CN102319569A - Low-temperature reduction type cobalt (Co)-based Fischer-Tropsch synthesis catalyst and preparation method thereof - Google Patents
Low-temperature reduction type cobalt (Co)-based Fischer-Tropsch synthesis catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-temperature reduction type cobalt (Co)-based Fischer-Tropsch synthesis catalyst and a preparation method thereof. The catalyst takes ZnO as a carrier and Co as an active ingredient; and the catalyst comprises 3-15wt% of Co and 85-97wt% of ZnO. The preparation method of the catalyst comprises the following steps of: carrying out coprecipitation reaction on a zinc nitrate aqueous solution and an ammonium carbonate aqueous solution to obtain ZnO, then loading Co on ZnO by an immersion method, drying at 120 DEG C, and then roasting at 500 DEG C to obtain the Co/ZnO Fischer-Tropsch synthesis catalyst. The catalyst and the preparation method have the following beneficial effects: by introducing Co by the immersion method, the content of Co can be accurately controlled, and the preparation method is easy to repeat and amplify; and the catalyst is suitable for reduction at low temperature, thus preventing Co from aggregation in the reduction process, being favorable for forming metallic Co with a small size, and ensuring the utilization ratio of Co in the reaction.
Description
(1) technical field
The present invention relates to a kind of hydrocarbon synthesis catalyst and preparation method thereof, particularly a kind of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst and preparation method thereof.
(2) background technology
Liquid fuel is the blood that modern society relies and turns round, and it is mainly produced through crude refining, processing.In recent years; Because the worry to the crude supply prospect has caused liquid fuel price continuous rise; A large amount of uses of liquid fuel have simultaneously also brought the serious environmental pollution problem, and setting up continuable clean fuel liquid production method is the effective means that solves above-mentioned two problems.
Fischer-tropsch synthesis process is meant that coal, natural gas, living beings etc. are contained carbon resource is converted into synthesis gas (CO and H earlier
2Mixture); Synthesis gas is polymerized to the process [Fuel Process.Technol.71 (2001) 149.Catal.Today 84 (2003) 83.] of gaseous state, liquid state and solid hydrocarbons on catalyst, the synthesis gas polymerization process of back is called as Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis) again.
If the gaseous hydrocarbon to wherein carries out aggregation processing, solid hydrocarbons is wherein carried out cracking processing; Can improve the productive rate [Catal.Today 71 (2002) 227.] of liquid hydrocarbon; These liquid hydrocarbons have the identical character of liquid fuel of producing with petroleum refining after the upgrading of process hydrogenation.Because the known reserves of coal, natural gas are much larger than the reserves of verifying of oil; Living beings are a kind of reproducible resources; Therefore fischer-tropsch synthesis process can be in the long time be the liquid fuel of representative for society provides sufficient with gasoline and diesel oil etc., be the desirable alternative oil-fired technology of production.
Fischer-tropsch reaction carries out on catalyst, and the catalyst (high activity, high selectivity, high stability) with excellent properties is the technical guarantee that realizes efficient fischer-tropsch synthesis process.Catalyst activity is high, can improve the specific productivity of reaction unit, and the selectivity height can improve the utilization rate of reaction raw materials, stable height help keeping reaction unit running at full capacity, reduce improper parking.
To the middle discovery of studying for a long period of time of fischer-tropsch reaction: nickel, ruthenium, iron and cobalt have fischer-tropsch reaction activity [Catal.Today 71 (2002) 227.A.C.Vosloo; P.Gibson; P.J.van Berge, 21st International Pittsburgh Coal Conference, 2004.9.13-17; Osaka, Japan.].
Nickel-base catalyst can produce too many methane under the fischer-tropsch reaction condition, the while self is easy to generate volatile carbonyl nickel and from reactor, runs off, and is difficult to realize commercial Application.
Ruthenium is a most active known fischer-tropsch reaction catalyst, but its high price and limited reserves have hindered its use on industrial Fischer-Tropsch device, and it generally is to add in iron-based and the cobalt-base catalyst, improve their reactivity worth with the auxiliary agent form.
Have only iron-based and cobalt-base catalyst successfully to be used in the Fischer-Tropsch compound probability.Ferrum-based catalyst and cobalt-base catalyst have than big difference on reactivity worth.
Ferrum-based catalyst can have very high reactivity, but research [Fuel 76 (1997) 273.] finds that the CO that reacts is converted into CO with higher ratio along with the CO conversion ratio raises
2Rather than hydrocarbon, the selectivity that promptly generates hydrocarbon raises along with the CO conversion ratio and descends.In order to obtain higher hydrocarbon productive rate; Ferrum-based catalyst is considered to suitable to lower CO conversion per pass work; Carry out the secondary response mode through the reaction end gas circulation and reach high CO total conversion (synthesis gas utilization rate) and high hydrocarbon-selective; But this working method has increased workload and corresponding energy consumptions such as tail gas separation, gas circulation compression, and the gross efficiency that has limited fischer-tropsch synthesis process improves.
What form contrast with the ferrum-based catalyst reactivity worth is cobalt-base catalyst, the influence of the water that its performance does not receive to generate in the fischer-tropsch reaction, and since its steam shift activity very a little less than, the CO in the synthesis gas is converted into hydrocarbon.So, use the fischer-tropsch synthesis process of cobalt-base catalyst to work with high conversion per pass mode, can save operation to the reaction end gas compression cycle, shortened technological process, help improving the gross efficiency of fischer-tropsch synthesis process.
Because cobalt is the higher metal of price; When it is used as catalyst; Generally be to adopt infusion process that it is loaded on the carrier of high-specific surface area; Decentralization through improving cobalt reduces its use amount, and can strengthen the mechanical strength of catalyst, reduces or eliminates the wearing and tearing of catalyst in course of reaction.Load on cobalt on the carrier with Co
3O
4Form occurs, and when being used for fischer-tropsch reaction, need be reduced to the chain carrier that metallic state Co just can become the polymerization of CO hydrogenation.Patent CN1401736A discloses a kind of cobalt-base catalyst method of reducing that is used for the zirconia load, adopts pure hydrogen in-situ reducing, reduction temperature 300-500 ℃; Patent CN1454714A utilizes the Co catalysts of pure hydrogen at 300-500 ℃ of in-situ reducing silica gel load; Patent CN1417291A discloses activated carbon supported cobalt-base catalyst method of reducing, in nitrogen atmosphere, reduces, and temperature range is 250-500 ℃; Patent CN1981927A is 400-800 ℃ to the preferred reduction temperature of the Co catalysts of alumina load; US4039302A1 adopts hydrogen at 300-450 ℃ of reduction CoAlZnMo oxide catalyst.
High reduction temperature reason is adopted in above-mentioned work, mainly is that the interaction between cobalt and the carrier is strong, Co
3O
4Particle needs at high temperature just can be reduced into metallic state Co; Yet reduction temperature is high, causes the sintering of metallic state Co easily, reduces cobalt-base catalyst after being reduced, the decentralization of metallic state Co, and promptly fischer-tropsch reaction activated centre number is lower.So strengthen the reducing property of cobalt-base catalyst, it can be reduced at a lower temperature, help forming the metallic state Co of small grain size, guarantee the utilization ratio of cobalt in reaction.CN101224430A is employed in the processing of grafted hydrophobic group on the cobalt-base catalyst of silica gel load; Reduction temperature in pure hydrogen is reduced to 200-300 ℃; But, hydrophobic grouping grafting and toluene and acetone extracting two steps operation have been increased with respect to the immersion process for preparing catalyst process of routine.Because toluene and acetone have toxicity to human body, operating personnel's health has been constituted potential threat.The method that EP0261870B1 discloses on ZnO dipping cobalt and co-precipitation Co, Zn prepares the CoZnO catalyst, and it is to activating treatment method complicacy of catalyst, prepared catalyst in baking oven after 150 ℃ of dryings; Again in blanket of nitrogen in 450 ℃ of heat treatments 6 hours; And then subsequent use after 6 hours in 320 ℃ of processing in nitrogen atmosphere, the fixed bed reactors of packing into behind the above-mentioned shaping of catalyst use hydrogen in 225 ℃ of activation 14 hours again; Owing to after 320 ℃ of reduction for the first time, generate metal Co; It is very active, meets oxygen and burns easily, brings danger for storage and use.
To the preparation method's complicacy of existing low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst or the defective of activation processing complicated steps, the present invention provides Co/ZnO fischer-tropsch synthetic catalyst that a kind of preparation method is easy, reduction temperature is low and preparation method thereof.
(3) summary of the invention
The object of the invention provides a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof, and easy, the made catalyst reduction temperature of this preparation method is low.
The technical scheme that the present invention adopts is:
A kind of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst, described catalyst is a carrier with ZnO, is active component with Co, described catalyst quality percentage is formed as follows, Co:3～15wt%, ZnO:85～97wt%.
The mass percent of active component Co described in the said catalyst is preferably 4～12wt%.
Low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst of the present invention prepares as follows: form Co:3～15wt% by described catalyst quality percentage; ZnO:85～97wt%; The ZnO of composition amount is dropped into the cobalt nitrate aqueous solution dipping; Together place 120 ℃ of oven dryings to spend the night ZnO and maceration extract again, obtain the Co/ZnO fischer-tropsch synthetic catalyst 500 ℃ of roastings then.
ZnO of the present invention makes as follows: with zinc nitrate and ammonium carbonate mixing carrying out coprecipitation reaction; And 40 ℃-70 ℃ of reaction temperatures of control; The pH value is controlled at 6～7, and reaction gained deposition is filtered after being washed with distilled water to no ammonia flavor; Filter cake obtains ZnO 500 ℃ of roastings then 120 ℃ of dried overnight; Described zinc nitrate and ammonium carbonate mass ratio are 1: 0.70～0.80, and said zinc nitrate adds with the form of zinc nitrate aqueous solution, and said ammonium carbonate adds with the form of ammonium carbonate solution.
Concrete; Said low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst makes as follows: (1) is dissolved in the zinc nitrate aqueous solution that distilled water is processed mass concentration 10～20% with zinc nitrate, and ammonium carbonate is dissolved in the ammonium carbonate solution that distilled water is processed mass concentration 10～20%; The mass ratio of described zinc nitrate and ammonium carbonate is 1: 0.70～0.80; (2) described zinc nitrate aqueous solution and described ammonium carbonate solution are pumped into sedimentation basin simultaneously and carry out coprecipitation reaction, precipitation temperature is 40～70 ℃, and the pH value is controlled at 6～7, and the sedimentation time is 10～100min; The gained deposition is washed with distilled water to no ammonia flavor, filters, and filter cake obtains ZnO 500 ℃ of roastings then 120 ℃ of dried overnight; (3) cobalt nitrate is dissolved in the cobalt nitrate aqueous solution that distilled water is processed mass concentration 25～50%; The ZnO of step (2) preparation dropped into dipping reaction 6～24h in 15～40 ℃ the cobalt nitrate aqueous solution; After the reaction; Together place 120 ℃ of oven dryings to spend the night ZnO and maceration extract, obtain the Co/ZnO fischer-tropsch synthetic catalyst 500 ℃ of roastings then; The mass ratio of ZnO and cobalt nitrate is 1: 0.10～0.55.
The mass concentration of preferred zinc nitrate aqueous solution is 12～18% in the step of the present invention (1), and the mass concentration of ammonium carbonate solution is 12～18%.
The mass ratio of preferred zinc nitrate and ammonium carbonate is 1: 0.72～0.77 in the said step (1).
In the step of the present invention (3) mass ratio of ZnO and cobalt nitrate be preferably 1: 0.13～0.42; Described cobalt nitrate preferably adds with the form of the cobalt nitrate aqueous solution of mass concentration 30～45%.
Low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst of the present invention can be in Fischer-Tropsch synthesis synthesizes the application of hydrocarbon as catalyst.
Catalyst of the present invention at first, is formed the requirement that calculates cobalt nitrate based on preset catalyst, behind the wiring solution-forming zinc oxide is flooded the reaction certain hour; After the reaction zinc oxide and maceration extract are together put into oven drying, can not produce the loss of cobalt like this, can guarantee that the actual composition of catalyst is close with preset composition, thereby accurately control the mass percent of cobalt in the catalyst.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: (1) adopts infusion process to introduce Co, can accurately control its content in catalyst, and the preparation method is easy to repetition and is exaggerated; (2) Co based Fischer-Tropsch synthesis catalyst of the present invention is in Fischer-Tropsch synthesis; When the reduction temperature of catalyst is reduced to 230 ℃; Catalyst activated still has fischer-tropsch reaction activity preferably, explains that catalyst is suitable for reducing at low temperatures, can prevent that like this clustering phenomena of cobalt in reduction process from taking place; Help forming the metallic state Co of small grain size, guarantee the utilization ratio of cobalt in reaction.
(4) description of drawings
Reduction temperature is to the catalyst crystalline phases effect on structure among Fig. 1 embodiment 3: the spectral line among the figure is from being respectively the oxidation state sample down, 230 ℃ of reduction passivation samples, 250 ℃ of reduction passivation samples, 270 ℃ of reduction passivation samples, 300 ℃ of reduction passivation samples.
(5) specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
With 219.31g Zn (NO
3)
26H
2O is dissolved in 852g distilled water and processes Zn (NO
3)
2Mass concentration 15% zinc nitrate aqueous solution is with 102.0g (NH
4)
2CO
3Be dissolved in 531g distilled water and process mass concentration 16% ammonium carbonate solution.Zinc nitrate aqueous solution and ammonium carbonate solution are pumped into sedimentation basin simultaneously carry out coprecipitation reaction, precipitation temperature is 50 ± 2 ℃, and the pH value is controlled at 6.2 ± 0.2, reaction time 36min.The gained deposition is washed with distilled water to no ammonia flavor, filters, and filter cake obtains ZnO carrier 60g, called after carrier 1 at 500 ℃ of roasting 6h then 120 ℃ of dried overnight
#
Embodiment 2
With 73.1g Zn (NO
3)
26H
2O is dissolved in 250g distilled water and processes Zn (NO
3)
2Mass concentration 17% zinc nitrate aqueous solution is with 35.42g (NH
4)
2CO
3Be dissolved in 177g distilled water and process mass concentration 17% ammonium carbonate solution.Zinc nitrate aqueous solution and ammonium carbonate solution are pumped into sedimentation basin simultaneously carry out coprecipitation reaction, precipitation temperature is 55 ± 2 ℃, and the pH value is controlled at 6.4 ± 0.2, reaction time 13min.The gained deposition is washed with distilled water to no ammonia flavor, filters, and filter cake obtains ZnO carrier 20g, called after carrier 2 at 500 ℃ of roasting 6h then 120 ℃ of dried overnight
#
Embodiment 3
With 2.6g Co (NO
3)
26H
2O is dissolved in 4.0g distilled water and processes Co (NO
3)
2Mass concentration 33% cobalt nitrate aqueous solution, the carrier 1 that embodiment 1 is prepared
#Be shaped to 150～280 μ m particles, get 10.0g ZnO and drop in the above-mentioned cobalt nitrate aqueous solution, behind 20 ℃ of dipping 10h, carrier is together put into 120 ℃ of oven dryings with the surplus liquid of dipping and is spent the night, and then at 500 ℃ of roasting 6h, obtains the Co/ZnO catalyst, called after catalyst 3
#, the mass percent of this activity of such catalysts component Co is 5wt%.
Get the catalyst 3 of 0.5g method for preparing respectively
#Put into fixed bed reactors (ZJGD-XJ2009-041; Tianjin roc Xiang Science and Technology Ltd.) reduce with pure hydrogen, reduction temperature is respectively 230 ℃, 250 ℃, 270 ℃ and 300 ℃, and the recovery time is 6h; Reduction finishes the back and in hydrogen, is cooled to 150 ℃; Switch generated nitrogen blowing and cleaning 0.5h again, in blanket of nitrogen, reduce to room temperature then, the injection air carries out Passivation Treatment.Reduce resulting passivation sample in different temperatures and carried out the crystalline phase analysis above-mentioned, the equipment of use is: and X-ray diffractometer (X ' Pert PRO, Dutch PNAlytical company), the result sees Fig. 1.Compare with oxidized catalyst, zinc species all exists with ZnO crystal before and after reduction, and the cobalt species are with Co before reduction
3O
4Crystal exists, and then is converted into the CoO crystal after the reduction, and the reason that does not detect metallic cobalt possibly be that metallic cobalt is changed into due to the CoO by partial oxygen when going back raw sample and carry out Passivation Treatment.Visible from Fig. 1, the catalyst crystalline phases structure that 230 ℃ of reduction obtain is identical with the catalyst structure that 300 ℃ of reduction obtain, and explain that the catalyst that employing the method for the invention prepares is easy to reduce at low temperatures.
Embodiment 4
Respectively that 1.0g embodiment 3 methods are prepared catalyst 3
#, put into fixed bed reactors (ZJGD-XJ2009-041, Tianjin roc Xiang Science and Technology Ltd.) and carry out activity rating by following reaction condition; Adopt pure hydrogen reducing catalyst under different temperature; Reduction temperature is respectively 230 ℃, 250 ℃, 270 ℃, constant temperature reduction 6h, and reduction pressure is normal pressure; Reduction is cooled to room temperature after finishing in hydrogen, again gas is switched to H
2The reaction gas of/CO=2, pressure are 2.0MPa, and air speed is 1.8Lh
-1G-cat.
-1, being warming up to 220 ℃ subsequently and reacting 48h, reaction finishes, and catalyst performance evaluation result sees table 1.
Embodiment 5
With 5.5g Co (NO
3)
26H
2O is dissolved in 6.0g distilled water and processes Co (NO
3)
2Mass concentration 43% cobalt nitrate aqueous solution, the carrier 2 that embodiment 2 is prepared
#Be shaped to 150～280 μ m particles, get 10.0g ZnO and drop in the above-mentioned cobalt nitrate aqueous solution, behind 30 ℃ of dipping 18h, carrier is together put into 120 ℃ of oven dryings with the surplus liquid of dipping and is spent the night, and it is catalyst based to obtain Co/ZnO at 500 ℃ of roasting 6h then, called after catalyst 4
#, the mass percent of this catalyst activity component Co is 10wt%.
Catalyst 4 with the 1.0g method for preparing
#Put into fixed bed reactors (ZJGD-XJ2009-041, Tianjin roc Xiang Science and Technology Ltd.) and carry out activity rating by following reaction condition, earlier 250 ℃ with the pure hydrogen reduction 6h of normal pressure, reduction is cooled to room temperature after finishing in hydrogen, again gas is switched to H
2The reaction gas of/CO=2, pressure are 2.0MPa, and air speed is 1.8Lh
-1G-cat.
-1, being warming up to 220 ℃ subsequently and reacting 48h, reaction finishes, and catalyst performance evaluation result sees table 1.
Catalyst reaction performance among table 1 embodiment 4,5
Claims (9)
1. low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst, it is characterized in that: described catalyst is a carrier with ZnO, is active component with Co, described catalyst quality percentage is formed as follows, Co:3～15wt%, ZnO:85～97wt%.
2. low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 1, the mass percent that it is characterized in that described active component Co is 4～12wt%.
3. the preparation method of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 1; It is characterized in that described preparation method is: form Co:3～15wt% by described catalyst quality percentage; ZnO:85～97wt%; The ZnO of composition amount is dropped into dipping reaction in the cobalt nitrate aqueous solution, together place 120 ℃ of oven dryings to spend the night ZnO and maceration extract after the reaction, obtain the Co/ZnO fischer-tropsch synthetic catalyst 500 ℃ of roastings then.
4. the preparation method of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 3; It is characterized in that described ZnO makes as follows: with zinc nitrate and ammonium carbonate mixing carrying out coprecipitation reaction, and control 40 ℃～70 ℃ of reaction temperatures, the pH value is controlled at 6～7; After reaction gained deposition is washed with distilled water to no ammonia flavor; Filter, filter cake obtains ZnO 500 ℃ of roastings then 120 ℃ of dried overnight; Described zinc nitrate and ammonium carbonate mass ratio are 1: 0.70～0.80, and said zinc nitrate adds with the form of zinc nitrate aqueous solution, and said ammonium carbonate adds with the form of ammonium carbonate solution.
5. the preparation method of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 4; It is characterized in that said preparation method carries out as follows: (1) is dissolved in the zinc nitrate aqueous solution that distilled water is processed mass concentration 10～20% with zinc nitrate, and ammonium carbonate is dissolved in the ammonium carbonate solution that distilled water is processed mass concentration 10～20%; Described zinc nitrate and ammonium carbonate mass ratio are 1: 0.70～0.80; (2) described zinc nitrate aqueous solution and described ammonium carbonate solution are pumped into sedimentation basin simultaneously and carry out coprecipitation reaction, precipitation temperature is 40～70 ℃, and the pH value is controlled at 6～7, and the sedimentation time is 10～100min; The gained deposition is washed with distilled water to no ammonia flavor, filters, and filter cake obtains ZnO 500 ℃ of roastings then 120 ℃ of dryings; (3) cobalt nitrate is dissolved in the cobalt nitrate aqueous solution that distilled water is processed mass concentration 25～50%; The ZnO of step (2) preparation dropped into dipping reaction 6～24h in 15～40 ℃ the cobalt nitrate aqueous solution; After the reaction; Together place 120 ℃ of oven dryings to spend the night ZnO and maceration extract, obtain the Co/ZnO fischer-tropsch synthetic catalyst 500 ℃ of roastings then; ZnO and cobalt nitrate mass ratio are 1: 0.10～0.55.
6. the preparation method of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 5 is characterized in that the mass concentration of zinc nitrate aqueous solution in the said step (1) is 12～18%, and the mass concentration of ammonium carbonate solution is 12～18%.
7. the preparation method of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 5 is characterized in that the mass ratio of middle zinc nitrate of said step (1) and ammonium carbonate is 1: 0.72～0.77.
8. the preparation method of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 5 is characterized in that the mass ratio of middle ZnO of said step (3) and cobalt nitrate is 1: 0.13～0.42; Described cobalt nitrate adds with the form of the cobalt nitrate aqueous solution of mass concentration 30～45%.
9. low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst as claimed in claim 1 synthesizes the application of hydrocarbon as catalyst in Fischer-Tropsch synthesis.
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| CN102000588A (en) * | 2010-11-11 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Modified zinc oxide-loaded cobalt catalyst and preparation method thereof |
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| CN101297022A (en) * | 2005-10-25 | 2008-10-29 | 英国石油勘探运作有限公司 | Fischer tropsch process |
| CN101784340A (en) * | 2007-06-19 | 2010-07-21 | 巴斯夫催化剂有限公司 | Process for the preparation of a cobalt-zinc oxide fischer-tropsch catalyst |
| CN102000588A (en) * | 2010-11-11 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Modified zinc oxide-loaded cobalt catalyst and preparation method thereof |
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Application publication date: 20120118 |