CN100434169C - Microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature and production thereof - Google Patents
Microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature and production thereof Download PDFInfo
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Abstract
The present invention relates to a microspherical iron-based catalyst for Fischer-Tropsch synthesis at high temperature and a preparation method thereof. The catalyst has a composition of weight ratio: Fe: Cu: Cr: K2 O: Na2 O=100: 0.01 to 10: 0.03 to 10: 0.01 to 6: 0.01 to 5; the preparation method for the catalyst comprises: iron powder is dissolved in nitric acid to obtain iron nitrate solution, the iron nitrate solution is diluted and is added with ammonium bicarbonate solution, precipitate slurry is obtained and is filtered and wasted to obtain a filter cake, a certain amount of water and an auxiliary agent are added for beating, impregnation of definite time is carried out to obtain slurry, and the microspherical iron-based catalyst for Fischer-Tropsch synthesis is obtained by centrifugal type spray drying and roasting. The present invention overcomes the defects of other precipitation agents, such as ammonia water and sodium carbonate, the prepared catalyst has high strength, good antifriction performance, narrow particle size distribution, good particle sphericity degree, high activity and higher selectivity for C<5+> hydrocarbon, and the catalyst is suitable for fluidized-bed reactors.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, relate in particular to a kind of Fischer-Tropsch high temperature synthesis iron base 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 gasification by coal.The Fischer-Tropsch synthesis temperature has the branch of low temperature and high temperature, and corresponding catalyst is divided into two kinds of low temperature catalyst and high temperature catalysts.The temperature that low temperature catalyst uses is generally at 200 ℃～250 ℃, and the hard wax proportion is higher in the reaction products therefrom, needs just can be converted into vapour, diesel oil and other chemical products through deep processing, has increased production cost and complex process degree.The temperature that high temperature catalyst uses is generally at 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.The general fusion method or the precipitation method of adopting of Fischer-Tropsch high temperature catalyst preparation prepare, the precipitation method prepare the used precipitating reagent of catalyst and generally adopt ammoniacal liquor, because ammoniacal liquor is volatile, add that reaction temperature is higher, the stirring of reactor has aggravated the volatilization of ammoniacal liquor, makes severe operational environment.
Summary of the invention
Purpose of the present invention is exactly that a kind of narrow size distribution, more high strength, anti abrasive microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature that is applicable to fluidized-bed reactor and preparation method thereof are provided in order to overcome the defective that above-mentioned prior art exists, this preparation method's production cost is low, simple to operate, be convenient to control, pollute few kind.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature is characterized in that, this catalyst weight ratio consists of Fe: Cu: Cr: K
2O: Na
2O=100: 0.01～10: 0.03～10: 0.01～6: 0.01～5.
A kind of preparation method of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature is characterized in that, this preparation method comprises following processing step:
(1) iron powder is dissolved in the salpeter solution of 30～40% weight, obtains the solution that Fe content is 10～100g/l;
(2) add iron nitrate solution in ammonium bicarbonate soln 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) add the deionized water making beating in the co-precipitation filter cake, obtain the slurries of solid content 6～18% weight, add then and contain Na
+, K
+, Cr
3+, Cu
2+Mixing salt solution, and Na
+Molar concentration is 0.03～4 mol, K
+Molar concentration is 0.35～3.5 mol, Cr
3+Molar concentration is 0.03～4 mol, Cu
2+Molar concentration is 0.02～3.7 mol, floods 0.5～5 hour down at 10～60 ℃, obtains flooding slurries;
(4) will flood slurries and send in the centrifugal spray dryer, be 200～400 ℃ 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 that obtains after the spray-drying is carried out roasting, sintering temperature is 300～600 ℃, and roasting time is 1～8 hour;
Obtain a kind of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature through behind the above-mentioned processing step, this catalyst weight ratio consists of Fe: Cu: Cr: K
2O: Na
2O=100: 0.01～10: 0.03～10: 0.01～6: 0.01～5.
Described step (3) catalyst soakage concentration of slurry is 10～20% weight.
Described step (4) hot-wind inlet temperature is 260～375 ℃, and the wind exhausting outlet temperature is 110～150 ℃.
Described step (5) sintering temperature is 300～500 ℃, and roasting time is 1～5 hour.
Making the catalyst microsphere diameter with the inventive method is that the yield rate of 20～200 μ m reaches more than 90%, and 30～80 μ m finished products account for more than 80%, and specific area is 30～60m
2/ g, pore volume are 0.2～0.5ml/g.It is the catalyst that precipitating reagent obtains that intensity and wearability obviously are better than with ammoniacal liquor.
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 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 catalyst opposing friction, capability.Adopt catalyst abrasion experimental provision and Particle Size Analyzer to measure the ability of catalyst opposing friction and impact grinding.
Average grain diameter * 100% before average grain diameter before wear intensity=experiment-experiment back average grain diameter/experiment
5. scanning electron microscopic observation microsphere surface pattern.
The present invention compared with prior art has the following advantages:
1. the present invention adopts carbonic hydroammonium as precipitating reagent, because carbonic hydroammonium and iron nitrate solution all are quantitative addings, precipitation reaction is simple to operate, the precise control of reacted pH value, and reaction temperature is low, can react at normal temperatures, and the specificity of catalyst favorable reproducibility.Greatly reduce the volatilization of ammonia simultaneously, reduced injury personnel and environment.
2. adopt centrifugal spray drying process moulding in the method for preparing catalyst provided by the present invention, compare with the press spray drying means, the catalyst granules outer surface that it obtains is good, ball-type degree height, the narrow particle size distribution of catalyst, pipeline are difficult for stopping up, operate simplyr, be suitable for suitability for industrialized production.
3. adopting the intensity of the high temperature iron-base fischer-tropsch synthesis catalyst that the present invention makes to be better than with ammoniacal liquor is the catalyst of precipitating reagent preparation, has better shock resistance and antiwear property, is applicable in fluidized-bed reactor and uses.
4. the present invention adopts carbonic hydroammonium can accurately control Na in the catalyst as precipitating reagent than making precipitating reagent with sodium carbonate
2The content of O, precipitation filter simultaneously and easier washing can be saved 40% washings.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited by the following example.
Embodiment 1
The 7kg iron powder is dissolved in the 60L45% nitric acid, filter also and 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
2O3.2kg, Cu (NO
3)
2.3H
2O120g, KNO
34.4g, NaNO
3450g is dissolved in the deionized water, 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 300 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out the press spray drying under 140 ℃, and 500 ℃ of roastings 3 hours obtain the final catalyst of 9.8kg, above catalyst called after A.
Embodiment 2
The 7kg iron powder is dissolved in the 62L45% nitric acid, filters and be diluted to 90 liters, above-mentioned iron-containing liquor is added in the reactor.35kg carbonic hydroammonium is formulated as 10% ammonium bicarbonate soln, at the uniform velocity joins formation precipitation slurries in the iron-containing liquor, endpoint pH about 7 30 ℃ of following stirrings.Obtain the co-precipitation filter cake after filtering, washing.The co-precipitation filter cake is moved in the beaker, add deionized water 25L making beating, weighing Cr (NO
3)
3.9H
2O3.2kg, Cu (NO
3)
2.3H
2O120g, KNO
34.4g, NaNO
3450g is dissolved in the deionized water, is made into 8 liters of solution, adds in the above-mentioned slurries, stirs under the room temperature and makes it abundant mixing, stirs 120 minutes.The slurry that obtains is 300 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out centrifugal spray-drying under 140 ℃, and 500 ℃ of roastings 3 hours obtain the final catalyst of 9.5kg, above catalyst called after B.
Embodiment 3
With 43kgFe (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 65 ℃, in stirring fast 5% ammoniacal liquor being splashed into iron-containing liquor and form the precipitation slurries, is 7 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
2O2.8kg, Cu (NO
3)
2.3H
2O11g, 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 120 minutes down at 50 ℃.The slurry that obtains is 260 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out the press spray drying under 125 ℃, and 450 ℃ of roastings 3 hours obtain the final catalyst of 8.2kg, this catalyst called after C.
Embodiment 4
With 45kgFe (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 30 ℃, 30kg carbonic hydroammonium is formulated as 10% ammonium bicarbonate soln, the limit is stirred at the uniform velocity to join and is formed the precipitation slurries in the iron-containing liquor, and endpoint pH about 7 obtains the co-precipitation filter cake after filtering, washing.The co-precipitation filter cake is added deionized water 30L making beating, weighing Cr (NO
3)
3.9H
2O2.8kg, Cu (NO
3)
2.3H
2O11g, 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, and dipping is 120 minutes under the room temperature.The slurry that obtains is 260 ℃ at control inlet hot blast temperature, and the outlet hot blast temperature is to carry out centrifugal spray-drying under 125 ℃, and 450 ℃ of roastings 3 hours obtain the final catalyst of 8.1kg, this catalyst called after D.
Catalyst to preparation has carried out detailed physical property analysis, the results are shown in Table 1
The performance indications of table 1 embodiment catalyst
The Fischer-Tropsch of catalyst closes the reaction evaluating experiment to carry out on the fluidized bed reaction of laboratory.Air speed 1400-1450 (ml)/g.cat./h, 350 ℃ of reaction temperatures.Reaction pressure 2.5MPa, unstripped gas proportioning H
2/ CO=3.0, evaluation result is listed in table 2
The evaluation result of table 2 catalyst
By table 2 as seen, this catalyst has high reaction activity and high and good selectivity equally in fluidized-bed reactor under above-mentioned reaction condition, and adopting carbonic hydroammonium to do precipitating reagent does not have much influences to activity of such catalysts.
Claims (5)
1. a microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature is characterized in that, this catalyst weight ratio consists of Fe: Cu: Cr: K
2O: Na
2O=100: 0.01～10: 0.03～10: 0.01～6: 0.01～5.
2. the preparation method of a microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature is characterized in that, this preparation method comprises following processing step:
(1) iron powder is dissolved in the salpeter solution of 30～40% weight, obtains the solution that Fe content is 10～100g/l;
(2) add iron nitrate solution in ammonium bicarbonate soln 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) add the deionized water making beating in the co-precipitation filter cake, obtain the slurries of solid content 6～18% weight, add then and contain Na
+, K
+, Cr
3+And Cu
2+Mixing salt solution, and Na
+Molar concentration is 0.03～4 mol, K
+Molar concentration is 0.35～3.5 mol, Cr
3+Molar concentration is 0.03～4 mol, Cu
2+Molar concentration is 0.02～3.7 mol, floods 0.5～5 hour down at 10～60 ℃, obtains flooding slurries;
(4) will flood slurries and send in the centrifugal spray dryer, be 200～400 ℃ 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 that obtains after the spray-drying is carried out roasting, sintering temperature is 300～600 ℃, and roasting time is 1～8 hour;
Obtain a kind of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature through behind the above-mentioned processing step, this catalyst weight ratio consists of Fe: Cu: Cr: K
2O: Na
2O=100: 0.01～10: 0.03～10: 0.01～6: 0.01～5.
3. the preparation method of a kind of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature according to claim 2 is characterized in that, described step (3) catalyst soakage concentration of slurry is 10～20% weight.
4. the preparation method of a kind of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature according to claim 2 is characterized in that, described step (4) hot-wind inlet temperature is 260～375 ℃, and the wind exhausting outlet temperature is 110～150 ℃.
5. the preparation method of a kind of microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature according to claim 2 is characterized in that, described step (5) sintering temperature is 300～500 ℃, and roasting time is 1～5 hour.
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| CN101829580B (en) * | 2009-03-12 | 2012-10-03 | 中科合成油技术有限公司 | Fischer-Tropsch synthetic catalyst, preparation method and application thereof |
| CN101869840A (en) * | 2009-04-22 | 2010-10-27 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN102453492B (en) * | 2010-10-21 | 2014-03-26 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method for heavy hydrocarbons |
| CN112138665B (en) * | 2020-10-21 | 2022-10-28 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN114192157B (en) * | 2021-12-29 | 2023-11-21 | 上海兖矿能源科技研发有限公司 | Nano iron-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| US6277895B1 (en) * | 1999-09-21 | 2001-08-21 | Hydrocarbon Technologies, Inc. | Skeletal iron catalyst having improved attrition resistance and product selectivity in slurry-phase synthesis processes |
| CN1395992A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Process for preparing microspherical Fischer-Tropsch catalyst |
| US20040106517A1 (en) * | 2000-05-23 | 2004-06-03 | Dlamini Thulani Humphrey | Chemicals from synthesis gas |
| CN1600421A (en) * | 2003-09-22 | 2005-03-30 | 上海兖矿能源科技研发有限公司 | Micro sphere type catalyst of Fischer-Tropsch synthesis and preparation method |
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| US6277895B1 (en) * | 1999-09-21 | 2001-08-21 | Hydrocarbon Technologies, Inc. | Skeletal iron catalyst having improved attrition resistance and product selectivity in slurry-phase synthesis processes |
| US20040106517A1 (en) * | 2000-05-23 | 2004-06-03 | Dlamini Thulani Humphrey | Chemicals from synthesis gas |
| CN1395992A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Process for preparing microspherical Fischer-Tropsch catalyst |
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