CN113751017B - Fischer-Tropsch synthesis catalyst, and preparation method and application thereof - Google Patents

Fischer-Tropsch synthesis catalyst, and preparation method and application thereof Download PDF

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CN113751017B
CN113751017B CN202010508022.4A CN202010508022A CN113751017B CN 113751017 B CN113751017 B CN 113751017B CN 202010508022 A CN202010508022 A CN 202010508022A CN 113751017 B CN113751017 B CN 113751017B
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titanium dioxide
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CN113751017A (en
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秦绍东
李加波
段雪成
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National Institute of Clean and Low Carbon Energy
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group

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Abstract

The invention relates to the field of Fischer-Tropsch synthesis catalysts, in particular to a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof. The Fischer-Tropsch synthesis catalyst comprises, based on the total weight of the catalyst: 10-50 wt% Co,0.01-5 wt% Mn,0.01-2.5 wt% Cl,0.5-10 wt% ZrO 2 35-85% by weight of titanium dioxide. The Fischer-Tropsch synthesis catalyst has high activity, excellent stability and low methane selectivity, and is particularly suitable for a fixed bed cobalt-based Fischer-Tropsch synthesis process.

Description

Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis catalysts, in particular to a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof.
Background
The Fischer-Tropsch synthesis reaction is a process of converting synthesis gas into hydrocarbons through a catalyst, and the reaction equation is as follows:
nCO+(2n+1)H 2 →C n H2 n +2+nH 2 OΔH＝-165KJ/mol
the commonly used Fischer-Tropsch synthesis catalysts are of two types, namely iron-based and cobalt-based, and compared with the iron-based catalysts, the cobalt-based catalysts have high Fischer-Tropsch synthesis activity and low CO 2 The significant advantage of selectivity has thus gained more widespread attention and application worldwide. Besides hydrocarbons, a large amount of steam is generated in the Fischer-Tropsch synthesis reaction, so that in industrial production, particularly, a tubular fixed bed reactor is used, and the hydrothermal stability of a cobalt-based catalyst is strictly required.
Furthermore, since the Fischer-Tropsch reaction is a strongly exothermic reaction, the heat control of the Fischer-Tropsch reaction is critical to the stable operation of the apparatus in industrial applications. In industrial operation, particularly at the beginning of plant operation, the plant has not reached steady state and the plant temperature is subject to fluctuations, which present a significant challenge to the heat resistance of the catalyst.
To improve cobalt baseFischer-Tropsch catalyst activity and stability, the active component cobalt is usually supported on Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 And on a carrier. And gamma-Al 2 O 3 The carrier has poor hydrothermal stability, and gradually undergoes a hydrothermal reaction in a high-hydrothermal atmosphere, and is converted into AlO (OH). And SiO 2 Although not prone to chemical reaction with steam, the shaped particles tend to fracture over time, resulting in a rapid decrease in catalyst strength. Furthermore SiO 2 Interaction with the active component cobalt is weak, so Co/SiO 2 When the temperature of the catalyst fluctuates greatly, the catalyst is easy to be subject to sintering deactivation.
CN1291116a and WO99/42214 both disclose a process for the production of hydrocarbons from synthesis gas and catalysts therefor. The carrier is mainly alumina, and in order to improve the hydrothermal stability and acid resistance of the catalyst carrier, components such as organic silicon and the like are used for treating the catalyst carrier. The specific modification method comprises the following steps: and dissolving precursors of required components such as silicon and the like in a solvent, mixing alumina carrier particles with the obtained solution, drying and roasting to obtain a modified catalyst carrier, and finally preparing the Fischer-Tropsch synthesis cobalt catalyst by an impregnation method.
CN101801525a discloses a modified TiO using silicon or titanium compounds containing alkyl or aryl groups 2 The supported cobalt-based Fischer-Tropsch catalyst is further used for improving the hydrothermal resistance of the catalyst, but the method needs organic matters such as toluene and the like, and is not friendly to operators and environment.
TiO 2 The hydrothermal stability of (C) is obviously better than that of gamma-Al 2 O 3 With SiO 2 Thus TiO in industry 2 Are also commonly used as supports for cobalt-based fischer-tropsch catalysts. TiO as catalyst support 2 Usually consisting of two crystalline phases of anatase and rutile, CN101801525a reports the carrier TiO in the fischer-tropsch reaction 2 TiO, which causes anatase phase in long-term contact with water vapor 2 TiO to rutile phase 2 The transition ultimately results in deactivation of the catalyst.
Although the prior art can to a certain extentImproving the hydrothermal stability, acid resistance and activity of the catalyst, but CH 4 And C 2 H 6 The selectivity of the isogaseous hydrocarbon is still higher, and the main target products of the Fischer-Tropsch synthesis reaction are liquid and solid hydrocarbons with high added value, CH 4 Is a byproduct that needs to be minimized.
Therefore, a synthesis process is needed to be simple, the hydrothermal stability is good, and CH is needed to be high 4 And C 2 H 6 Fischer-tropsch catalysts with low iso-selectivity.
Disclosure of Invention
The invention aims to overcome the defects of low hydrothermal stability, easy inactivation, complicated preparation and CH existing in the Fischer-Tropsch synthesis catalyst in the prior art 4 And C 2 H 6 The problems of high selectivity of gaseous hydrocarbon and the like, and provides a Fischer-Tropsch synthesis catalyst, a preparation method and application thereof.
The inventor of the invention discovers that the supported cobalt-based catalyst is easy to deactivate in the Fischer-Tropsch synthesis reaction process, and the mechanism of deactivation mainly comprises sintering of catalyst metal cobalt, carbon deposition on the surface of the catalyst, phase transition of cobalt phase and carrier, sulfur poisoning and the like. The inventors have also found that for TiO 2 Supported cobalt-based catalyst, carbon deposition and carrier TiO 2 The conversion of the crystalline form from anatase to rutile is the primary cause of catalyst deactivation.
The inventors have found that by directing at TiO 2 Zr auxiliary agent is introduced into the supported cobalt-based catalyst, so that the carrier TiO in the catalyst can be obviously improved 2 Stability of (2); and Zr auxiliary agent mainly adopts ZrO 2 The phase is present in the catalyst.
The inventors have also found that further introduction of a Cl source into the catalyst can further obtain a catalyst having excellent stability.
There is a synergistic effect between Cl and Zr in the catalyst, cl and ZrO 2 Not only can obviously inhibit TiO 2 The conversion from anatase crystal form to rutile crystal form in the carrier keeps the stability of the specific surface area of the catalyst, can inhibit carbon deposition on the surface of the catalyst, keeps the activity of the catalyst in the reaction process, and in addition, the selectivity of the obtained catalyst to methane is higherLow.
In order to achieve the above object, a first aspect of the present invention provides a fischer-tropsch synthesis catalyst, comprising, based on the total weight of the catalyst: 10-50 wt% Co,0.01-5 wt% Mn,0.01-2.5 wt% Cl,0.5-10 wt% ZrO 2 35-85% by weight of titanium dioxide.
In a second aspect the invention provides a process for preparing a fischer-tropsch synthesis catalyst comprising: kneading a Co source, a Mn source, a Cl source, a Zr source, a titanium source and an optional peptizing agent, and then drying and roasting to obtain the Fischer-Tropsch synthesis catalyst, wherein the content of Co, mn source, cl source, zr source and titanium source is 10-50 wt%, the content of Mn is 0.01-5 wt%, the content of Cl is 0.01-2.5% and the content of ZrO is calculated based on the total weight of the catalyst 2 The content of (2) is 0.5-10 wt%, and the content of titanium dioxide is 35-85 wt%.
The third aspect of the invention provides the use of the Fischer-Tropsch catalyst of the first aspect of the invention and/or the Fischer-Tropsch catalyst prepared by the method of the second aspect of the invention in a Fischer-Tropsch reaction.
The Fischer-Tropsch synthesis catalyst provided by the invention has high activity, excellent stability and low methane selectivity, and is particularly suitable for a fixed bed cobalt-based Fischer-Tropsch synthesis process. In a preferred embodiment, the Fischer-Tropsch catalyst of the invention is used in a Fischer-Tropsch reaction at 215℃and 2MPa and 3L/(g) cat At airspeed of H), H 2 In the synthesis gas with/CO=2, the catalyst activity is not deactivated in 2500h at the single-pass CO conversion rate of 65%, and the catalyst CH after the reaction is stabilized 4 The selectivity of (2) is not more than 6% and even less than 5%.
Drawings
FIG. 1 shows the CO conversion change with increasing reaction time for the Fischer-Tropsch synthesis of catalyst A1 according to the invention and catalyst D5 according to the prior art.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a fischer-tropsch synthesis catalyst, comprising, based on the total weight of the catalyst: 10-50 wt% of Co,0.01-5 wt% of Mn,0.01-2.5 wt% of Cl,0.5-10 wt% of Zr and 35-85 wt% of titanium dioxide.
Preferably, the titanium dioxide comprises anatase titanium dioxide and rutile titanium dioxide, and the content of anatase titanium dioxide in the titanium dioxide is larger than that of rutile titanium dioxide.
The content of anatase titanium dioxide is greater than 50 wt%, preferably greater than 60 wt%, based on the total amount of titanium dioxide; the content of rutile titanium dioxide is less than 40% by weight, preferably less than 30% by weight.
In this context, the content of anatase titanium dioxide is determined by XRD.
Preferably, in the catalyst, the content of Co is 15 to 40 wt%, for example, 16 wt%, 20 wt%, 30 wt%, 35 wt%, and any one of any two of the above ranges, based on the total weight of the catalyst; the Mn content is 0.05 to 2 wt%, and may be, for example, 0.06 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 1.8 wt%, or any one of the ranges of any two of the above values; the Cl content is 0.05 to 2 wt%, preferably 0.05 to 1.5 wt%, for example, 0.06 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 1.3 wt% and any value in the range of any two of the above values; zrO (ZrO) 2 The content of (C) is 0.5-7.5 wt%, for example, 2 wt%, 3 wt%, 5 wt%, 7 wt%, and any one of the ranges of any two of the above values, and the content of titanium dioxide is 45-80 wtThe percentage may be, for example, 48 wt%, 55 wt%, 65 wt%, 70 wt%, 75 wt%, 78 wt%, or any value in the range of any two of the above values.
In the catalyst of the invention, zr is expressed as ZrO 2 Is present in the form of (c). ZrO (ZrO) 2 Remarkably inhibit TiO 2 The conversion from anatase crystal form to rutile crystal form in the carrier ensures that the specific surface area of the catalyst is kept stable, thereby maintaining the stability of the catalyst.
In the catalyst of the invention, cl can inhibit carbon deposition on the surface of the catalyst. When the Cl content is less than 0.01 wt%, the chloride ions cannot effectively suppress carbon deposition; when the Cl content is more than 2.5 wt%, the activity of the catalyst is inhibited.
In the catalyst according to the invention, cl and ZrO in the catalyst 2 There is a synergistic effect between Cl and ZrO 2 Not only can obviously inhibit TiO 2 The conversion from anatase crystal form to rutile crystal form in the carrier keeps the stability of the specific surface area of the catalyst, can inhibit carbon deposition on the surface of the catalyst, keeps the activity of the catalyst in the reaction process, and has low selectivity to methane.
The catalyst of the invention requires a reduction treatment prior to use to form a reduced fischer-tropsch catalyst. In reduced Fischer-Tropsch catalysts, zr is represented by ZrO 2 In the form of (2); co exists mostly in the form of metallic Co, and a small amount exists as CoO.
In a second aspect the invention provides a process for preparing a fischer-tropsch synthesis catalyst comprising: kneading a Co source, a Mn source, a Cl source, a Zr source, a titanium source and an optional peptizing agent, and then drying and roasting to obtain the Fischer-Tropsch synthesis catalyst, wherein the content of Co, mn source, cl source, zr source and titanium source is 10-50 wt%, the content of Mn is 0.01-5 wt%, the content of Cl is 0.01-2.5 wt%, and the content of ZrO is based on the total weight of the Fischer-Tropsch synthesis catalyst 2 The content of (2) is 0.5-10 wt%, and the content of titanium dioxide is 35-85 wt%.
Preferably, the Co source is selected from at least one of cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt hydroxide, and cobalt chloride.
Preferably, the Zr source is selected from ZrO 2 At least one of zirconyl nitrate and zirconyl chloride.
Preferably, the Mn source is selected from MnO 2 At least one of manganese acetate, manganese nitrate and manganese chloride.
Preferably, the titanium source is selected from TiO 2 At least one of titanium chloride, titanium oxychloride, titanium hydroxide and tetrabutyl titanate.
Preferably, the Cl source is selected from at least one of cobalt chloride, zirconium oxychloride, manganese chloride, and hydrochloric acid.
In a preferred embodiment, the Co source and/or the Cl source is cobalt chloride.
In the present invention, when the Co source, mn source, cl source, zr source, and Ti source are all solid substances, it is preferable to add thereto a peptizing agent for adding TiO for the convenience of kneading and molding 2 、ZrO 2 The isostere peptizes, thereby making it easier to shape and interact with other components in the catalyst. Preferably, the peptizing agent is selected from at least one of glacial acetic acid, citric acid, nitric acid, hydrochloric acid, aqueous ammonia and ammonium bicarbonate.
Preferably, the drying conditions include: the temperature is 80-130 ℃ and the time is 2-48h.
Preferably, the roasting conditions include: the temperature is 300-650 ℃, preferably 400-580 ℃; the time is 1-40h; preferably 2-20h.
For ease of transportation and further to increase the activity of the catalyst, it is preferred that the catalyst is reduced prior to use without reduction during the preparation process to provide a reduced Fischer-Tropsch catalyst.
In a preferred embodiment, the conditions of the reduction treatment include: at H 2 Reducing for 5-50h at 300-400 ℃.
The method provided by the invention has the advantages of simple process steps, low methane selectivity and high activity of the obtained catalyst, and more particularly, the catalyst has excellent stability and is particularly suitable for a fixed bed Fischer-Tropsch synthesis process.
The third aspect of the invention provides the use of the Fischer-Tropsch catalyst of the first aspect of the invention and/or the Fischer-Tropsch catalyst prepared by the method of the second aspect of the invention in a Fischer-Tropsch reaction.
The present invention will be described in detail by examples.
The tests related to the examples and the comparative examples are as follows:
the content of each component in the catalyst was measured by XRF;
the content of anatase crystal forms in the titanium dioxide powder and the catalyst was measured by XRD.
Example 1
200g of TiO 2 Powder (specific surface area of 30-70 m) 2 Per g, wherein the anatase content is 90% by weight, and 30.4g of cobalt hydroxide were placed in a kneader. 3.3g of manganese nitrate (Mn (NO) 3 ) 2 ) 21.7g of zirconyl nitrate (ZrO (NO) 3 ) 2 ·2H 2 O), 96.5g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O), 1.5g of anhydrous cobalt chloride (CoCl) 2 ) And 15g of glacial acetic acid were dissolved in 100g of deionized water and then fed into a kneader. After being uniformly mixed by a kneader, the mixture is extruded and shaped, dried for 10 hours at 120 ℃, and then baked for 3 hours at 550 ℃ to prepare the catalyst A1.
XRF test shows that the catalyst A1 has Co content of 15 wt%, mn content of 0.4 wt%, cl content of 0.3 wt% and ZrO content 2 The content of (a) was 4.3 wt.%, and the content of titanium dioxide was 74.9 wt.% (in the titanium dioxide, the content of anatase titanium dioxide was 72 wt.%, and the content of rutile titanium dioxide was 28 wt.%).
Example 2
200g of TiO 2 The powder (same as in example 1) and 91.2g of cobalt hydroxide were placed in a kneader. 13.2g of manganese nitrate (Mn (NO) 3 ) 2 ) 43.4g of zirconyl nitrate (ZrO (NO) 3 ) 2 ·2H 2 O), 96.5g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O), 4.5g of anhydrous cobalt chloride (CoCl) 2 ) 25g of glacial acetic acidIn 100g of deionized water, a kneader was then added. After being uniformly mixed in a kneader, the mixture is extruded and shaped, dried for 18 hours at 130 ℃, and then baked for 20 hours at 400 ℃ to prepare the catalyst A2.
According to XRF test, the catalyst A2 has a Co content of 23.7 wt%, a Mn content of 1.2 wt%, a Cl content of 0.6 wt%, and a ZrO content 2 The content of (a) was 6.9 wt.%, and the content of titanium dioxide was 59.8 wt.% (in the titanium dioxide, the content of anatase titanium dioxide was 85 wt.%, and the content of rutile titanium dioxide was 15 wt.%).
Example 3
200g of TiO 2 The powder (same as in example 1) and 162.4g of cobalt hydroxide were placed in a kneader. 22g of manganese nitrate (Mn (NO) 3 ) 2 ) 43.4g of zirconyl nitrate (ZrO (NO) 3 ) 2 ·2H 2 O), 193g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O), 13g of anhydrous cobalt chloride (CoCl) 2 ) And 15g of glacial acetic acid are dissolved in 80g of deionized water, and then are fed into a kneader. After being uniformly mixed in a kneader, the mixture is extruded and shaped, dried for 5 hours at 90 ℃, and then baked for 10 hours at 500 ℃ to prepare the catalyst A3.
XRF test shows that the catalyst A3 has Co content of 33 wt%, mn content of 1.5 wt%, cl content of 1.1 wt%, and ZrO content 2 The content of (a) was 5.2 wt.%, and the content of titania was 45 wt.% (in the titania, the content of anatase titania was 75 wt.%, and the content of rutile titania was 25 wt.%).
Example 4
200g of TiO 2 The powder (same as in example 1) and 236.7g of cobalt hydroxide were placed in a kneader. 77.1g of manganese nitrate (Mn (NO) 3 ) 2 ) 21.7g of zirconyl nitrate (ZrO (NO) 3 ) 2 ·2H 2 O), 96.5g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O), 36g of anhydrous cobalt chloride (CoCl) 2 ) And 25g of glacial acetic acid are dissolved in 130g of deionized water, and then fed into a kneader. After being uniformly mixed by a kneader, the mixture is extruded and shaped, and is dried for 12 hours at 100 ℃ and thenRoasting for 5 hours at 600 ℃ to obtain the catalyst A4.
XRF test shows that the catalyst A4 has Co content of 40 wt%, mn content of 4.2 wt%, cl content of 2.5 wt% and ZrO content 2 The content of (2.1 wt.%) titanium dioxide was 36 wt.% (in the titanium dioxide, the content of anatase titanium dioxide was 54 wt.%, and the content of rutile titanium dioxide was 46 wt.%).
Example 5
248g TiO 2 Powder, 6.4g MnO 2 With 41.7g ZrO 2 122g of cobalt hydroxide was placed in a kneader. 8g of titanium oxychloride (TiOCl) 2 ·8H 2 O) and 19g of glacial acetic acid are dissolved in 115g of deionized water and then fed into the kneader. After being uniformly mixed in a kneader, the mixture is extruded and shaped, dried for 24 hours at 80 ℃, and then baked for 10 hours at 350 ℃ to prepare the catalyst A5.
According to XRF test, the catalyst A5 has a Co content of 17.1 wt%, a Mn content of 0.9 wt%, a Cl content of 0.05 wt%, and a ZrO content 2 The content of (a) was 9.2 wt.%, and the content of titanium dioxide was 56 wt.% (in the titanium dioxide, the content of anatase titanium dioxide was 88 wt.%; the content of rutile titanium dioxide was 12 wt.%).
Example 6
Fischer-Tropsch catalyst was prepared as described in reference to example 1, except that anhydrous cobalt chloride (CoCl 2 ) Catalyst A6 was finally obtained in the same manner as in example 1 except that the amount of (C) was 0.15 g.
XRF test shows that the catalyst A6 has Co content of 14.9 wt%, mn content of 0.4 wt%, cl content of 0.03 wt%, and ZrO content 2 The content of (a) was 3.9 wt%, and the content of titanium dioxide was 75.1 wt% (in the titanium dioxide, the content of anatase titanium dioxide was 72 wt%, and the content of rutile titanium dioxide was 28 wt%).
Example 7
Fischer-Tropsch catalyst prepared according to the method described in example 1, withoutLikewise, anhydrous cobalt chloride (CoCl) 2 ) The amount of (C) was 15g, and the rest was the same as in example 1, to finally obtain catalyst A7.
XRF test shows that the catalyst A7 has Co content of 17.4 wt%, mn content of 0.4 wt%, cl content of 2 wt% and ZrO content 2 The content of (a) was 3.7 wt%, and the content of titanium dioxide was 75.2 wt% (in the titanium dioxide, the content of anatase titanium dioxide was 72 wt%, and the content of rutile titanium dioxide was 28 wt%).
Example 8
A Fischer-Tropsch catalyst was prepared as described in example 1, except that the calcination temperature was 680℃and the remainder was the same as in example 1, to finally prepare catalyst A8.
XRF test shows that the catalyst A8 has Co content of 15.1 wt%, mn content of 0.4 wt%, cl content of 0.1 wt%, and ZrO content 2 The content of (a) was 4.4 wt%, and the content of titanium dioxide was 75 wt% (in the titanium dioxide, the content of anatase titanium dioxide was 35 wt%, and the content of rutile titanium dioxide was 65 wt%).
Example 9
Fischer-Tropsch catalysts were prepared as described in reference to example 1, except that TiO was used 2 The anatase titania content in the powder was 50% by weight, and the remainder was the same as in example 1, to finally obtain a catalyst A9.
XRF test shows that the catalyst A9 has Co content of 15.2 wt%, mn content of 0.5 wt%, cl content of 0.3 wt% and ZrO content 2 The content of (a) was 3.8 wt%, and the content of titanium dioxide was 75.6 wt% (in the titanium dioxide, the content of anatase titanium dioxide was 34 wt%, and the content of rutile titanium dioxide was 66 wt%).
Comparative example 1
44g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 15g of deionized water and is prepared into solution by stirring; adding 100g of dried TiO into the solution 2 Drying and dewatering the carrier at 85 ℃ for 4 hours, and then heating to 120 ℃ and drying for 10 hours. 36.9g of Co (NO) 3 ) 2 ·6H 2 O was dissolved in 15g of deionized water to prepare a solution, and the dried sample was added to the solution, dried again at 85℃for 4 hours, and then heated to 120℃to dry for 10 hours. Then heating to 250 ℃ at a speed of 1 ℃/min, and roasting for 4 hours to prepare the catalyst D1.
The XRF test shows that the Co content is 14.2 wt.% and the titania content is 81.3 wt.%, based on the total weight of catalyst D1.
Comparative example 2
TiO in comparative example 1 2 Replaced by ZrO 2 Catalyst D2 was prepared in the same manner as in comparative example 1.
According to XRF test, the content of Co is 14.5% by weight, based on the total weight of the catalyst D2, zrO 2 The content of (2) was 81% by weight.
Comparative example 3
Catalyst D3 was prepared by the same procedure as in example 1, except that zirconyl nitrate was not used.
The XRF test shows that the catalyst comprises 15.5 wt% of Co, 0.5 wt% of Mn, 0.3 wt% of Cl and 76 wt% of titanium dioxide, based on the total weight of the catalyst D3.
Comparative example 4
Catalyst D4 was prepared by the same procedure as in example 1, except that anhydrous cobalt chloride was not used.
XRF test shows that the catalyst D4 has Co content of 15.1 wt%, mnO content of 0.5 wt% and ZrO content 2 The content of (2) was 3.7% by weight and the content of titanium dioxide was 75.6% by weight.
Comparative example 5
Fischer-Tropsch catalyst was prepared as described in reference to example 1, except that anhydrous cobalt chloride (CoCl 2 ) Catalyst D5 was finally obtained in the same manner as in example 1 except that the amount of (C) was 40 g.
XRF test shows that the catalyst comprises Co 16.8 wt%, mn 0.4 wt%, cl 3 wt% and ZrO 5 based on the total weight of the catalyst 2 The content of (a) was 4 wt%, and the content of titanium dioxide was 73.8 wt% (in the titanium dioxide, the content of anatase titanium dioxide was 72 wt%, and the content of rutile titanium dioxide was 28 wt%).
Comparative example 6
A Fischer-Tropsch catalyst was prepared as described in example 1, except that zirconyl nitrate was used in an amount of 2.17g, and the remainder was the same as in example 1, to finally prepare catalyst D6.
XRF test shows that the catalyst D6 has Co content of 15.1 wt%, mnO content of 0.5 wt%, cl content of 0.3 wt% and ZrO content 2 The content of (a) was 0.4 wt%, and the content of titanium dioxide was 76.2 wt% (in the titanium dioxide, the content of anatase titanium dioxide was 72 wt%, and the content of rutile titanium dioxide was 28 wt%).
Comparative example 7
A Fischer-Tropsch catalyst was prepared as described in example 1, except that zirconyl nitrate was used in an amount of 75.1g, and the remainder was the same as in example 1, to finally obtain catalyst D7.
XRF test shows that the catalyst comprises Co 15.3 wt%, mn 0.4 wt%, cl 0.3 wt% and ZrO 7 based on the total weight of the catalyst 2 The content of (a) was 13.9 wt.%, and the content of titanium dioxide was 69.1 wt.% (in the titanium dioxide, the content of anatase titanium dioxide was 87 wt.%, and the content of rutile titanium dioxide was 13 wt.%).
Catalyst Performance test
Catalysts A1 to A9 and D1 to D7 were each packed in a 10mL fixed bed reactor with a catalyst loading of 0.5g. The catalyst is first in a fixed bed reactor, in H 2 And (3) in the atmosphere at 300-400 ℃ for 5-50h, cooling to 180 ℃ after the reduction is completed, switching into reaction gas, and increasing to the reaction temperature to evaluate the performance of the catalyst.
The conditions for evaluating the catalyst performance include: h 2 In the synthesis gas of/CO (molar ratio) =2, 215 ℃, 2MPa, space velocity is 3L/(g) cat· h)。
The catalyst performance results are shown in table 1.
TABLE 1
As can be seen from the results of Table 1, the catalyst of the present invention has a CO conversion of 50% or more, CH 4 The selectivity is below 6%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (9)

1. A fischer-tropsch synthesis catalyst, characterized in that it comprises, based on the total weight of the catalyst: 10-50 wt% Co,0.01-5 wt% Mn,0.01-2.5 wt% Cl,0.5-10 wt% ZrO 2 35-85% by weight of titanium dioxide;
wherein the titanium dioxide comprises anatase titanium dioxide and rutile titanium dioxide,
the anatase titanium dioxide content is greater than 50 wt.% and the rutile titanium dioxide content is less than 40 wt.%, based on the total amount of titanium dioxide.
2. A fischer-tropsch catalyst as claimed in claim 1, wherein the content of anatase titania is greater than 60 wt% and the content of rutile titania is less than 30 wt%, based on the total amount of titania.
3. The fischer-tropsch synthesis catalyst according to claim 1 or 2, wherein the fischer-tropsch synthesis catalyst comprises, based on the total weight of the catalyst: 15-40 wt% Co,0.05-2 wt% Mn,0.05-1.5 wt% Cl,0.5-7.5 wt% ZrO 2 45-80 wt% of titanium dioxide.
4. A process for the preparation of a fischer-tropsch synthesis catalyst as claimed in any one of claims 1 to 3, comprising: kneading a Co source, a Mn source, a Cl source, a Zr source, a titanium source and an optional peptizing agent, and then drying and roasting to obtain the Fischer-Tropsch synthesis catalyst, wherein the content of Co, mn source, cl source, zr source and titanium source is 10-50 wt%, the content of Mn is 0.01-5 wt%, the content of Cl is 0.01-2.5% and the content of ZrO is calculated based on the total weight of the catalyst 2 The content of (2) is 0.5-10 wt%, and the content of titanium dioxide is 35-85 wt%.
5. The method of claim 4, wherein the Co source is selected from at least one of cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt hydroxide, and cobalt chloride;
and/or Zr source is selected from ZrO 2 At least one of zirconyl nitrate and zirconyl chloride;
and/or Mn source is selected from MnO 2 At least one of manganese acetate, manganese nitrate and manganese chloride;
and/or the titanium source is selected from TiO 2 At least one of titanium chloride, titanium oxychloride, titanium hydroxide and tetrabutyl titanate.
6. The method of claim 4, wherein the peptizing agent is selected from at least one of glacial acetic acid, citric acid, nitric acid, hydrochloric acid, aqueous ammonia, and ammonium bicarbonate.
7. The method of claim 4, wherein the Cl source is selected from at least one of cobalt chloride, zirconium oxychloride, manganese chloride, and hydrochloric acid.
8. The method of any of claims 4-7, wherein the drying conditions comprise: the temperature is 80-130 ℃ and the time is 2-48h;
and/or, the roasting conditions include: the temperature is 300-650 ℃ and the time is 1-40h.
9. Use of a fischer-tropsch synthesis catalyst according to any one of claims 1 to 3 in a fischer-tropsch synthesis reaction.
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