CN1562475A - Fischer-Tropsch synthesis catalyzer of microsphere shaped ferro manganese and preparation method - Google Patents
Fischer-Tropsch synthesis catalyzer of microsphere shaped ferro manganese and preparation method Download PDFInfo
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- CN1562475A CN1562475A CN 200410012189 CN200410012189A CN1562475A CN 1562475 A CN1562475 A CN 1562475A CN 200410012189 CN200410012189 CN 200410012189 CN 200410012189 A CN200410012189 A CN 200410012189A CN 1562475 A CN1562475 A CN 1562475A
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Abstract
A microspherical Fe-Mn catalyst for the slurry-bed Fischer-Tropsch synthesis contains Fe, Mn, Mg, K and SiO2 proportionally. It is prepared from the deposit slurry containing Mg assistant and the catalyst slurry prepared from K salt solution and silicon sol through spray drying, and calcining.
Description
Technical field
The present invention relates to a kind of iron/manganese catalyst and preparation method thereof, concrete is exactly a kind of synthetic iron/manganese catalyst of syrup state bed Fischer Tropsch and preparation method thereof that is used for.
Technical background
Ferrum-based catalyst is a most frequently used class fischer-tropsch synthetic catalyst, is the Fischer-Tropsch synthesis of raw material because of it has the active coal based synthetic gas that is specially adapted to low hydrogen-carbon ratio of higher Water gas shift/WGS.That successfully realize at present catalyst that the Sasol company in the South Africa of the synthetic heavy industrialization operation of Fischer-Tropsch adopts is exactly ferrum-based catalyst (M.E.Dry et al, Catalysis Today, 1990,6 (3) 183-206).The synthetic reactor that adopts of Fischer-Tropsch has fixed bed reactors, fluidized-bed reactor and paste state bed reactor.Higher production efficiency, catalyst are easy to loading and unloading, the reaction system heat transfer boundary condition is better because paste state bed reactor has, and are not prone to the hot-spot phenomenon, can directly use low H
2The coal based synthetic gas of/CO ratio, and demonstrate bigger technical advantage.The oily process industrialization of the natural gas base synthesis gas synthetic mesophase fraction that South Africa Sasol company adopted ferrum-based catalyst and paste state bed reactor technology to realize 2500 barrel per days in 1993 (Kott, Oil and Gas Journal, 1997,95 (25), 16-21).
The ferrum-based catalyst that paste state bed reactor adopts need have certain granular size and mar proof, with the ON-LINE SEPARATION that helps product wax and catalyst and the stability of catalyst runs.But most at present research and development concentrate on the Fe/Cu catalyst, disclose the preparation method (WO 99/49965) of used for slurry bed Fischer-Tropsch synthetic iron-based catalyst as South Africa Sasol company in patent, be specially: the sedimentation type ferrum-based catalyst particle that will support certainly obtained less than the synthetic ferrum-based catalyst of using of the wear-resistant syrup state bed Fischer Tropsch of 45 μ m 360～390 ℃ of roastings in 0.5～4 hour.This preparation method does not relate to spray-drying, and the particle of catalyst is less and be continuous distributed, is unfavorable for starching separating of attitude bed reacting middle catalyst and wax; U.S. Rentech company has developed a kind of preparation method (USP 5504118 and CN 1113905A) who is used for the Fischer-Tropsch synthetic iron-based catalyst of paste state bed reactor, be specially: obtain ferrous nitrate with nitric acid dissolve metallic iron and copper, the mixed liquor of ferric nitrate and copper nitrate, then ammoniacal liquor is added in the nitrate mixed liquor of heat, the precipitation slurries, the washing back adds solution of potassium carbonate, making beating, the weight percentage of catalyst in slurries is about 8-12%, use the spray dryer spray-drying then, diameter range is 5-50 μ m, at last 315 ℃ of roastings, but catalyst is spherical relatively poor, does not add anti abrasive SiO in the catalyst
2Binding agent, and particle is little; The somebody uses Si (OC
2H
5)
4The intensity that improves catalyst as the silicon source adopts spray drying technology to prepare 100Fe/5Cu/4.2K/xSiO
2The catalyst of (x=3.85～21.6) (Zhao et al, Ind.Eng.Chem.Res., 2001,40,1065-1075) but because of using Si (OC
2H
5)
4Cost is higher not to have industrial operation and is worth.
About being applicable to the synthetic SiO that contains of syrup state bed Fischer Tropsch
2, and the method that the utilization spray drying technology prepares the Fe/Mn catalyst do not appear in the newspapers as yet,
Summary of the invention:
The purpose of this invention is to provide a kind of synthetic Fe/Mn Catalysts and its preparation method of using of industrial mass production syrup state bed Fischer Tropsch that is suitable for.
Catalyst of the present invention is by Fe, Mn, Mg, K and SiO
2Form, its weight ratio is
Fe: Mn: Mg: K: SiO
2=100: (4-100): (1-50): (0.5-10): (1-45), be preferably Fe: Mn: Mg: K: SiO
2=100: (5-40): (3-20): (1-5): (5-40).
The synthetic Fe/Mn Preparation of catalysts method of Fischer-Tropsch provided by the present invention comprises: form by above-mentioned catalyst, with total concentration of metal ions is 0.05-10.0 mol ferric nitrate, the ammoniacal liquor of the mixing salt solution of manganese nitrate and magnesium nitrate and 0.1-5.0 mol is at 30-95 ℃, co-precipitation under the pH=7.0-11.5 condition, washing, getting solid content after the filtration is the wet slurry of 5-45wt%, with Ludox, sylvite and deionized water add in the wet slurry, making beating mixes and makes catalyst pulp, the solid content of catalyst pulp is 5-45wt%, then catalyst pulp is sent into and carried out spray-drying in the spray dryer, the hot-wind inlet temperature is 180-360 ℃, outlet temperature is 80-170 ℃, be dried to microspheric catalyst at 300-750 ℃ of following roasting 2-12 hour, promptly obtain the synthetic ferrimanganic catalyst of using of syrup state bed Fischer Tropsch.
The concentration of total metal ion of described mixing salt solution is preferably the 0.10-5.00 mol; The concentration of ammoniacal liquor is preferably the 0.5-3.0 mol, and precipitation temperature is preferably 55-95 ℃; The precipitation pH value is preferably 7.5-11.0.
Described Ludox can be acidic silicasol, alkaline silica sol or potassium silicate water glass, SiO in the Ludox
2Weight percentage 5-45wt%, be preferably 15-40wt%.
Described sylvite can be potash, saleratus or potassium acetate.
Described catalyst pulp, its solid content is preferably 10-38wt%.
Described spray-drying hot-wind inlet temperature is preferably 220-280 ℃, and spray-drying wind exhausting outlet temperature is preferably 105-120 ℃.
Described spray-drying can also adopt pressure atomization drier spray-drying to be shaped, and pressure atomization dry feed pressure is 0.2-4.0MPa, is preferably 0.5-2.0MPa, and all the other conditions are identical with said method.
Described catalyst sintering temperature is preferably 350-700 ℃, and roasting time is preferably 3-7 hour.
The Fe/Mn/Mg/K/SiO that the present invention makes
2The yield rate of microsphere diameter 30～120 mu m ranges reaches more than 95% in the catalyst prod;
The present invention makes the Application of Catalyst condition:
(1) reducing condition is: 0.1-2.0MPa, 500-4000h
-1, 200-400 ℃ condition under with hydrogen, carbon monoxide or H
2/ CO reduced 12-60 hour than the synthesis gas for 0.5-3.0.
(2) reaction condition is: 230-380 ℃, 500-5000h
-1, 2.50MPa, unstripped gas H
2/ CO is 0.5-3.0.
The prepared spherical Fe/Mn/MG/K/SiO of the present invention
2Catalyst particle size distributes and adopts the laser particle size distribution instrument to measure.
The present invention has following advantage:
1, catalyst preparation process is simple, is applicable to large-scale industrial production;
2, add cheap Ludox in the catalyst, promptly improved catalyst strength, can reduce the cost of catalyst again;
3, adopt spray drying technology first, catalyst spherical that makes and uniformity are all better, are applicable to that extensive syrup state bed Fischer Tropsch is synthetic,
The specific embodiment
The following examples will the present invention is described further, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
At 80 ℃, under the condition of pH=9.0 with Fe/Mn/Mg (weight ratio is: Fe: Mn: Mg=100: 15: the 10) solution of 2.0 mol and the ammoniacal liquor co-precipitation of 3.0 mol, after slurries washing, the filtration, the filter cake that to get 10 kilograms of solid contents be 39wt% is to the acidic silicasol (SiO that wherein adds 1.44 kilograms
2Content: 30wt%), 112 gram potash and 1 kilogram of deionized water, making beating, the gained slurry solid content is 35.7wt%.Above-mentioned slurry is 270 ℃ at EAT, and leaving air temp is under 95 ℃ the condition, centrifugal spray drying, and the gained dry microspheres is remembered finished catalyst 450 ℃ of following roastings 6 hours.The proportioning of this catalyst activity component is: Fe/Mn/Mg/K/SiO
2=100: 15: 10: 3: 20, its key technical indexes, reducing condition, reaction condition and Fischer-Tropsch synthesis the results are shown in subordinate list.
Embodiment 2
At 50 ℃, under the condition of pH=11.0 with Fe/Mn/Mg (weight ratio is: Fe: Mn: Mg=100: 7: the 19) solution of 4.0 mol and the ammoniacal liquor co-precipitation of 3.0 mol, after slurries washing, the filtration, the filter cake that to get 12 kilograms of solid contents be 18wt% is to the alkaline silica sol (SiO that wherein add 235 grams
2Content: 40wt%), 45.1 gram saleratus and 2 kilograms of deionized waters, making beating, the gained slurry solid content is 16.1wt%.Above-mentioned slurry is 220 ℃ at EAT, and leaving air temp is under 120 ℃ the condition, centrifugal spray drying, and the gained dry microspheres is remembered finished catalyst 350 ℃ of following roastings 7 hours.The proportioning of this catalyst activity component is: Fe/Mn/Mg/K/SiO
2=100: 7: 19: 1.5: 8, its key technical indexes, reducing condition, reaction condition and Fischer-Tropsch synthesis the results are shown in subordinate list.
Embodiment 3
At 85 ℃, under the condition of pH=9.5 with Fe/Mn/Mg (weight ratio is: Fe: Mn: Mg=100: 40: the 15) solution of 1 mol and the ammoniacal liquor co-precipitation of 0.5 mol, after slurries washing, the filtration, the filter cake that to get 11 kilograms of solid contents be 35wt% is to the alkaline silica sol (SiO that wherein adds 2.37 kilograms
2Content: 25wt%), 191 gram potassium acetate and 1 kilogram of deionized water, making beating, the gained slurry solid content is 31.8wt%.Above-mentioned slurry is 250 ℃ at EAT, and leaving air temp is under 100 ℃ the condition, centrifugal spray drying, and the gained dry microspheres is remembered finished catalyst 550 ℃ of following roastings 4 hours.The proportioning of this catalyst activity component is: Fe/Mn/Ca/K/SiO
2=100: 40: 15: 4.5: 35, its key technical indexes, reducing condition, reaction condition and Fischer-Tropsch synthesis the results are shown in subordinate list.
Embodiment 4
At 90 ℃, under the pH=8.0 condition with Fe/Mn/Mg (weight ratio is: Fe: Mn: Mg=100: 20: the 7) solution of 1.0 mol and the ammoniacal liquor co-precipitation of 1.0 mol, after slurries washing, the filtration, the filter cake that to get 15.2 kilograms of solid contents be 23.5wt% is to the alkaline silica sol (SiO that wherein add 960 grams
2Content: 25wt%), 600 the gram 30wt% potassium silicate (SiO
2/ K
2The O mol ratio is 3: 1) and 1 kilogram of deionized water, making beating, the gained slurry solid content is 22.73wt%.Above-mentioned slurry is 265 ℃ at EAT, and leaving air temp is under 120 ℃ the condition, the pressure atomization drying, and slurry sample introduction pressure 0.7MPa, the gained dry microspheres is remembered finished catalyst 550 ℃ of following roastings 4 hours.The proportioning of this catalyst activity component is: Fe/Mn/Mg/K/SiO
2=100: 20: 7: 4: 20, its key technical indexes, reducing condition, reaction condition and Fischer-Tropsch synthesis the results are shown in subordinate list.
Embodiment 5
At 75 ℃, under the condition of pH=8.5 with Fe/Mn/Mg (weight ratio is: Fe: Mn: Mg=100: 10: the 10) solution of 0.5 mol and the ammoniacal liquor co-precipitation of 2.0 mol, after slurries washing, the filtration, the filter cake that to get 13.5 kilograms of solid contents be 26.7wt% is to the acidic silicasol (SiO that wherein adds 1.38 kilograms
2Content: 15wt%), 108 gram potash and 3 kilograms of deionized waters, making beating, the gained slurry solid content is 22.0wt%.Above-mentioned slurry is 255 ℃ at EAT, and leaving air temp is under 100 ℃ the condition, the pressure atomization drying, and slurry sample introduction pressure 1.8MPa, the gained dry microspheres is remembered finished catalyst 650 ℃ of following roastings 2.5 hours.The proportioning of this catalyst activity component is: Fe/Mn/Mg/K/SiO
2=100: 10: 10: 2: 10, its key technical indexes, reducing condition, reaction condition and Fischer-Tropsch synthesis the results are shown in subordinate list.
Subordinate list: the technical indicator of Preparation of Catalyst, reducing condition, reaction condition and Fischer-Tropsch synthesis result.
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Catalyst particle size | ??30-85 | ??25-75 | ????30-70 | ????50-90 | ????55-110 |
| Yield rate (%) | ??93 | ??92 | ????94 | ????97 | ????97.5 |
| Reducing condition | |||||
| Temperature (℃) | ??280 | ??285 | ????290 | ????270 | ????280 |
| Pressure (MPa) | ??0.2 | ??0.1 | ????0.6 | ????0.3 | ????0.5 |
| Air speed (h -1) | ??1000 | ??2000 | ????2000 | ????1000 | ????1000 |
| Gas and time (h) | ??H 2，20h | ??H 2/CO＝ ??0.7，32h | ????H 2/CO＝0.7， ????20h | ????CO，16h | ????H 2/CO＝ ????2.0，24h |
| Reaction condition | |||||
| Temperature (℃) | ??260 | ??250 | ????260 | ????270 | ????275 |
| Pressure (MPa) | ??1.5 | ??1.0 | ????2.0 | ????2.5 | ????1.5 |
| Air speed (h -1) | ??2000 | ??1000 | ????2000 | ????3000 | ????2000 |
| H 2/CO | ??0.70 | ??1.5 | ????2.0 | ????0.67 | ????1.1 |
| The Fischer-Tropsch synthesis result | |||||
| CO conversion ratio (%) | ??73 | ??57 | ????65 | ????75 | ????67 |
| CO 2Selectivity (%) | ??31 | ??27 | ????36 | ????28 | ????35 |
| C 1(wt％) | ??4.7 | ??6.5 | ????5.3 | ????4.1 | ????5.1 |
| C 2-4(wt％) | ??11.2 | ??14.7 | ????13.9 | ????10.4 | ????12.1 |
| C 5 +(wt％) | ??84.1 | ??78.8 | ????80.8 | ????85.5 | ????82.8 |
| C 2-4＝/C 2-4 0 | ??5.2 | ??4.3 | ????3.6 | ????6.2 | ????5.1 |
Claims (11)
1, a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst is characterized in that catalyst is by Fe, Mn, Mg, K and SiO
2Form, its weight ratio is
Fe∶Mn∶Mg∶K∶SiO
2＝100∶(4-100)∶(1-50)∶(0.5-10)∶(1-45)。
2, a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 1 is characterized in that described weight ratio is
Fe∶Mn∶Mg∶K∶SiO
2＝100∶(5-40)∶(3-20)∶(1-5)∶(5-40)。
3, a kind of preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 1 or 2 is characterized in that comprising the steps:
With total concentration of metal ions is 0.05-10.0 mol ferric nitrate, the ammoniacal liquor of the mixing salt solution of manganese nitrate and magnesium nitrate and 0.1-5.0 mol is at 30-95 ℃, co-precipitation under the pH=7.0-11.5 condition, washing, getting solid content after the filtration is the wet slurry of 5-45wt%, with Ludox, sylvite and deionized water add in the wet slurry, making beating mixes and makes catalyst pulp, the solid content of catalyst pulp is 5-45wt%, then catalyst pulp is sent into and carried out spray-drying in the spray dryer, the hot-wind inlet temperature is 180-360 ℃, outlet temperature is 80-170 ℃, be dried to microspheric catalyst at 300-750 ℃ of following roasting 2-12 hour, promptly obtain the synthetic ferrimanganic catalyst of using of syrup state bed Fischer Tropsch.
4, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3, the concentration that it is characterized in that total metal ion of described mixing salt solution is the 0.10-5.00 mol; The concentration of ammoniacal liquor is the 0.5-3.0 mol, and precipitation temperature is 55-95 ℃; The precipitation pH value is 7.5-11.0.
5, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3 is characterized in that described Ludox is acidic silicasol, alkaline silica sol or potassium silicate water glass, SiO in the Ludox
2Weight percentage 5-45wt%.
6, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 5 is characterized in that SiO in the described Ludox
2Weight percentage be 15-40wt%.
7, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3 is characterized in that described sylvite can be potash, saleratus or potassium acetate.
8, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3 is characterized in that its solid content of described catalyst pulp is 10-38wt%.
9, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3 is characterized in that described spray-drying hot-wind inlet temperature is 220-280 ℃, and spray-drying wind exhausting outlet temperature is 105-120 ℃.
10, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3 is characterized in that described catalyst sintering temperature is 350-700 ℃, and roasting time is 3-7 hour.
11, the preparation method of a kind of microspheroidal ferrimanganic fischer-tropsch synthetic catalyst as claimed in claim 3, it is characterized in that spray-drying can also adopt pressure atomization drier spray-drying to be shaped, pressure atomization dry feed pressure is 0.2-4.0MPa, be preferably 0.5-2.0MPa, all the other conditions are identical with the described method of claim 3.
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| WO2010121516A1 (en) * | 2009-04-22 | 2010-10-28 | 中科合成油技术有限公司 | Fischer–tropsch synthesis catalyst, preparation and application thereof |
| CN102381844A (en) * | 2011-07-26 | 2012-03-21 | 西安工程大学 | Method for modifying hollow glass microspheres by chemical precipitation process |
| CN102441384A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin catalyst by high-activity-stability carrier-type iron-based synthetic gas |
| CN103521239A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin through Fischer-Tropsch synthesis and preparation method of catalyst |
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| AU2010239013B2 (en) * | 2009-04-22 | 2013-01-31 | Synfuels China Technology Co., Ltd. | Fischer-Tropsch synthesis catalyst, preparation and application thereof |
| RU2477654C1 (en) * | 2009-04-22 | 2013-03-20 | Синфьюэлс Чайна Текнолоджи Ко., Лтд | Fischer-tropsh synthesis catalyst, its production and application |
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| CN102381844A (en) * | 2011-07-26 | 2012-03-21 | 西安工程大学 | Method for modifying hollow glass microspheres by chemical precipitation process |
| CN102381844B (en) * | 2011-07-26 | 2013-08-07 | 西安工程大学 | Method for modifying hollow glass microspheres by chemical precipitation process |
| CN103521239A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin through Fischer-Tropsch synthesis and preparation method of catalyst |
| CN103521239B (en) * | 2012-07-03 | 2015-12-09 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of F-T synthesis producing light olefins |
| CN105688926A (en) * | 2014-11-24 | 2016-06-22 | 神华集团有限责任公司 | Fischer-tropsch iron-based catalyst high in low carbon olefin yield, and preparation method thereof |
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| CN107243347A (en) * | 2017-07-06 | 2017-10-13 | 中国科学院上海高等研究院 | A kind of ferrum-based catalyst of synthesis gas alkene and its production and use |
| CN107243347B (en) * | 2017-07-06 | 2020-08-07 | 中国科学院上海高等研究院 | Iron-based catalyst for preparing olefin from synthesis gas and preparation method and application thereof |
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