CN101920204B - Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst - Google Patents
Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a cobalt-based Fischer-Tropsch synthesis catalyst. Silica gel is used as a carrier, and a two-time dipping method is used for loading an active component Co, wherein when the primary dipping process is carried out, the pH of a cobalt salt dipping solution is higher; and when the secondary dipping process is carried out, the pH of the cobalt salt dipping solution is lower. When the cobalt-based Fischer-Tropsch synthesis catalyst prepared by the method of the invention is applied to Fischer-Tropsch synthesis reaction, higher conversion rate and more than C5 product selectivity are kept, and simultaneously, the selectivity of carbon dioxide and methane is lower. The invention has ideal economical efficiency and is environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst, relating in particular to a kind of is carrier with the modified silica-gel, the preparation method of the high-activity cobalt-based fischer-tropsch synthetic catalyst that low carbon dioxide and methane generate.
Background technology
The synthetic reaction that is meant synthesis gas (carbon monoxide and hydrogen) catalysis synthetic hydrocarbon liquid fuel on catalyst of Fischer-Tropsch.Have advantages such as not relying on oil, product cleaning because Fischer-Tropsch is synthetic, and change to coal, oil and natural gas alliance type from single oil dependent form with the world energy sources structure, improve day by day with environmental requirement, the Fischer-Tropsch synthetic technology will be developed rapidly.
The co-based fischer-tropsch catalyst is one of key technology in the Fischer-Tropsch synthetic technology efficiently, and each major oil companies has successively developed with amorphous Si O
2, TiO
2And Al
2O
3Co based Fischer-Tropsch synthesis catalyst for main carrier.
CN1981927A discloses a kind of with the catalyst that cobalt aluminate mixes with aluminium oxide or aluminium oxide precursor and method of roasting makes, and at 220 ℃, 2.5MPa and synthesis gas flow are in the agitated reactor of 100ml/min, the total conversion (CO+H of catalyst
2) be 54.5%, C
5 +Selectivity is 87.2%, CO
2Selectivity is 1.86%, CH
4Selectivity is 5.74%, though this catalyst has lower CO
2And CH
4Selectivity, but total conversion is not high, a large amount of unconverted unstripped gas need recycle.
CN101134164A discloses a kind of catalyst that contains effective cobalt metal component and preparing carriers, and dipping satisfies at V
L/ Vc=0.01～0.99, wherein V
LBe maceration extract volume, V
CPore volume for carrier.After this catalyst placed fixed bed reactors, at 210 ℃, 2.5MPa and synthesis gas air speed were 500 (in the status of criterion, per hour per volume of catalyst is required with going into the synthesis gas volume) per hour, the total conversion (CO+H of catalyst
2) be 85.27%, C
5 +Selectivity is 79.35%, CO
2Selectivity is 1.52%, CH
4Selectivity is 9.89%.In this technology, conversion of raw material increases, but C
5 +Selectivity is not high, and this technological methane production is higher, and the purpose selectivity of product still needs further to improve.
Summary of the invention
Deficiency to prior art; The present invention provides a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst; When this catalyst is used for Fischer-Tropsch synthesis, has the selectivity of lower carbon dioxide and methane when keeping the above product selectivity of higher conversion ratio and C5.
The preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention comprises following process: be carrier with silica gel, adopt infusion process load active component Co twice, when flooding for the first time, the pH 3.1 to 5 of cobalt salt dipping solution is preferably 4～5; When flooding for the second time, the pH of cobalt salt dipping solution below 3, is preferably 0.1～3.It is higher more than 1 than double-steeping cobalt salt dipping solution pH value to flood for the first time cobalt salt dipping solution pH value, preferred high more than 2.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, the weight content of Co is 15%～40% in the final catalyst, and is preferred 15%～30%, and the load capacity of Co counts 1%～12% by final catalyst weight, preferred 5%～10% when flooding for the first time.The cobalt salt dipping solution is generally cobalt nitrate, and the pH value of cobalt salt dipping solution adopts various suitable materials to regulate, and regulates as adopting nitric acid, ammonium nitrate, ammoniacal liquor etc.Heat-treat behind the dipping for the first time, heat treatment can comprise drying and roasting, also can only carry out drying, carries out drying and calcination process behind the dipping for the second time, and this area conventional method and condition are adopted in dry and roasting.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention; Can add required auxiliary agent at arbitrary steps; As flooding suitable auxiliary agent before or simultaneously at dipping active metal component Co, auxiliary agent can adopt the single-steeping mode of loading, also can adopt the dip loading mode twice; Auxiliary agent generally is one or more among Re, Zr, the Ce etc., preferred Zr.Promoter addition generally accounts for 0.5%～10% of catalyst weight.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, silica gel can adopt the commercially available prod, also can be by prior art for preparing, as adopting Prepared by Sol Gel Method.The preliminary treatment that silica gel can suit before the supported active metal component as required, as comprise and take off that sodium is handled or surface modification treatment etc.
Take off sodium processing method and condition and be generally, earlier with nitric acid or ammonium nitrate solution washing, use the distilled water cyclic washing again under the room temperature, take off in the silica gel of sodium that sodium content is general to require to be lower than 500 μ g/g.
Surface modification treatment is as carrying out surface modification treatment with aqueous slkali.Aqueous slkali can be inorganic alkaline solution or organic basic solution.Surface modifying treatment is well-known to those skilled in the art.
Compared with prior art; Among the preparation method of the inventive method Co based Fischer-Tropsch synthesis catalyst; Through the step impregnation of active metal component, the step impregnation of the dipping solution of particularly different pH values makes active metal component and carrier form different effects and dispersion results; Compared with prior art, the activity of such catalysts of the inventive method preparation and selectivity all obviously improve.Experimental data shows, the catalyst of the inventive method preparation, and the conversion per pass of reaction raw materials can reach more than 85%, does not need the tail gas cycling, saves equipment investment and operating cost.Accessory substance CO
2And CH
4Productive rate obviously reduces, and the purpose product yield improves, and the economy when helping improving the application of Fischer-Tropsch synthetic technology is environmentally friendly simultaneously, meets the environmental requirement of increasingly stringent.Simultaneously, to the silica-gel carrier raw material properties, the processing that suits can further improve the serviceability of preparing product.
The specific embodiment
A kind of concrete fischer-tropsch synthetic catalyst preparation method of the present invention is following; At first silica-gel carrier being taken off sodium handles; With the ammonium salt solution of solubility silica-gel carrier is flooded modification more afterwards; Dipping can adopt saturated dipping or supersaturation dipping, carries out drying behind the dipping, carries out calcination process then.The impregnation process temperature is 70～100 ℃, is preferably 75～90 ℃, and the impregnation process time is 1～100h, preferred 10～80h.Baking temperature is 60～120 ℃, and be 1～30h drying time, preferably at 70～100 ℃ of down dry 8～24h.300-600 ℃ of following roasting 2～15 hours, preferably 350～500 ℃ of following roastings 4～10 hours.
Adopt the method for fractional steps to add among metal promoter Re, Zr, the Ce etc. one or more, preferred Zr again.Dipping can adopt step impregnation, floods 0.5%～2% Zr earlier by final catalyst weight, and baking temperature was 60～120 ℃, 300～500 ℃ of following roastings 4～12 hours.Regulate cobalt nitrate salting liquid pH value 3.1 to 5 with ammonium nitrate then, be preferably 4～5, carry out drying behind the dipping, also can proceed calcination process.Flood with nitric acid again and regulate metal promoter salting liquid pH value below 3, the pH value is excellent to be 1～3, and pickup is 0.3%～5% of a final catalyst weight, preferred 2%～3%.It is below 3 that final impregnating uses nitric acid to regulate cobalt nitrate solution pH value, preferred 0.1～3, and making the total weight of cobalt percentage in the final catalyst is 15%～40%, preferred 15%～30%.Described baking temperature is 60～120 ℃, and roasting condition is 300～450 ℃ of following roastings 2～12 hours.
Further specify the inventive method and effect through embodiment below.
Embodiment 1
(1) (pore volume is 1.06ml/g, and specific area is 386.81m to take by weighing commercially available silica gel
2/ g, following examples are all used this silica gel) 30g, take off sodium and handle, take off sodium and handle method of operating and with condition be: earlier with nitric acid or ammonium nitrate solution washing, use the distilled water cyclic washing again under the room temperature, requirement takes off that sodium content is lower than 500 μ g/g in the silica gel behind the sodium.
(2) silica gel that takes off after sodium is handled carries out the alkali modification processing, and processing method and condition are: with the 50ml weight concentration is 5% sal volatile, adds in the silica gel down at 50 ℃, handles 10 hours.60 ℃ of dryings 24 hours are then 280 ℃ of roastings 15 hours.
(3) silica gel after alkali treatment dipping active component and auxiliary agent by catalyst zirconium content 1wt%, take by weighing zirconium nitrate 1g and are dissolved in the carrier silica gel after 34ml adds above-mentioned modification and flood, and aging 2 hours, 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.
(4) earlier by catalyst cobalt content 10wt%, take by weighing cobalt nitrate 10.49g and be dissolved in 34ml, add in the sample behind the above-mentioned dipping zirconium, and regulate pH value with ammonium nitrate and equal 4, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.
(5) according to the final zirconium content 3% of catalyst, take by weighing zirconium nitrate 2g and be dissolved in the carrier silica gel after 34ml adds above-mentioned modification and flood, regulate pH value with nitric acid more simultaneously and equal 2, aging 2 hours, 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.
(6) by catalyst cobalt total content 30wt%, take by weighing cobalt nitrate 20.99g and be dissolved in 34ml, add in the above-mentioned sample, and regulate pH value with nitric acid and equal 0.5, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-1.
Evaluating catalyst test (following examples are identical with comparative example), was reduced 12 hours down for 350 ℃ with pure hydrogen as solvent with paraffin in the high pressure CSTR, and pressure is 1.0MPa.The cooling back is switched synthesis gas and is reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 180-250 ℃, 500h
-1, 2.0MPa, H
2/ CO=2 (mol ratio).The result is as shown in table 1 for C-1 catalyst Fischer-Tropsch synthesis.
Comparative example 1
Pressing embodiment 1 described process, is that required active metal component Co single-steeping loads on the silica-gel carrier, obtains catalyst B-1, and evaluation result is seen table 1.
Embodiment 2
Press embodiment 1 described process, just, take by weighing cobalt nitrate 5.29g and be dissolved in 34ml earlier by catalyst cobalt content 5wt%; Add in the sample behind the above-mentioned dipping zirconium, and regulate pH value with ammonium nitrate and equal 5, aging 2 hours; 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.Afterwards according to the final zirconium content 2% of catalyst, take by weighing zirconium nitrate 1g and be dissolved in the carrier silica gel after 34ml adds above-mentioned modification and flood, regulate pH value with nitric acid more simultaneously and equal 2, aging 2 hours, 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.By catalyst cobalt total content 30wt%, take by weighing cobalt nitrate 25.78g and be dissolved in 34ml at last, add in the above-mentioned sample, and regulate pH value with nitric acid and equal 0.5, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-2.Evaluation result is seen table 1.
Embodiment 3
Press embodiment 1 described process,, take by weighing cobalt nitrate 5.29g and be dissolved in 34ml just at last by catalyst cobalt total content 15wt%; Add in the above-mentioned sample, and equal 0.5, aging 3 hours with nitric acid adjusting pH value; 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-3.Evaluation result is seen table 1.
Embodiment 4
Press embodiment 1 described process,, take by weighing cobalt nitrate 20.99g and be dissolved in 34ml just at last by catalyst cobalt total content 30wt%; Add in the above-mentioned sample, and equal 1, aging 4 hours with nitric acid adjusting pH value; 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-4.Evaluation result is seen table 1.
Embodiment 5
Press embodiment 1 described process, just, take by weighing cobalt nitrate 10.49g and be dissolved in 34ml earlier by catalyst cobalt content 10wt%; Add in the sample behind the above-mentioned dipping zirconium, and regulate pH value with ammonium nitrate and equal 5, aging 2 hours; 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.Afterwards according to the final zirconium content 3% of catalyst, take by weighing zirconium nitrate 2g and be dissolved in the carrier silica gel after 34ml adds above-mentioned modification and flood, regulate pH value with nitric acid more simultaneously and equal 3, aging 3 hours, 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.By catalyst cobalt total content 20wt%, take by weighing cobalt nitrate 10.49g and be dissolved in 34ml at last, add in the above-mentioned sample, and regulate pH value with nitric acid and equal 1, aging 4 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-5.Evaluation result is seen table 1.
Embodiment 6
Press embodiment 1 described process, just, take by weighing cobalt nitrate 10.49g and be dissolved in 34ml earlier by catalyst cobalt content 10wt%; Add in the sample behind the above-mentioned dipping zirconium, and regulate pH value with ammonium nitrate and equal 4, aging 2 hours; 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.Afterwards according to the final zirconium content 2% of catalyst, take by weighing zirconium nitrate 1g and be dissolved in the carrier silica gel after 34ml adds above-mentioned modification and flood, regulate pH value with nitric acid more simultaneously and equal 3, aging 3 hours, 80 ℃ of dryings 6 hours, roasting is 4 hours in 350 ℃.By catalyst cobalt total content 15wt%, take by weighing cobalt nitrate 5.29g and be dissolved in 34ml at last, add in the above-mentioned sample, and regulate pH value with nitric acid and equal 0.3, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-6.Evaluation result is seen table 1.
The reactivity worth of table 1 embodiment catalyst
| Catalyst | Reaction temperature/℃ | CO conversion ratio (%) | C 5 +Selectivity (wt%) | CH 4Selectivity (wt%) | CO 2Selectivity (wt%) |
| C-1 | 220 | 90.4 | 91.7 | 4.61 | 0.48 |
| B-1 | 220 | 80.6 | 76.3 | 11.58 | 1.46 |
| C-2 | 220 | 88.2 | 88.9 | 5.98 | 0.75 |
| C-3 | 220 | 85.9 | 90.1 | 4.63 | 0.46 |
| C-4 | 220 | 89.1 | 88.9 | 5.24 | 0.57 |
| C-5 | 220 | 87.2 | 89.8 | 4.92 | 0.49 |
| C-6 | 220 | 85.3 | 91.2 | 4.71 | 0.66 |
Claims (10)
1. the preparation method of a Co based Fischer-Tropsch synthesis catalyst is a carrier with silica gel, it is characterized in that: adopt infusion process load active component Co twice, and when flooding for the first time, the pH 3.1 to 5 of cobalt salt dipping solution; When flooding for the second time, the pH of cobalt salt dipping solution is below 3.
2. according to the described method of claim 1, it is characterized in that: when flooding for the first time, the pH 4 to 5 of cobalt salt dipping solution; When flooding for the second time, the pH of cobalt salt dipping solution is 0.1～3.
3. according to the described method of claim 1, it is characterized in that: among the preparation method of Co based Fischer-Tropsch synthesis catalyst, the weight content of Co is 15%～40% in the final catalyst, and the load capacity of Co counts 1%～12% by final catalyst weight when flooding for the first time.
4. according to claim 1 or 3 described methods; It is characterized in that: among the preparation method of Co based Fischer-Tropsch synthesis catalyst; The weight content of Co is 15%～30% in the final catalyst, and the load capacity of Co counts 5%～10% by final catalyst weight when flooding for the first time.
5. according to the described method of claim 1, it is characterized in that: the cobalt salt dipping solution is a cobalt nitrate solution, and the pH value of cobalt salt dipping solution adopts nitric acid, ammonium nitrate or ammoniacal liquor to regulate.
6. according to the described method of claim 1, it is characterized in that: heat-treat behind the dipping for the first time, heat treatment comprises drying and roasting, perhaps only carries out drying, carries out drying and calcination process behind the dipping for the second time.
7. according to the described method of claim 1, it is characterized in that: among the preparation method of Co based Fischer-Tropsch synthesis catalyst, before dipping active metal component Co or flood auxiliary agent simultaneously, auxiliary agent adopts the single-steeping mode of loading, perhaps adopts the dip loading mode twice.
8. according to the described method of claim 7, it is characterized in that: auxiliary agent is one or more among Re, Zr, the Ce, and promoter addition accounts for 0.5%～10% of catalyst weight.
9. according to the described method of claim 1, it is characterized in that: silica-gel carrier carried out preliminary treatment before the supported active metal component.
10. according to the described method of claim 9, it is characterized in that: the preliminary treatment that silica-gel carrier carried out before the supported active metal component comprises that taking off sodium handles or surface modification treatment.
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| CN102861580B (en) * | 2011-07-04 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of preparation method of syngas conversion catalyst |
| CN102908957B (en) * | 2011-08-01 | 2015-04-15 | 中国石油化工股份有限公司 | Method for Fischer-Tropsch synthesis |
| US8936662B2 (en) | 2012-10-02 | 2015-01-20 | Integrated Global Services, Inc. | Apparatus and methods for large particle ash separation from flue gas using screens having semi-elliptical cylinder surfaces |
| CN110876933B (en) * | 2018-09-05 | 2023-03-31 | 国家能源投资集团有限责任公司 | Composite oxide carrier, cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN109759051B (en) * | 2019-01-15 | 2021-10-22 | 昆明理工大学 | Preparation method of catalyst for modifying white carbon black by using Zr-Nd-O |
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| CN1460546A (en) * | 2003-05-29 | 2003-12-10 | 中国科学院山西煤炭化学研究所 | Preparation method fo cobalt zirconium Fischer-Tropsch synthesis catalyst |
| CN101020137A (en) * | 2006-02-15 | 2007-08-22 | 中国石油天然气股份有限公司 | Catalyst for preparing heavy hydrocarbon with synthetic gas and its prepn process |
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