CN104785277A - Cobalt-based catalyst for Fischer-Tropsch synthesis and preparation method for cobalt-based catalyst - Google Patents
Cobalt-based catalyst for Fischer-Tropsch synthesis and preparation method for cobalt-based catalyst Download PDFInfo
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Abstract
The invention discloses a cobalt-based catalyst for Fischer-Tropsch synthesis. The cobalt-based catalyst comprises 10-50 wt% of Co and 10-90 wt% of MnO; the Co and the MnO form CoO-MnO solid solution. The invention further discloses a preparation method for the cobalt-based catalyst. The preparation method comprises the following steps: enabling the active metal Co and an additive Mn to form the CoO-MnO solid solution through conventional impregnating and calcining; reducing the CoO-MnO solid solution with hydrogen comprising 1-30% of Co to obtain the cobalt-based catalyst. According to the invention, the active site on the cobalt-based catalyst is controlled; the activity in the catalyst form in-situ reduction with the hydrogen comprising Co at low temperature high pressure; heavy hydrocarbon is obtained while light hydrocarbon is obtained; the yields of the heavy hydrocarbon and the light hydrocarbon are improved at the same tine in cobalt-based Fischer-Tropsch synthesis.
Description
Technical field
The present invention relates to coal chemical technology, particularly relate to a kind of cobalt-base catalyst for F-T synthesis and preparation method thereof.
Background technology
Along with the exhaustion of world petroleum resource, future source of energy consumption will based on coal and natural gas.In view of the national conditions of the few oily lean gas of the rich coal of China, the coal chemical technologies such as Development of Coal liquefaction, coal gas seem very important and have market prospects, and this is also one of important channel ensureing Chinese energy safety.Following shale gas also may can bring new synthetic fuel industry in the potentiality of China.
F-T synthesis refers to and under certain temperature, pressure and under the effect of catalyst, reacts generation hydro carbons (C by synthesis gas
1~ C
50) process.The active metal of F-T synthesis mainly comprises Ru, Ni, Fe and Co.Wherein, the Fischer-Tropsch catalytic activity of Ru is the strongest, and get final product the hydrocarbon product that catalysis generates carbon number wider range at low temperatures, but its reserves in the whole world are very limited, price is also very expensive.This make in the catalyst based research of Ru almost complete set in theoretical research, the commercial Application of open report.The catalyst based activity of Ni is also comparatively strong, but Ni is catalyst based easily loses with the volatilization of the form of carbonyl nickel in course of reaction, and in course of reaction, methane selectively is high.And Fe is catalyst based has 2 outstanding features: one, Fe belongs to common metal, its rich reserves, cheap, and this can reduce the cost of catalyst; Its Water gas shift/WGS of two, Fe is active strong.Water gas shift reaction is conducive to improving the H in reaction system
2/ CO, thus can promote H
2the utilization of the synthesis gas that/CO is lower.The price of Co catalyst, higher than Fe, lower than Ru, does not belong to the category of noble metal.In addition, catalyst based F-T synthesis activity and the hydrogenation activity with appropriateness of Co, is suitable for catalysis and generates generate longer-chain hydrocarbons.Co is catalyst based does not substantially have Water gas shift/WGS active in certain temperature range, is therefore applicable to H
2the synthesis gas (synthesis gas as from natural gas) that/CO is higher is as raw material.
Fischer-Tropsch synthetic distribution is comparatively extensive, according to the model of chain growth, generally meets Anderson-Schulz-Flory distribution, mainly at C
4-C
12in linear relation in scope, the researcher thus had only calculates to obtain the chain growth factor with line interval.Generally speaking, the primary bias that actual distribution and ideal distribution exist is the higher and C of methane distribution
2-C
3component is on the low side.Methane content is higher may be because alhpa olefin generation hydrogenolysis can generate methane, C
2-C
3component is on the low side then mainly due to the alkene generation secondary reaction of short chain, and such as absorption causes chain growth or inserts carbochain again, and low-carbon (LC) hydrocarbon product is reduced.
Heavy hydrocarbon (C in Fischer-Tropsch product
5~ C
50) or wax can further by conversion generate gasoline, diesel oil and base oil.Because generated fuel oil purity is high, can as high-quality power fuel, comparing nuisance in the exhaust emissions after having burning than the gasoline, diesel of routine less, is environmentally friendly fuel.Secondly, it can also based on oil, full synthetic lubricant fluid can be formed further, there is better economic worth.In addition, the heavy wax that F-T synthesis is formed inherently can be used as fine chemical product, as surfactant precursor.For making synthesis gas be converted into heavy hydrocarbon efficiently, especially more than diesel oil distillate, developing high selectivity, high activity, long-life catalyst and optimize its process conditions and just seem very important.
In Fischer-Tropsch synthesis, accessory substance is commonly considered as methane and C
2-C
4lower carbon number hydrocarbons, but in these lower carbon number hydrocarbons, ethene, propylene and butylene are at the base stock being chemicals market.These light olefins (C is improved in recent years by the development of catalyst
2-C
4alkene) selective also have important.Also be studied in this regard both at home and abroad, the units such as main Shanxi coalification institute, the Dalian Chemistry and Physics Institute, East China University of Science, Xiamen University.Main catalyst type belongs to Fe base, and the research that light olefin produced by Co base is less.
The development of current catalyst often or pay close attention to heavy hydrocarbon, or pays close attention to light olefin, and both can not take into account, and yield in the reaction both therefore how simultaneously improving is a very crucial problem.To this, cheap Fe both can be taked catalyst based, the Co of good stability also can be taked catalyst based.For Co is catalyst based, is mainly completed by the method for dipping at present, certainly also have the report of the precipitation method.Conventional process first prepares the carrier (such as silica bead, clover aluminium oxide or titanium dioxide) with a fixed structure, and be impregnated on these carriers by the presoma of Co or other auxiliary agents by the method for dipping.But do not relate to the measure of the yield simultaneously improving light olefin and heavy hydrocarbon.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of cobalt-base catalyst for F-T synthesis, and its activity is high, good stability, and the selective height to light olefin and heavy hydrocarbon.
For solving the problems of the technologies described above, the cobalt-base catalyst for F-T synthesis of the present invention, includes Co and MnO, and the content of Co is the content of 10 ~ 50wt%, MnO is that 10 ~ 90wt%, Co and MnO form CoO-MnO solid solution
Preferably, the content of Co is the content of 10 ~ 20wt%, MnO is 10 ~ 20wt%.
Content can also be included not higher than the carrier of 80wt% in described catalyst.Preferably, the content of carrier is not higher than 60wt%.Carrier can adopt SiO
2or TiO
2(MnO
2also can as carrier).
Two of the technical problem to be solved in the present invention is to provide the preparation method of above-mentioned cobalt-base catalyst, and the method is simple, can improve the yield of light olefin and heavy hydrocarbon in F-T synthesis simultaneously.
For solving the problems of the technologies described above, the preparation method of cobalt-base catalyst of the present invention, step comprises:
1) by dipping, roasting, active metal Co and auxiliary agent Mn is made to form CoO-MnO solid solution;
2) with containing the hydrogen of 1% ~ 30%CO as CoO-MnO solid solution described in reducing gases process, cobalt-base catalyst according to claim 1 is obtained; Reducing condition is: temperature 190 ~ 250 DEG C, pressure 0.1 ~ 3.0MPa, time 16 ~ 200h, air speed 1000 ~ 10000kg/hL.
Preferably, in described reducing gases, the percent by volume of CO is 5% ~ 30%.
Preferably, described reducing condition is: temperature 210 ~ 230 DEG C, pressure 0.5 ~ 2.0MPa, air speed 2000 ~ 5000kg/hL.
Preferably, before with described reducing gases process, first use cobalt-base catalyst described in atmospheric hydrogen prereduction, prereduction condition is: temperature 200 ~ 220 DEG C, air speed 2000kg/hL, time 24 ~ 48h.
Step 1) in, the temperature of roasting at 200 ~ 500 DEG C, preferably 250 ~ 350 DEG C.
F-T synthesis catalytic reaction condition is: the temperature of catalytic reaction is 150 ~ 320 DEG C, preferably 200 ~ 220 DEG C; H
2be 1.0 ~ 5.0MPa, preferably 2.0 ~ 3.0MPa with CO stagnation pressure; H
2be 1.5 ~ 2.5 with the mol ratio of CO, preferably 1.7 ~ 2.3; Air speed is 500 ~ 50000h
-1, preferably 100 ~ 4000h
-1.
The present invention is by controlling the active sites on cobalt-base catalyst, and under lower temperature and elevated pressures, the activity in catalyst is formed in-situ reducing with the hydrogen containing CO, heavy hydrocarbon is obtained while obtaining light olefin, thus achieve in co-based fischer-tropsch synthesis and while light olefin and heavy hydrocarbon yield, improve that (CO conversion ratio can reach 15 ~ 60%, 70% is reached to the selective of heavy hydrocarbon, more than 15% is reached to the selective of light olefin).
Accompanying drawing explanation
XRD (X-ray diffraction) figure after the Co/MnO catalyst of Fig. 1 to be Co content of the present invention be 10wt% reduces under different reducing atmospheres.Wherein, 1) for 5bar is containing 10%CO and 90%H
2synthesis gas atmosphere; 2) be 10bar 1%CO/H2 hydrogen atmosphere; 3) be 1bar hydrogen atmosphere.Can see from Fig. 1, although adopt different atmosphere, the XRD diffraction finally obtained is identical, all presents CoO-MnO solid solution.
TEM (transmission electron microscope) figure after the Co/MnO catalyst of Fig. 2 to be Co content of the present invention be 10wt% reduces under 1bar hydrogen atmosphere.On figure, display does not have obvious Co particle.
Fig. 3 ~ Fig. 5 is the CO conversion ratio under the differential responses moment of Co/MnO catalyst at Fischer-Tropsch synthesis of embodiment 1 ~ 3, different air speed respectively.In figure, numerical value is volume space velocity (h
-1).As seen from the figure, catalyst activated centre in course of reaction of embodiment 1,2 constantly increases, and the activity of catalyst constantly increases, and the catalyst activity of embodiment 3 is without obviously increasing process.
Detailed description of the invention
Embodiment 1
Co/MnO catalyst (300 DEG C after roasting, it is 40 ~ 60 orders that screening obtains particle diameter, 1.3g, wherein Co content is 10wt%,) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h; Then gas is switched to 10%CO and 90%H
2mist, temperature adjusts to 210 DEG C, and pressure adjusting is to 0.5MPa, and air speed remains on 2000kg/ (h.L), reduce 132 hours the XRD of the catalyst after reduction (figure as the data wire 1 in Fig. 1) shown).By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 220 DEG C, and pressure is adjusted to 2.0MPa, and air speed is adjusted to 1000kg/ (h.L), carries out Fischer-Tropsch synthesis, and reaction result is in table 1 and Fig. 3.
Embodiment 2
Co/MnO catalyst (300 DEG C after roasting, it is 40 ~ 60 orders that screening obtains particle diameter, 1.3g, wherein Co content is 10wt%) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h; Then gas is switched to 1%CO and 99%H
2mist, temperature adjusts to 220 DEG C, and pressure adjusting is to 1.0MPa, and air speed remains on 1000kg/ (h.L), reduction 135h.By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 220 DEG C, and pressure is adjusted to 2.0MPa, and air speed is adjusted to 600kg/ (h.L), carries out Fischer-Tropsch synthesis, and reaction result is in table 1 and Fig. 4.
Embodiment 3
Co/MnO catalyst (300 DEG C after roasting, it is 40 ~ 60 orders that screening obtains particle diameter, 1.3g, wherein Co content is 10wt%) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h; Then be warmed up to 400 DEG C gradually, air speed remains on 1000kg/ (h.L), reduction 72h.By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 220 DEG C, and pressure is adjusted to 2.0MPa, and air speed is adjusted to 3000kg/ (h.L), carries out Fischer-Tropsch synthesis, and reaction result is in table 1 and Fig. 5.
Embodiment 4
Co/MnO-TiO after roasting
2(300 DEG C, it is 40 ~ 60 orders that screening obtains particle diameter to catalyst, and 1.3g, wherein Co content is 20wt%, Mn content is 20wt%, remaining as TiO
2) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h, then gas is switched to 10%CO and 90%H
2mist, temperature adjusts to 220 DEG C, and pressure adjusting is to 0.5MPa, and air speed remains on 8000kg/ (h.L), reduction 48h.By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 225 DEG C, and pressure is adjusted to 3.0MPa, and air speed is adjusted to 3000kg/ (h.L), and carry out Fischer-Tropsch synthesis, reaction result is in table 1.
Embodiment 5
Co/MnO-SiO after roasting
2(300 DEG C, it is 40 ~ 60 orders that screening obtains particle diameter to catalyst, and 1.3g, wherein Co content is 20wt%, Mn content is 20wt%, remaining as SiO
2) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h, then gas is switched to 20%CO and 80%H
2mist, temperature adjusts to 200 DEG C, and pressure adjusting is to 1.0MPa, and air speed remains on 8000kg/ (h.L), reduction 48h.By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 225 DEG C, and pressure is adjusted to 3.0MPa, and air speed is adjusted to 3000kg/ (h.L), and carry out Fischer-Tropsch synthesis, reaction result is in table 1.
Embodiment 6
Co/MnO after roasting
2-TiO
2(300 DEG C, it is 40 ~ 60 orders that screening obtains particle diameter to catalyst, and 1.3g, wherein Co content is 20wt%, Mn content is 20wt%, remaining as TiO
2) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h; Then gas is switched to 30%CO and 70%H
2mist, temperature adjusts to 200 DEG C, and pressure adjusting is to 2.0MPa, and air speed remains on 4000kg/ (h.L), reductase 12 4h.By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 225 DEG C, and pressure is adjusted to 3.0MPa, and air speed is adjusted to 3000kg/ (h.L), and carry out Fischer-Tropsch synthesis, reaction result is in table 1.
Embodiment 7
Co/ZrO after roasting
2-TiO
2(300 DEG C, it is 40 ~ 60 orders that screening obtains particle diameter to catalyst, and 1.3g, wherein Co content is 20wt%, Zr content is 5wt%, remaining as TiO
2) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 400 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h; Then gas is switched to 10%CO and 90%H
2mist, temperature adjusts to 200 DEG C, and pressure adjusting is to 0.5MPa, and air speed remains on 8000kg/ (h.L), reduction 48h.By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 230 DEG C, and pressure is adjusted to 3.0MPa, and air speed is adjusted to 3000kg/ (h.L), and carry out Fischer-Tropsch synthesis, reaction result is in table 1.
Embodiment 8
Co/ZrO after roasting
2-TiO
2(300 DEG C, it is 40 ~ 60 orders that screening obtains particle diameter to catalyst, and 1.3g, wherein Co content is 20wt%, Zr content is 5wt%, remaining as TiO
2) mix with quartz sand after, be loaded in isothermal reactor, first with atmospheric hydrogen 220 DEG C, air speed be 2000kg/ (h.L) condition under pretreatment 24h; Then gas is switched to 30%CO and 70%H
2mist, temperature adjusts to 200 DEG C, and pressure adjusting is to 0.8MPa, and air speed remains on 4000kg/ (h.L).By CO and H in mist
2mol ratio switch to 1:2, temperature is adjusted to 230 DEG C, and pressure is adjusted to 3.0MPa, and air speed is adjusted to 3000kg/ (h.L), and carry out Fischer-Tropsch synthesis, reaction result is in table 1.
Table 1 catalyst of the embodiment of the present invention carries out the result of Fischer-Tropsch synthesis
Claims (10)
1. for the cobalt-base catalyst of F-T synthesis, it is characterized in that: include Co and MnO in described catalyst, the content of Co is the content of 10 ~ 50wt%, MnO is that 10 ~ 90wt%, Co and MnO form CoO-MnO solid solution.
2. cobalt-base catalyst according to claim 1, is characterized in that, the content of Co is the content of 10 ~ 20wt%, MnO is 10 ~ 20wt%.
3. cobalt-base catalyst according to claim 1 and 2, is characterized in that, also include content in described catalyst not higher than the carrier of 80wt%, described carrier comprises SiO
2or TiO
2.
4. cobalt-base catalyst according to claim 3, is characterized in that, the content of described carrier is not higher than 60wt%.
5. the preparation method of cobalt-base catalyst described in claim 1, is characterized in that, step comprises:
1) by dipping, roasting, active metal Co and auxiliary agent Mn is made to form CoO-MnO solid solution;
2) with containing the hydrogen of 1% ~ 30%CO as CoO-MnO solid solution described in reducing gases process, cobalt-base catalyst according to claim 1 is obtained; Reducing condition is: temperature 190 ~ 250 DEG C, pressure 0.1 ~ 3.0MPa, time 16 ~ 200h, air speed 1000 ~ 10000kg/hL.
6. method according to claim 5, is characterized in that, in described reducing gases, the percent by volume of CO is 5% ~ 15%.
7. method according to claim 5, is characterized in that, described temperature is 210 ~ 230 DEG C.
8. method according to claim 5, is characterized in that, described pressure is 0.5 ~ 2.0MPa.
9. method according to claim 5, is characterized in that, described air speed is 2000 ~ 5000kg/hL.
10. method according to claim 5, is characterized in that, step 2) before with described reducing gases process, first use cobalt-base catalyst described in atmospheric hydrogen prereduction, prereduction condition is: temperature 200 ~ 220 DEG C, air speed 2000kg/hL, time 24 ~ 48h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043421A (en) * | 2017-12-13 | 2018-05-18 | 太原理工大学 | A kind of preparation method of the nanometer cobalt-manganese catalyst of synthesis gas conversion preparing low carbon hydrocarbons |
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| CN103160307A (en) * | 2011-12-14 | 2013-06-19 | Ifp新能源公司 | Method for producing hydrocarbons with continuous loading of the catalyst |
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2015
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160307A (en) * | 2011-12-14 | 2013-06-19 | Ifp新能源公司 | Method for producing hydrocarbons with continuous loading of the catalyst |
Non-Patent Citations (2)
| Title |
|---|
| FERNANDO MORALES ET AL.: "X-ray Absorption Spectroscopy of Mn/Co/TiO2 Fischer-Tropsch Catalysts: Relationships between Preparation Method, Molecular Structure, and Catalyst Performance", 《J. PHYS. CHEM. B》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043421A (en) * | 2017-12-13 | 2018-05-18 | 太原理工大学 | A kind of preparation method of the nanometer cobalt-manganese catalyst of synthesis gas conversion preparing low carbon hydrocarbons |
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