CN1159098C - Fe-base catalyst for Fischer-Tropsch syuthesis and its preparing process - Google Patents
Fe-base catalyst for Fischer-Tropsch syuthesis and its preparing process Download PDFInfo
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- CN1159098C CN1159098C CNB011204176A CN01120417A CN1159098C CN 1159098 C CN1159098 C CN 1159098C CN B011204176 A CNB011204176 A CN B011204176A CN 01120417 A CN01120417 A CN 01120417A CN 1159098 C CN1159098 C CN 1159098C
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Abstract
The present invention relates to a method for preparing an iron based catalyst used for Fischer-Tropsch synthesis. Cheap raw material of ferrous sulphate is used, and ferrous sulphate is oxidized by an oxidizing agent of H2O2 to obtain iron sulfate solution; then, the iron sulfate solution is mixed with the mixed solution of lanthanum nitrate and copper salt, and fast coprecipitation is carried out by using an alkaline reacting compound; after precipitation slurry is washed, the water glass solution of potassium metasilicate of different module is further added into the slurry; then, the iron based catalyst is prepared by spray drying, or the material is tableted into the iron based catalyst which is suitable for a fixed bed reactor after being drying and roasting. The cost of the preparing method is low, and the present invention is suitable for large-scale production of industrial serialization. The prepared catalyst can be used for the fixed bed Fischer-Tropsch synthetic reaction and can also be used for the Fischer-Tropsch synthetic reaction of a slurry bed.
Description
Technical field:
The invention belongs to a kind of Preparation of catalysts method, it is synthetic with containing ferrum-based catalyst of lanthanum auxiliary agent and preparation method thereof to relate in particular to a kind of Fischer-Tropsch.
Background technology:
Fischer-Tropsch is synthetic be find the twenties in last century by synthesis gas (CO+H
2) a kind of method of synthetic liquid fuel, and since the fifties, realized that in South Africa coal-based synthetic liquid fuel heavy industrialization (is published in Catalysis Today referring to Dry ME, paper on 1990,6 (3) 183-206 " The Fischer-Tropsch Process-Commercial Aspects ").What Fischer-Tropsch synthesized normal employing is ferrum-based catalyst, synthesis gas reacts in being equipped with the fixed bed of ferrum-based catalyst, fluid bed or paste state bed reactor, produce required hydrocarbon products, comprise gasoline, diesel oil, wax, naphtha, low-carbon alkene etc., synthesis gas can have carbon raw materials such as coal, natural gas, coal bed gas, coke, living beings to make.Be the type of reactor that the transformation efficiency, hydrocarbon products selectivity and the adaptation that improve synthesis gas are adopted, new iron-based Study of Catalyst is being carried out always.
U.S. Mobil company discloses a kind of method that adopts the Fe-Cu-K fischer-tropsch synthetic catalyst of the low nitrogen content of continuous coprecipitation preparation in U.S. Pat P4617288, be specially: the ammonia spirit of the ferric nitrate of metered proportions and copper nitrate mixed solution and debita spissitudo is maintained the temperature at 80-90 ℃, the head tank of pH between 6.6-6.8 with what pump squeezed into that a band stirs with water vapour, the precipitation slurries import a subsider continuously, suction filtration, spend deionised water to there not being nitrate anion, add a certain amount of K again
2CO
3Solution, making beating, oven dry, 300 ℃ of roastings make the catalyst that nitrogen content is lower than 100ppm, and this method is fit to industrialization and produces continuously.
U.S. Rentech company discloses a kind of preparation method who is used for the Fischer-Tropsch synthesis iron base catalyst of paste state bed reactor in U.S. Pat P5504118 and Chinese invention patent CN1113905A, be specially: the mixed liquor that obtains ferrous nitrate, ferric nitrate and copper nitrate with nitric acid dissolve metallic iron and copper, must be in solution during dissolving aerating oxygen, to reduce content of nitric oxide, the small amount of N O that overflows
2Remove with the absorption of KOH solution.Ammoniacal liquor is added in the nitrate mixed liquor of heat, pH is controlled at 7.4, obtains the precipitation slurries, then with the high-quality water washing of no chlorine to there not being ammonium nitrate, add solution of potassium carbonate subsequently, making beating, the weight percentage of catalyst in slurries is about 8-12%, use the spray dryer spray-drying then, remove most of moisture, obtaining is spherical catalyst granules roughly, and diameter range is 5-50 μ m, last catalyst is heated to about 315 ℃ and removes residual moisture in air, make catalyst stabilising.
U.S. Texas A﹠amp; People such as the Burkur of M university are at magazine Ind.Eng.Chem.Res., and 1990,29, a kind of Fe/Cu/K/SiO is disclosed among the 1588-1599
2The Preparation of catalysts method is specially: add ammonia spirit and carry out continuous co-precipitation in the ferric nitrate of 82 ℃ of the maintenances of proper ratio and copper nitrate mixed solution, precipitate with deionized water is washing and suction filtration thoroughly, adds a certain amount of 26wt%K
2SiO
3Solution, reslurry also makes pH≤6, after the vacuum drying, uses a certain amount of KHCO again
3Solution impregnation is dried then and was made in 5 hours 300 ℃ of roastings, subsequently at Ind.Eng.Chem.Res., and 1999,38, will fill a prescription among the 3270-3275 is 100Fe/3Cu/4K/16SiO
2The catalyst of (weight meter) is used to starch the reaction of attitude bed, finds that this catalyst is to low H
2The raw material of synthetic gas of/CO ratio has high activity and high C
5 +With selectivity of light olefin.
But above-mentioned several catalyst are because the cost of material that uses is more expensive, cause the cost height, on the high side of catalyst.
Summary of the invention:
It is low and have high activity and a C to the purpose of this invention is to provide a kind of price
5Fischer-Tropsch synthetic iron-based catalyst of the high selectivity of above hydrocarbon and low-carbon alkene and preparation method thereof.
The object of the present invention is achieved like this: adopt cheap ferrous sulfate raw material, by oxidant H
2O
2Oxidation obtains ferrum sulfuricum oxydatum solutum, mix with lanthanum nitrate and mantoquita mixed solution then, carry out quick co-precipitation with alkali compounds, after the washing of precipitation slurries, slip further adds the potassium silicate water glass solution of different moduluses, spray-drying makes ferrum-based catalyst then, or compression molding makes the ferrum-based catalyst that is suitable for fixed bed reactors after the oven dry roasting.
Catalyst weight ratio of the present invention consists of: Fe: La: Cu: K: SiO
2=100: 0.02～2: 0.01～5: 0.5～10: 5～30.
Aforesaid K weight ratio is preferably 1～7.
Aforesaid SiO
2Weight ratio is preferably 8～27.
Preparation method of the present invention comprises the steps:
(1) with molar concentration be 0.5～10mol/L copperas solution, the concentrated sulfuric acid and weight percent concentration be 3～30wt% hydrogen peroxide solution in molar ratio for ferrous sulfate: sulfuric acid: the ratio of hydrogen peroxide=1: 1.6～2.0: 3.7 is mixed, in oxidizing temperature is under 20～80 ℃ of conditions, oxidation time is 1～10 hour, makes ferrum sulfuricum oxydatum solutum;
(2) consist of Fe: La: Cu: K: SiO by the catalyst weight ratio
2=100: 0.02-2: 0.01-5: 0.5-10: 5-30 is made into the copper lanthanum aqueous solution that total mol concentration is 1～4mol/L with mantoquita and lanthanum nitrate;
(3) alkaline precipitating agent being mixed with molar concentration is 1～6mol/L precipitating reagent aqueous solution;
(4) pressing catalyst and form, after ferrum sulfuricum oxydatum solutum and copper lanthanum aqueous solution, is under 20～95 ℃ of conditions at precipitation temperature, adds the precipitating reagent aqueous solution, makes pH value of solution=5～10, and the rapid precipitation time is 5～60 minutes;
(5) left standstill ageing time 1～2 hour, suction filtration washs sediment repeatedly with deionized water, till the sulfate radical-free ion;
(6) to add that deionized water carries out adding mol ratio after the pulp be SiO to sediment again
2: K
2The potassium silicate water glass of O=1～10, the addition of its potassium silicate water glass are pressed catalyst and are formed adding, stir, and obtain catalyst pulp;
(7) a. is dried catalyst pulp, roasting, and the compression molding fragmentation is chosen 20～40 orders as the fixed bed fischer-tropsch synthetic catalyst;
B. catalyst pulp is carried out spray-drying, roasting is chosen 50～100 μ m as the syrup state bed Fischer Tropsch synthetic catalyst.
Aforesaid copperas solution molar concentration is preferably 1～5mol/L.
Aforesaid ferrous sulfate can be the byproduct of titanium powder plant, steel mill.
The weight percent concentration of aforesaid hydrogen peroxide solution is preferably 10～20%.
Aforesaid oxidizing temperature is preferably 25～60 ℃.
Aforesaid oxidation time is preferably 2～6 hours.
The mol ratio of aforesaid ferrous sulfate, sulfuric acid and hydrogen peroxide is preferably 1: 1.8～and 1.95: 4～6.
Aforesaid mantoquita is copper nitrate, copper sulphate, Schweinfurt green.
Aforesaid lanthanum nitrate and mantoquita total mol concentration are preferably 1.5～3.0mol/L.
Aforesaid precipitating reagent is Na
2CO
3, ammoniacal liquor, NaOH, KOH, K
2CO
3Deng, preferentially select Na
2CO
3, ammoniacal liquor, NaOH, preferentially select the concentration of 1.5～4.5mol/L.
Aforesaid precipitating reagent aqueous solution molar concentration is preferably 1.5～4.5mol/L.
Aforesaid precipitation temperature is preferably 60～90 ℃.
Aforesaid pH value is preferably 7～8.5.
The aforesaid sedimentation time is preferably 10～30 minutes.
Aforesaid SiO
2With K
2The O mol ratio is preferably 2～5.
The present invention compared with prior art has following advantage:
(1) to prepare source of iron raw material described in the ferrum-based catalyst process be ferrous sulfate in the present invention, low price, and the source is wide, can be the byproduct ferrous sulfate of titanium powder plant, steel mill, compares with preparation method in the past, can reduce the Catalyst Production cost greatly.
(2) to prepare the oxidant of ferrous sulfate described in the ferrum-based catalyst process be H in the present invention
2O
2, it is few to have addition, and oxidation is complete, is difficult for bringing into the characteristics of impurity.
(3) the present invention prepares in the ferrum-based catalyst process lanthanum auxiliary agent and realizes by adding lanthanum nitrate hexahydrate, the lanthanum auxiliary agent in catalyst with iron phase than proportion 0.01% to 5%, usually account for 0.02% to 2%, proportion is less in the catalyst cost, can obviously not improve the manufacturing cost of catalyst.
(4) ferrum-based catalyst that makes of the present invention has high reactivity and to above hydrocarbon of C5 and the high selectivity of low-carbon alkene, is particularly useful in paste state bed reactor by coal based synthetic gas combined diesel oil, gasoline and wax product.
The specific embodiment:
Below be detailed content of the present invention and Fischer-Tropsch synthesis effect embodiment, protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
FeSO with 100kg
47H
2O is dissolved in the 360L deionized water, adds the sulfuric acid solution 6.5L of 3mol/L again.H to this mixed solution adding 15%
2O
2Aqueous solution 45L, oxidation is 4 hours under 35 ℃ of following high degree of agitation, stops air inlet then.2.3kg Cu (NO
3)
23H
2O and 12.6gLa (NO
3)
36H
2O dissolves in the 10L deionized water, obtains nitric acid and lanthanum nitrate mixed solution.Copper nitrate and lanthanum nitrate mixed solution are added in the above-mentioned ferrum sulfuricum oxydatum solutum that makes, obtain the mixing salt solution of iron content, lanthanum, copper.The Na of 120kg
2CO
3Dissolve in the 400L deionized water and obtain aqueous sodium carbonate.Mixed acid salting liquid and sodium carbonate liquor are heated respectively by the chuck mode with water vapour and to remain to 85 ℃, with identical flow velocity squeeze in the jar of a high degree of agitation with sodium carbonate liquor the mixed acid salting liquid with acid-proof pump continuously with lye pump, maintain the temperature at 85 ℃, the PH=8-8.5 of mixed solution mixes even
Continuous coprecipitation process was finished in 20 minutes, and the pH value is 8.2.Left standstill aging 2 hours, suction filtration is used the deionized water cyclic washing, to using BaCl
2Aqueous assay is till the sulfate radical-free.Filter cake adds 50L water reslurry again, is 3.6 the 20wt%SiO that contains with modulus
2Potassium silicate water glass solution 7.3L add in these slurries, high degree of agitation is even, with slurry 110 ℃ of oven dry in baking oven, 350 ℃ of following roastings 5 hours, obtains the 32kg ferrum-based catalyst more then, the catalyst weight ratio is Fe/La/Cu/K/SiO
2=100: 0.02: 3: 3: 10, this catalyst is designated as C.After this catalyst screening, get the catalyst of 20-40 order particle and in the fixture bed experiment chamber device, choose the Fischer-Tropsch synthesis performance.
Embodiment 2
According to embodiment 1 step, after the filter cake of the acquisition making beating, with modulus 3.6 the 20wt%SiO that contains
2Potassium silicate water glass solution 7.3L add in these slurries, high degree of agitation evenly after.The deionized water that adds 180L again, making beating is carried out spray-drying with this slurry again, obtains the powder of approximate spherical particles, and this powder through 350 ℃ of following roastings 5 hours, obtains the 32.5kg ferrum-based catalyst again, and the catalyst weight ratio is Fe/La/Cu/K/SiO
2=100: 0.02: 3: 3: 10, this catalyst is designated as D.After this catalyst screening, get 50-100 μ m section particle competition Fischer-Tropsch synthesis performance in slurry attitude bed laboratory installation.
Embodiment 3
FeSO with 60kg
47H
2O is dissolved in the 150L deionized water, adds the sulfuric acid solution 4L of 3mol/L again.The H of adding 5% in this mixed solution
2O
2Aqueous solution 75L, oxidation is 5.5 hours under 50 ℃ of high degree of agitation.2.3kg Cu (NO
3)
23H
2O and 18.8g La (NO
3)
3.6H
2O dissolves in the 10L deionized water, obtains copper nitrate and lanthanum nitrate mixing salt solution.Copper nitrate and lanthanum nitrate mixing salt solution are added in the above-mentioned ferrum sulfuricum oxydatum solutum that makes, obtain the mixing salt solution of iron content, lanthanum, copper.The 9.5wt% ammonia spirit of 240L places in another storage tank.Mixed acid salting liquid and ammonia spirit are heated respectively by the chuck mode with water vapour and to remain to 65 ℃, with identical flow velocity squeeze in the jar of a high degree of agitation with ammonia spirit the mixed acid salting liquid with acid-proof pump continuously with lye pump, maintain the temperature at 65 ℃, mix continuous coprecipitation process and finished in 30 minutes, the pH value is 7.5.Left standstill aging 1 hour, suction filtration is used the deionized water cyclic washing, to using BaCl
2Aqueous assay is till the sulfate radical-free.Filter cake adds 35L water reslurry again, is 2.5 the 25wt%SiO that contains with modulus
2Potassium silicate water glass solution 3.6L add in these slurries, high degree of agitation is even, with slurry 110 ℃ of oven dry in baking oven, 400 ℃ of following roastings 3 hours, obtains the 20kg ferrum-based catalyst more then, part by weight is Fe/La/Cu/K/SiO
2=100: 0.5: 5: 5: 10, this catalyst is designated as E.After this catalyst screening, be used for fixing bed reaction competition by embodiment 1 subsequently.
Embodiment 4
According to embodiment 1 step, after filter cake making beating and adding potassium silicate water glass solution stir again.The deionized water that adds 120L again, making beating is carried out spray-drying with this slurry again, obtains the powder of approximate spherical particles, through 400 ℃ of following roastings 3 hours, obtains ferrum-based catalyst 21kg again, and part by weight is Fe/La/Cu/K/SiO
2=100: 0.5: 5: 5: 10, this catalyst is designated as F.After this catalyst screening, get 50-100 μ m section particle competition Fischer-Tropsch synthesis performance in slurry attitude bed laboratory installation.
Embodiment 5
FeSO with 150kg
47H
2O is dissolved in the 450L deionized water, adds the sulfuric acid solution 14L of 2mol/L again.The H of adding 20% in this mixed solution
2O
2Aqueous solution 50L, oxidation is 2 hours under 40 ℃ of high degree of agitation.4.6kg Cu (NO
3)
23H
2O and 75.3g La (NO
3)
3.6H
2O dissolves in the 20L deionized water, obtains the mixing salt solution of copper nitrate and lanthanum nitrate.Mix the mixing salt solution that obtains iron content, lanthanum, copper with the ferrum sulfuricum oxydatum solutum that makes.The NaOH of 57kg dissolves in the 500L deionized water and obtains sodium hydrate aqueous solution.Mixed acid salting liquid and sodium hydroxide solution are heated respectively by the chuck mode with water vapour and to remain to 85 ℃, with identical flow velocity squeeze in the jar of a high degree of agitation with sodium hydroxide solution the mixed acid salting liquid with acid-proof pump continuously with lye pump, maintain the temperature at 80 ℃, mix continuous coprecipitation process and finished in 60 minutes, the pH value is 7.8.Left standstill aging 3 hours, suction filtration is used the deionized water cyclic washing, to using BaCl
2Aqueous assay is till the sulfate radical-free.Filter cake adds 80L water reslurry again, is 3.0 the 25wt%SiO that contains with modulus
2Potassium silicate water glass solution 13L add in these slurries, high degree of agitation is even, with slurry 100 ℃ of oven dry in baking oven, 350 ℃ of following roastings 4 hours, obtains the 48kg ferrum-based catalyst more then, part by weight is Fe/La/Cu/K/SiO
2=100: 0.8: 4: 6: 15, this catalyst is designated as G.After this catalyst screening, be used for fixing bed reaction competition by embodiment 1 subsequently.
Embodiment 6
According to embodiment 3 steps, after filter cake making beating and adding potassium silicate water glass solution stir again.The deionized water that adds 320L again, making beating is carried out spray-drying with this slurry again, obtains being similar to the powder of spherical particles, and roasting 4 hours under 350C again obtains ferrum-based catalyst 49kg, and part by weight is Fe/La/Cu/K/SiO
2=100: 0.8: 4: 6: 15, this catalyst is designated as H.After this catalyst screening, get 50-100 μ m section particle competition Fischer-Tropsch synthesis performance in slurry attitude bed laboratory installation.
Catalyst Fischer-Tropsch synthesis competition experiment is carried out on laboratory installation, and wherein C, E, G catalyst are chosen in fixed bed reactors, the unstripped gas H of employing
2/ CO=2, air speed 1500NL/Lcat.h, reaction temperature is that 250 ℃, reaction pressure are 2.0MPa; D, F, H catalyst are chosen in the mechanical agitation paste state bed reactor, catalyst granules 50-100 μ m, in atoleine is housed, the content of catalyst in atoleine is 15%, the unstripped gas H of employing
2/ CO=0.67, air speed 2000NL/kgFe.h, reaction temperature is that 260 ℃, reaction pressure are 2.0MPa.Selecting result is listed in the table 1.
Table 1 evaluating catalyst result
Catalyst numbering C D E F G H
The CO conversion ratio, % 87.0 78.0 86.0 81.0 87.36 75.35
CO is transformed into CO
2
32.0 48.3 28.3 47.5 27.89 48.5
Selectivity, %
Hydrocarbon-selective, wt%
CH
4 6.32 2.60 5.85 3.21 7.53 3.00
C
2-C
4 26.40 10.35 24.56 12.35 24.36 13.80
C
5-C
11 30.12 12.56 32.47 13.81 31.45 11.90
C
12 + 37.16 74.49 37.12 70.63 36.66 71.30
C
2 =-C
4 =At C
2-C
4Hydrocarbon
71.34 84.25 68.17 85.78 69.35 83.24
Middle ratio, %
By table 1 as seen, this catalyst has high reaction activity and high on fixed bed reactors, and methane selectively is lower than 8%, C
5Above hydrocarbon is more than 67%, and at C
2-C
4Low-carbon alkene accounts for more than 66% in the hydrocarbon, so this catalyst is the fixed bde catalyst of function admirable.This catalyst is used for paste state bed reactor, at low H
2Under the unstripped gas of/CO ratio and the high air speed, catalyst has very high reactivity, and the CO conversion ratio is more than 75%, and methane selectively is below 3.5%, and in hydrocarbon distributes, C
12Above hydrocarbon accounts for larger proportion, at C
2-C
4Low-carbon alkene accounts for more than 80% in the hydrocarbon, so this catalyst is particularly suitable in paste state bed reactor by products such as coal based synthetic gas combined diesel oil, gasoline, waxes.
Claims (18)
1. a Fe-base catalyst for Fischer-Tropsch syuthesis is characterized in that the catalyst weight ratio consists of: Fe: La: Cu: K: SiO
2=100: 0.02～2: 0.01～5: 0.5～10: 5～30.
2. a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 1 is characterized in that described K weight ratio is 1～7.
3. a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 1 is characterized in that described SiO
2Weight ratio is 8～27.
4. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 1 is characterized in that described preparation method comprises the steps:
(1) with molar concentration be 0.5～10mol/L copperas solution, the concentrated sulfuric acid and weight percent concentration be 3～30wt% hydrogen peroxide solution in molar ratio for ferrous sulfate: sulfuric acid: the ratio of hydrogen peroxide=1: 1.6～2.0: 3.7 is mixed, in oxidizing temperature is under 20～80 ℃ of conditions, oxidation time is 1～10 hour, makes ferrum sulfuricum oxydatum solutum;
(2) consist of Fe: La: Cu: K: SiO by the catalyst weight ratio
2=100: 0.02-2: 0.01-5: 0.5-10: 5-30 is made into the copper lanthanum aqueous solution that total mol concentration is 1～4mol/L with mantoquita and lanthanum nitrate;
(3) alkaline precipitating agent being mixed with molar concentration is 1～6mol/L precipitating reagent aqueous solution;
(4) pressing catalyst and form, after ferrum sulfuricum oxydatum solutum and copper lanthanum aqueous solution, is under 20～95 ℃ of conditions at precipitation temperature, adds the precipitating reagent aqueous solution, makes pH value of solution=5～10, and the rapid precipitation time is 5～60 minutes;
(5) left standstill ageing time 1～2 hour, suction filtration washs sediment repeatedly with deionized water, till the sulfate radical-free ion;
(6) to add that deionized water carries out adding mol ratio after the pulp be SiO to sediment again
2: K
2The potassium silicate water glass of O=1～10, the addition of its potassium silicate water glass are pressed catalyst and are formed adding, stir, and obtain catalyst pulp;
(7) a. is dried catalyst pulp, roasting, and the compression molding fragmentation is chosen 20～40 orders as the fixed bed fischer-tropsch synthetic catalyst;
B. catalyst pulp is carried out spray-drying, roasting is chosen 50～100 μ m as the syrup state bed Fischer Tropsch synthetic catalyst.
5. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described copperas solution molar concentration is 1～5mol/L.
6. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described ferrous sulfate is the byproduct of titanium powder plant, steel mill.
7. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4, the weight percent concentration that it is characterized in that described hydrogen peroxide solution is 10～20%.
8. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described oxidizing temperature is 25～60 ℃.
9. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described oxidation time is 2～6 hours.
10. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4, the mol ratio that it is characterized in that described ferrous sulfate, sulfuric acid and hydrogen peroxide is 1: 1.8～1.95: 4～6.
11. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described mantoquita is copper nitrate, copper sulphate or Schweinfurt green.
12. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described lanthanum nitrate and mantoquita total mol concentration are 1.5～3.0mol/L.
13. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described precipitating reagent is Na
2CO
3, ammoniacal liquor, NaOH, KOH or K
2CO
3, preferentially select Na
2CO
3, ammoniacal liquor or NaOH.
14. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described precipitating reagent aqueous solution molar concentration is 1.5～4.5mol/L.
15. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described precipitation temperature is 60～90 ℃.
16. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described pH value is 7～8.5.
17. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that the described sedimentation time is 10～30 minutes.
18. the preparation method of a kind of Fe-base catalyst for Fischer-Tropsch syuthesis as claimed in claim 4 is characterized in that described SiO
2With K
2The O mol ratio is 2～5.
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| US8506895B2 (en) | 2007-09-29 | 2013-08-13 | Synfuels China Technology Co. Ltd. | Gas-liquid-solid three-phase suspension bed reactor for fischer-tropsch synthesis and its applications |
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| CN100460066C (en) * | 2004-06-28 | 2009-02-11 | 华东理工大学 | Process for preparing synthetic hydrocarbon catalyst of synthetic gas |
| CN1297343C (en) * | 2004-11-30 | 2007-01-31 | 中国科学院山西煤炭化学研究所 | Iron/manganese catalyst used for Fischer Tropsch synthesis, its preparation method and application |
| CN101381615B (en) * | 2007-09-07 | 2012-12-26 | 新奥科技发展有限公司 | Catalyst for improving selectivity of synthesis gas conversion and preparation method thereof |
| BRPI0913296A2 (en) * | 2008-06-02 | 2018-02-06 | Rentech Inc | method for producing a catalyst precursor, catalyst precursor, method for producing a catalyst, and catalyst |
| EP2684936A1 (en) * | 2012-07-13 | 2014-01-15 | Dr.-Ing. Edmund Wagner | Method for producing hydrocarbons from carbon dioxide and hydrogen and a catalyst which can be used in the process |
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| CN1395993A (en) | 2003-02-12 |
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Application publication date: 20030212 Assignee: Huainan Catalyst Co., Ltd. of Synfuels China Assignor: Zhongke Synthetic Oil Technology Co., Ltd. Contract record no.: 2013340000100 Denomination of invention: Iron base catalyst for fischer-tropsch synthesis and preparation method thereof Granted publication date: 20040728 License type: Exclusive License Record date: 20130708 |
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