CN100500286C - Microsphere shaped iron based catalyst for Fischer-Tropsch synthesis under high temperature, and preparation method - Google Patents
Microsphere shaped iron based catalyst for Fischer-Tropsch synthesis under high temperature, and preparation method Download PDFInfo
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- CN100500286C CN100500286C CNB200510024821XA CN200510024821A CN100500286C CN 100500286 C CN100500286 C CN 100500286C CN B200510024821X A CNB200510024821X A CN B200510024821XA CN 200510024821 A CN200510024821 A CN 200510024821A CN 100500286 C CN100500286 C CN 100500286C
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Abstract
A microspherical Fe-based catalyst for high-temp Fischer-Tropsch synthesis contains proportionally Fe, Cu, Cr, K2O and Na2O, and is prepared through dissolving iron nitrate, adding the solution of sodium carbonate, depositing, filtering, washing to obtain filtered cake, adding water, beating, adding the solution containing Na, K, Cr and Cr, ageing, spray drying and calcining.
Description
Technical field
The invention belongs to a kind of Preparation of catalysts method, specifically belong to a kind of Fischer-Tropsch synthetic iron-based catalyst and preparation method thereof.
Background technology
Fischer-Tropsch synthesis (F-T Synthesis) is synthesis gas (CO+H
2) on catalyst, be converted into the core process of liquid hydrocarbon fuel, be that nineteen twenty-three is by Germanization scholar Fischer and Tropsch invention.Synthesis gas is produced by conversion of natural gas or is produced through coal gasification by coal.Synthetic iron-based or the cobalt-base catalyst of adopting of Fischer-Tropsch, generally speaking, cobalt-base catalyst is applicable to the synthesis gas that is obtained by conversion of natural gas, and ferrum-based catalyst has good shift activity and sulfur tolerance, and being suitable for the coal is the Fischer-Tropsch building-up process of base.In recent years, along with world economic growth is brought the huge liquid fuel market demand, crude oil price keeps the trend that raises up, and coal/natural gas liquefaction technology obtains paying attention to, and its core is fischer-tropsch synthetic catalyst and relative process.
At present, precipitated iron FTS catalyst and cobalt zirconium silica FTS catalyst are to have realized manufactureization in South Africa Sasol company and Dutch Shell company respectively; A kind of preparation method of microspheroidal Fischer-Tropsch synthetic iron-based catalyst is provided in the CN1395992A patent that Chinese Academy of Sciences's Shanxi coalification is applied for, this catalyst has size distribution and wear resistance preferably.But adopt in the above-mentioned catalyst products therefrom hard wax proportion higher, just can be converted into vapour, diesel oil and other chemical products, increased production cost and complex process degree through deep processing.
Be different from above-mentioned catalyst, the serviceability temperature of high temperature Fischer-Tropsch catalyst is generally 250 ℃～375 ℃, and the product major part is C
20With interior hydro carbons, can obtain the purpose product through simple process.Also rarely found about the research report of high temperature Fischer-Tropsch catalyst at present, and range of application only limits to laboratory stage: Sinopec Group and Chinese science research institute Dalian Chemical Physics Research Institute have narrated a kind of can be used for the iron catalyst of paste state bed reactor and fixed bed reactors in patent, with the activated carbon is carrier, and auxiliary agent is IA family metal and transition metal; Be used for the catalysis synthesis gas and select synthetic vapour, diesel component (＜C
20), serviceability temperature is 300 ℃.Davis etc. (U.S.A.Inc.) have applied for being entitled as and have obtained the patent of carbon number less than the process of the Fischer-Tropsch synthetic of 19 high olefin content, and they adopt the mode of adding the potassium component in ferrum-based catalyst to improve C
5～C
19The selectivity of middle alkene, the Fe-Si-K-Cu catalyst that makes is used for starching the attitude bed, and serviceability temperature can reach 270 ℃, C in the hydrocarbon product that obtains
19Selectivity surpasses 90%.Above-mentioned two exemplary application scopes only limit to the laboratory and prepare on a small scale, and all do not have the trial of spray drying forming.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of in order to overcome the defective that above-mentioned prior art exists and have certain specific surface area and pore structure, high strength, be applicable to fluidized-bed reactor, and production routine is simple, product yield is high and conform with that industrial production requires, is suitable for large-scale production be used for synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch that is used for is characterized in that the weight percentage that comprises Fe in this catalyst is 55～70, and the weight percentage of Cu is 0.05～8.0, and the weight percentage of Cr is 0.05～8.0, K
2The weight percentage of O is 0.05～5.0, Na
2The weight percentage of O is 0.03～5.0.
A kind of preparation method who is used for the synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch is characterized in that this preparation method comprises following processing step:
(1) the reagent ferric nitrate is dissolved in the deionized water, obtains containing the solution of Fe10～100g/mol;
(2) add ammonia spirit in metal salt solution and form the precipitation slurries, the precipitation endpoint pH is 4～10, and precipitation temperature is 10～80 ℃, obtains the co-precipitation filter cake after filtration, the washing;
(3) in the co-precipitation filter cake, add the deionized water making beating, obtain the slurries of solid content 6～18% weight, add then and contain Na
+, K
+, Cr
3+, Cu
2+, and the molar concentration of various ions is that the mixing salt solution of 0.05～4 mol floods, at 10～80 ℃ of dippings 0.5～5 hour down;
(4) slurries after will flooding are sent in the pressure spray dryer, are 250～400 ℃ in the hot-wind inlet temperature, and the wind exhausting outlet temperature is to carry out spray-drying under 100～200 ℃ of conditions;
(5) powder after the spray-drying carries out roasting, and sintering temperature is 300～600 ℃, and roasting time is 1～8 hour, obtains a kind of synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch that is used for.
Described catalyst soakage slurries liquid concentration is 8～15% weight.
Described hot-wind inlet temperature is 260～375 ℃, and the wind exhausting outlet temperature is 110～150 ℃.
Described sintering temperature is 300～500 ℃, and roasting time is 1～3 hour.
The catalyst microsphere diameter that makes with the inventive method is that the yield rate of 20～200 μ m reaches more than 90%, and specific area is 30～60m
2/ g, pore volume are that 0.2～0.5ml/g. intensity meets industrial requirements.
The analysis test method that the present invention is used:
1. the specific area of finished product microballoon ferrum-based catalyst, pore volume and pore-size distribution are measured: adopt low-temperature nitrogen adsorption method, specific area is the BET specific area.
2. the distribution of particles of finished product microballoon ferrum-based catalyst adopts laser particle size analyzer to obtain the catalyst particle size distributed data.
3. the impact strength analysis of microballoon ferrum-based catalyst adopts catalyst impact experiment device and Particle Size Analyzer to measure the ability of catalyst opposing friction and impact grinding.Adopt catalyst abrasion experimental provision and Particle Size Analyzer to measure the ability of catalyst opposing friction and impact grinding.The impact experiment step is as follows: a certain amount of microspherical catalyst is put into experimental provision, utilize the impulse force of gases at high pressure that the metallic plate in microspherical catalyst and the device is clashed into, the catalyst grain size of measuring respectively before and after impacting distributes, and utilizes to record the data computation catalyst strength.
Average grain diameter * 100% before average grain diameter before percentage of damage=experiment-experiment back average grain diameter/experiment
4. the tear strength analysis of microballoon ferrum-based catalyst adopts catalyst abrasion experimental provision and Particle Size Analyzer to measure the ability of catalyst opposing friction and impact grinding.Adopt catalyst abrasion experimental provision and Particle Size Analyzer to measure the ability of catalyst opposing friction and impact grinding.
Compared with prior art, the present invention has the following advantages:
(1) the present invention adopts the precipitation method and wet impregnation, has simplified technological process, and adopting cheap metallic iron and ammoniacal liquor is primary raw material, can reduce production costs.
(2) adopt the spray drying process moulding in the method for preparing catalyst provided by the present invention, employing spray drying process production treating capacity is big, shaping of catalyst is rapid, is suitable for suitability for industrialized production.
(3) the high temperature iron-base fischer-tropsch synthesis catalyst yield rate height that adopts method provided by the invention to make, the intensity of catalyst is good, has good shock resistance and antiwear property, and rational specific area and pore volume, smooth surface is applicable in the fluidized-bed reactor and uses.
Description of drawings
Fig. 1 is the scanning electron microscopic observation microsphere surface pattern of the embodiment of the invention 1 product;
Fig. 2 is the scanning electron microscopic observation microsphere surface pattern of the embodiment of the invention 2 products;
Fig. 3 is the scanning electron microscopic observation microsphere surface pattern of the embodiment of the invention 3 products;
Fig. 4 is the scanning electron microscopic observation microsphere surface pattern of the embodiment of the invention 4 products;
Fig. 5 is the scanning electron microscopic observation microsphere surface pattern of the embodiment of the invention 5 products.
The specific embodiment
Below will the invention will be further described by following examples.
Embodiment 1
With 43kg Fe (NO
3)
3.9H
2O molten with deionized water in, be diluted to 100 liters of solution, above-mentioned iron-containing liquor is added in the reactor, be heated to 62 ℃, in stirring fast 7% ammoniacal liquor being splashed into iron-containing liquor and form the precipitation slurries, is 8 to stop dropping ammonia to pH value, obtains the co-precipitation filter cake after filtering, washing.The co-precipitation filter cake is added deionized water 40L making beating, weighing Cr (NO
3)
3.9H
2O 2.8kg, Cu (NO
3)
2.3H
2O 11g, KNO
355g, NaNO
325g is dissolved in the deionization, is made into 7 liters of solution, adds in the above-mentioned slurries, stirs and makes it abundant mixing, floods 30 minutes down at 46 ℃.The slurry that obtains is 260 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out spray-drying under 125 ℃, and 350 ℃ of roastings 3 hours obtain the final catalyst of 8.2kg, this catalyst called after A.
Embodiment 2
According to embodiment 1 step, obtain the co-precipitation filter cake, add deionized water 30L making beating, weighing Cr (NO
3)
3.9H
2O 150g, Cu (NO
3)
2.3H
2O 1.3kg, KNO
340g, NaNO
344g is dissolved in the deionization, is made into 10 liters of solution, adds in the above-mentioned slurries, stirs and makes it abundant mixing, is heated to 75 ℃, stirs 120 minutes.The slurry that obtains is 350 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out spray-drying under 115 ℃, and 400 ℃ of roastings 6 hours obtain the final catalyst of 8.4kg, above catalyst called after B.
Embodiment 3
The 7kg iron powder is dissolved in the 70L45% nitric acid, be diluted to 90 liters, above-mentioned iron-containing liquor is added in the reactor, at room temperature stirring fast 5% ammoniacal liquor is splashed into iron-containing liquor and form the precipitation slurries, to the pH value is 5.6 to stop dropping ammonia, filters, obtains the co-precipitation filter cake after the washing.The co-precipitation filter cake is moved in the beaker, add deionized water 25L making beating, weighing Cr (NO
3)
3.9H
2O 3.2kg, Cu (NO
3)
2.3H
2O 120g, KNO
34.4g, NaNO
3450g is dissolved in the deionization, is made into 8 liters of solution, adds in the above-mentioned slurries, stirs and makes it abundant mixing, is heated to 70 ℃, stirs 120 minutes.The slurry that obtains is 375 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out spray-drying under 140 ℃, and 500 ℃ of roastings 3 hours obtain the final catalyst of 9.8kg, above catalyst called after C.
Embodiment 4
According to embodiment 3 steps, obtain the co-precipitation filter cake.Add deionized water 35L making beating.Weighing Cr (NO
3)
3.9H
2O 35g, Cu (NO
3)
2.3H
2O 1.5kg, KNO
360g, NaNO
324g is dissolved in the deionization, is made into 11 liters of solution, add in the above-mentioned slurries, stirring makes it abundant mixing, stirs fast to make it form uniform slurries, is heated to 50 ℃, continue then to stir 30 minutes, the slurry that obtains is 300 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out spray-drying under 140 ℃, 425 ℃ of roastings 3 hours, obtain the final catalyst of 9.4kg, above catalyst called after D.
Embodiment 5
In 70 liter of 45% nitric acid of 6.5kg iron powder, be diluted to 120 liters; Add 50 liters of deionized waters in reactor, be preheated to 50 ℃, middling speed stirs, by dropping funel 500ml iron nitrate solution and 4% ammonia spirit and drip are gone in the beaker, control pH value is 7～8, and temperature is 50 ℃ in the control stillpot, till dripping off to ferrous solution.Obtain the co-precipitation filter cake after filtering, washing.Weighing Cr (NO
3)
3.9H
2O 50g, Cu (NO
3)
2.3H
2O 100g, KNO
3600g, NaNO
32g, be dissolved in the deionization, be made into 8.5 liters of solution, add in the above-mentioned slurries, stir and make it abundant mixing, stirring at room 90 minutes, the slurry that obtains is 325 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out spray-drying under 150 ℃, 450 ℃ of roastings 2 hours, obtain the final catalyst of 11.0kg, above catalyst called after E.
The performance indications of table 1 embodiment catalyst
Claims (5)
1. one kind is used for the synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch, and it is characterized in that the consisting of of this catalyst: the weight percentage of Fe is 55～70, and the weight percentage of Cu is 0.05～8.0, and the weight percentage of Cr is 0.05～8.0, K
2The weight percentage of O is 0.05～5.0, Na
2The weight percentage of O is 0.03～5.0, the weight percentage of each component and be 100%.
2. preparation method who is used for the synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch is characterized in that this preparation method comprises following processing step:
(1) with 43kgFe (NO
3)
3.9H
2O is dissolved in the deionized water, is diluted to 100 liters of solution;
(2) add ammonia spirit in iron nitrate solution and form the precipitation slurries, the precipitation endpoint pH is 4～10, and precipitation temperature is 10～80 ℃, obtains the co-precipitation filter cake after filtration, the washing;
(3) in the co-precipitation filter cake, add the deionized water making beating, obtain the slurries of solid content 6～18% weight, add then and contain Na
+, K
+, Cr
3+, Cu
2+, and the molar concentration of various ions is that the mixing salt solution of 0.05～4 mol floods, at 10～80 ℃ of dippings 0.5～5 hour down;
(4) slurries after will flooding are sent in the pressure spray dryer, are 250～400 ℃ in the hot-wind inlet temperature, and the wind exhausting outlet temperature is to carry out spray-drying under 100～200 ℃ of conditions;
(5) powder after the spray-drying carries out roasting, and sintering temperature is 300～600 ℃, and roasting time is 1～8 hour, obtains a kind of synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch that is used for.
3. a kind of preparation method who is used for the synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch according to claim 2 is characterized in that described slurry solid content is 8～15% weight.
4. a kind of preparation method who is used for the synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch according to claim 2 is characterized in that described hot-wind inlet temperature is 260～375 ℃, and the wind exhausting outlet temperature is 110～150 ℃.
5. a kind of preparation method who is used for the synthetic microsphere shaped iron based catalyst of high temperature fischer-tropsch according to claim 2 is characterized in that described sintering temperature is 300～500 ℃, and roasting time is 1～3 hour.
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Non-Patent Citations (2)
| Title |
|---|
| 费－托合成制液态烃研究进展. 代小平等.化学进展，第12卷第3期. 2000 |
| 费－托合成制液态烃研究进展. 代小平等.化学进展，第12卷第3期. 2000 * |
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