1, H 2/ CO volume ratio=2.0-2.5.
9. the application at F-T synthesis of a kind of alumina load Co catalysts as claimed in claim 1 or 2, is characterized in that carrying out reducing, reacting in paste state bed reactor; Reducing condition is: 270-320 DEG C, 0.2-1.2MPa, GHSV=500-800h -1, constant temperature 12-36h, adopts hydrogen reduction gas in nitrogen, H 2volume content is 15%-85%, and rotating speed is 400-800rpm; Reaction condition is: 170-230 DEG C, 2.0-3.0MPa, GHSV=700-2500h -1, H 2/ CO volume ratio=2.0-3.0, rotating speed is 400-800rpm.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105861024A (en) * 2016-04-20 2016-08-17 中国科学院山西煤炭化学研究所 Application method of cobalt-based Fischer-Tropsch synthesis catalyst
CN107999081A (en) * 2017-12-13 2018-05-08 太原理工大学 A kind of carbon coating structure nano iron-base fischer-tropsch synthesis catalyst and its preparation method and application
CN110902769A (en) * 2019-11-04 2020-03-24 广东省测试分析研究所(中国广州分析测试中心) High-activity alumina three-dimensional electrode particle filler and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070394A2 (en) * 2000-03-17 2001-09-27 Energy International Corporation Highly active fischer-tropsch catalyst comprising doped, thermally stable catalyst support
CN102441393A (en) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof
CN102745729A (en) * 2011-10-26 2012-10-24 台州欧信环保净化器有限公司 High temperature-resistant activated alumina material and preparation method thereof
CN102962066A (en) * 2012-11-26 2013-03-13 中国科学院山西煤炭化学研究所 Alumina-loaded cobalt-based fischer-tropsch synthesis catalyst and preparation method and applications thereof
CN103071481A (en) * 2012-12-29 2013-05-01 烟台万华聚氨酯股份有限公司 Fischer-Tropsch synthesis cobalt-based catalyst and preparation method thereof
CN103831115A (en) * 2013-12-04 2014-06-04 中国科学院山西煤炭化学研究所 Slurry bed Fischer-Tropsch synthetic cobalt-based catalyst and its preparation method and use
CN104162429A (en) * 2014-08-19 2014-11-26 中国科学院山西煤炭化学研究所 Cobalt-based catalyst for Fischer-Tropsch synthesis and application of cobalt-based catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070394A2 (en) * 2000-03-17 2001-09-27 Energy International Corporation Highly active fischer-tropsch catalyst comprising doped, thermally stable catalyst support
CN102441393A (en) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof
CN102745729A (en) * 2011-10-26 2012-10-24 台州欧信环保净化器有限公司 High temperature-resistant activated alumina material and preparation method thereof
CN102962066A (en) * 2012-11-26 2013-03-13 中国科学院山西煤炭化学研究所 Alumina-loaded cobalt-based fischer-tropsch synthesis catalyst and preparation method and applications thereof
CN103071481A (en) * 2012-12-29 2013-05-01 烟台万华聚氨酯股份有限公司 Fischer-Tropsch synthesis cobalt-based catalyst and preparation method thereof
CN103831115A (en) * 2013-12-04 2014-06-04 中国科学院山西煤炭化学研究所 Slurry bed Fischer-Tropsch synthetic cobalt-based catalyst and its preparation method and use
CN104162429A (en) * 2014-08-19 2014-11-26 中国科学院山西煤炭化学研究所 Cobalt-based catalyst for Fischer-Tropsch synthesis and application of cobalt-based catalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
余常林等: ""碱土Sr对Co/Al2O3催化剂甲烷部分氧化反应的影响"", 《燃料化学学报》 *
储伟等: "《催化剂工程》", 30 September 2006 *
刘康慨等: "钼助剂对费托合成催化剂性能的影响", 《山西化工》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105861024A (en) * 2016-04-20 2016-08-17 中国科学院山西煤炭化学研究所 Application method of cobalt-based Fischer-Tropsch synthesis catalyst
CN107999081A (en) * 2017-12-13 2018-05-08 太原理工大学 A kind of carbon coating structure nano iron-base fischer-tropsch synthesis catalyst and its preparation method and application
CN110902769A (en) * 2019-11-04 2020-03-24 广东省测试分析研究所(中国广州分析测试中心) High-activity alumina three-dimensional electrode particle filler and preparation method and application thereof
CN110902769B (en) * 2019-11-04 2022-05-20 广东省测试分析研究所(中国广州分析测试中心) High-activity alumina three-dimensional electrode particle filler and preparation method and application thereof

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