CN105879875A - Supported Fe-based catalyst for Fischer-Tropsch synthesis reaction and preparation method thereof - Google Patents

Supported Fe-based catalyst for Fischer-Tropsch synthesis reaction and preparation method thereof Download PDF

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CN105879875A
CN105879875A CN201610252332.8A CN201610252332A CN105879875A CN 105879875 A CN105879875 A CN 105879875A CN 201610252332 A CN201610252332 A CN 201610252332A CN 105879875 A CN105879875 A CN 105879875A
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load
fischer
tropsch synthesis
preparation
agent
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李程根
李昌元
宋德臣
饶莎莎
詹晓东
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Priority to PCT/CN2017/078018 priority patent/WO2017181815A1/en
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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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy

Abstract

The invention discloses a supported Fe-based catalyst for Fischer-Tropsch synthesis reaction and a preparation method thereof. The catalyst comprises a carrier, an active component Fe, an additive Cu and an additive K; the mass ratio of the active component Fe to the carrier is 20-60%; the mass ratio of the active component Fe to the additive Cu to the additive K is 100 : (5-10) : (4-12); and the additive Cu and the additive K are uniformly distributed on the surface of the catalyst. The low-content additives Cu and K of the catalyst have modification effect much higher than those of the existing supported Fe-based catalyst. According to the preparation method, as one or multiple non-ionic surfactants are introduced, the non-ionic surfactants are mixed and dissolved with inorganic salt providing the active component to the catalyst, an ultrasonic or microwave method is introduced during impregnation, and both drying condition and roasting condition are improved, modification action of the additives Cu and K to the active component is improved, activity and stability of the catalyst are improved, and service life of the catalyst is prolonged.

Description

Load-type iron-based catalyst for Fischer-Tropsch synthesis and preparation method thereof
Technical field
The present invention relates to F-T synthesis technology, in particular to a kind of bearing for Fischer-Tropsch synthesis Load type ferrum-based catalyst and preparation method thereof.
Background technology
F-T synthesis is by synthesis gas (CO and H2) raw material is converted under the effect of catalyst The reaction of organic hydrocarbon, product is further processed obtain high-quality gasoline, diesel oil, The liquid fuels such as aerial kerosene and other chemicals.F-T synthesis technology is that a kind of acquisition is alternative Fuel and the effective way of large industrial chemicals, develop high activity, high selectivity and have excellent The fischer-tropsch synthetic catalyst of good engineering characteristic is core the most in F-T synthesis technical research One of content.
Fe, Co are the ideal fischer-tropsch synthetic catalysts through industry checking, exist at present Successful Application the most in industry.Compared with Co base catalyst, Fe base catalyst because of with low cost, There is the features such as higher water coal vapour shift activity, at coal based synthetic gas and Biomass Syngas Conversion has a wide range of applications.Fe base catalyst is divided into sedimentation type and support type, with precipitation Type ferrum-based catalyst is compared, and support type Fe base catalyst resistance against physical polishing machine is strong, has height The feature that specific surface area, anti-sintering property are good, before therefore embodying more preferable industrial applications Scape.But, the catalysis in Fischer-Tropsch synthesis of the load-type iron-based catalyst without auxiliary agent is lived Property, stability and selectivity are the most undesirable.Therefore, in the preparation process of ferrum-based catalyst, Need to add the auxiliary agents such as Cu, K to regulate the property indices of catalyst.Peace rosy clouds et al. Research shows, because of the difference of catalyst preparation conditions, Cu is to catalyst activity and stability Impact be also not quite similar (Journal of Fuel Chemistry and Technology, Vol39, 2011,212)；The result of study of Zhao et al. shows K and " hole " of carrier in catalyst Or the acidic site in duct combines, directly weaken contacting of Fe with K, it is suppressed that catalyst The facilitation of middle K (Journal of Molecular Catalysis A:Chemical, Vol286, 2008,137)；Chinese patent literature CN102649079A report a kind of activated carbon supported Fe base catalyst, the methane selectively of this catalyst be more than 20%, hence it is evident that higher.
In sum, conventional load type Fe base catalyst exists as follows in Fischer-Tropsch synthesis Problem: 1) auxiliary agent Cu is easily at catalyst particle surface segregation, and covering active sites, to work Property component promotor action die down, reduce reactivity and stability；2) auxiliary agent K easily and carries The defective bit of body combines, cause K at the skewness of catalyst surface, to active component In frared spectra reduces, C in product5+Selectivity declines；3) load-type iron-based catalyst CH4Selectivity is the most higher；4) prepare conventional load type Fe base catalyst and generally need to use many Secondary dipping and roasting, its operating procedure is complicated, the longest.The above shortcoming greatly limits Load-type iron-based catalyst is in the application in industry F-T synthesis field.
Summary of the invention
Present invention aim to provide a kind of load-type iron-based for Fischer-Tropsch synthesis Catalyst and preparation method thereof, this catalyst improves Cu, K auxiliary agent to active component Fe Promotor action, thus improve activity and the stability of catalyst, extend the use of catalyst Life-span.
For achieving the above object, the technical solution used in the present invention is: a kind of for F-T synthesis The load-type iron-based catalyst of reaction, including carrier, active component Fe, auxiliary agent Cu and auxiliary agent K, described active component Fe is 20～60% with the mass ratio of described carrier, described active component Fe with the mass ratio of described auxiliary agent Cu and described auxiliary agent K is: 100: 5～10: 4～12；And Described auxiliary agent Cu and described auxiliary agent K is uniformly distributed on the surface of catalyst.
Further, described active component Fe and described auxiliary agent Cu and the matter of described auxiliary agent K Amount ratio is: 100: 6～10: 8～12.
Further, described active component Fe is 30～40% with the mass ratio of described carrier.
A kind of preparation method of the above-mentioned load-type iron-based catalyst for Fischer-Tropsch synthesis, bag Include following steps:
1) by water with alcohol be by volume 1～3: 1 proportions become mixed liquor, then press The mass ratio of Cu: K be 5: 2～12 ratio weigh soluble Cu salt and solubility K salt stirs Mix and be dissolved in described mixed liquor, join to obtain mixed solution；
2) add solvable in described mixed solution in the ratio that mass concentration is 20～100g/L Nonionic surfactant, join to obtain presoma mother solution；
3) in the ratio that the mass ratio of Fe: Cu: K is 100: 5～10: 4～12 before described Drive addition Dissolvable Fe salt in body mother solution, join to obtain dipping mother solution, Fe in described dipping mother solution Concentration is 25～100g/L；
4) described load is weighed in the ratio of 20 that the load capacity of Fe is described carrier quality～60% Body, by described mother solution thorough impregnation to described carrier, uses supersonic vibration in dipping process Or microwave treatment, then carry out vacuum drying treatment, obtain sample；
5) described sample is carried out calcination process, i.e. can get described catalyst.
Further, described step 4) in, dip time is 8～48h, in dipping process Supersonic vibration or microwave treatment time are 0.5～1.0h；Vacuum drying temperature is 100～180 DEG C, The vacuum drying time is 8～36h.
Further, described step 4) in, dip time is 11～20h, in dipping process Ultrasonic or the microwave vibrations process time is 0.8～1.0h；Vacuum drying temperature is 120～130 DEG C, The vacuum drying time is 12～24h.
Further, described step 5) in, sintering temperature is 300～600 DEG C, roasting time It is 2～8h.
Further, described step 5) in, sintering temperature is 400～500 DEG C, roasting time It is 4～6h.
Further, described step 2) in, in the ratio that mass concentration is 60～90g/L to Described mixed solution adds solvable nonionic surfactant.
Further, described step 2) in, it is heated to 30～50 DEG C and uses microwave Or ultrasonic vibration treatment, the process time is 10～30min.
Further, described step 3) in, continue to be heated to 30～50 DEG C, and use Microwave or ultrasonic vibration treatment, the process time is 10～30min.
Further, described step 1) in, described soluble Cu salt is copper nitrate hydrate Or the mixing of one or both in acetate hydrate.
Further, described step 1) in, described solubility K salt is potassium nitrate or potassium acetate In one or both mixing.
Further, described step 1) in, described alcohol is in methanol, ethanol or butanol The mixing of one or more.
Further, described step 2) in, described nonionic surfactant is polypropylene Acid PAA, PVAC polyvinylalcohol, Polyethylene Glycol PEG, poly(ethylene oxide) PEO or tween The mixing of one or more in-80.
Further, described step 3) in, described Dissolvable Fe salt is ferric nitrate hydrate Or one or both in iron acetate hydrate.
Further, described step 4) in, it is described carrier quality by the load capacity of Fe 30～40% ratio weigh described carrier.
Further, described step 4) in, described carrier be silicon dioxide, aluminium oxide, The mixing of one or more in activated carbon or ZSM-5.
Compared with prior art, the invention have the advantages that
One, the present invention is by introducing one or more nonionic surfactant, and by non- Ionic surfactant is the most miscible with the inorganic salt providing catalyst active component, and in leaching Introducing the ultrasonic or method of microwave during stain, improve drying condition and roasting condition, raising helps Agent Cu, the auxiliary agent K promotor action to active component, thus improve the activity of catalyst with steady Qualitative, extend the service life of catalyst.
Its two, the excellent reason of catalyst performance prepared by the present invention is, is prepared by optimization Condition, have adjusted Cu, K component strong promotor action to Fe component in catalyst particle, Improve reactivity and the selectivity of product of catalyst, effectively eliminate in course of reaction and be catalyzed Carbon deposit on agent active particle, prevents the growth of CNT, maintains catalyst load knot The stability of structure, and slow down the sintering of active specy so that auxiliary agent Cu and auxiliary agent K is urging The surface of agent can be uniformly distributed.
Its three, auxiliary agent Cu and the auxiliary agent K content of catalyst of the present invention are low, but for activity The promotor action of component is significantly stronger than existing load-type iron-based catalyst.
Its four, for improving builder efficiency and auxiliary agent promotor action, conventional load type ferrum-based catalyst Preparation technology generally need to use repeatedly impregnating complicated approach, and in the preparation process of the present invention Only need to impregnate once, operation is simple, and operation is convenient.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, it is simple to becomes apparent from The present invention is understood on ground, but they do not constitute restriction to the present invention.
Embodiment 1
Weigh 0.68g nitrate trihydrate copper, 0.50g potassium nitrate, with 30ml methanol and 30ml water Mixed liquor nitrate trihydrate copper and potassium nitrate are dissolved, add the Polyethylene Glycol of 5.4g, 30 DEG C supersound process 30min, after adding 17.31g nine water ferric nitrate, ultrasonic 50 DEG C of continuation 15min, prepares dipping mother solution, then weighs the activated carbon of 6g, be added dropwise over by dipping mother solution On absorbent charcoal carrier, after dropping, supersound process 30min, impregnation process time 12h, 12h, then 500 DEG C of roasting 4h under nitrogen atmosphere is protected it are dried under 130 DEG C of vacuum conditions, The catalyst of gained is designated as 40%Fe100Cu6.0K8.0/AC。
Embodiment 2
Weigh 0.26g mono-water acetic acid copper, 0.19g potassium nitrate, with 20ml methanol and 40ml water Mixed liquor one water acetic acid copper and potassium nitrate are dissolved, add the PVAC polyvinylalcohol of 4.8g, 50 DEG C of supersound process 10min, after adding 7.49g iron acetate, continue ultrasonic 15min at 40 DEG C, Prepare dipping mother solution, then weigh the silicon dioxide of 6g, dipping mother solution is added dropwise to two On silica support, after dropping, microwave treatment 30min, impregnation process time 15h, 16h, the most in atmosphere, roasting 6h at 400 DEG C, institute it is dried under 125 DEG C of vacuum conditions The catalyst obtained is designated as 30%Fe100Cu5.0K4.0/SiO2。
Embodiment 3
Weigh 0.36g mono-water acetic acid copper, 0.22g potassium nitrate, with 20ml ethanol and 50ml water Mixed liquor one water acetic acid copper and potassium nitrate are dissolved, add the polyacrylic acid PAA of 4.8g, 40 DEG C of supersound process 15min, after adding 15.15g nine water ferric nitrate, continue super at 50 DEG C Sound 15min, prepares dipping mother solution, then weighs the silicon dioxide of 6g, will dipping mother solution by It is added dropwise on silica supports, after dropping, supersound process 45min, impregnation process Time 15h, is dried 16h under 125 DEG C of vacuum conditions, the most in atmosphere, roasts at 400 DEG C Burning 6h, the catalyst of gained is designated as 35%Fe100Cu6.0K4.0/SiO2。
Embodiment 4
Weigh 0.92g nitrate trihydrate copper, 0.60g potassium nitrate, with 30ml butanol and 30ml water Mixed liquor nitrate trihydrate copper and potassium nitrate are dissolved, add the PVAC polyvinylalcohol of 3.6g, 40 DEG C of supersound process 20min, after adding 8.00g iron acetate, continue ultrasonic 15min at 45 DEG C, Prepare dipping mother solution, then weigh the ZSM-5 of 6g, dipping mother solution is added dropwise to ZSM-5 On carrier, after dropping, microwave treatment 45min, impregnation process time 18h, 120 24h, the most in atmosphere, roasting 5h at 450 DEG C, urging of gained it is dried under DEG C vacuum condition Agent is designated as 32%Fe100Cu10.0K12.0/ZSM-5。
Embodiment 5
Weigh 0.30g mono-water acetic acid copper, 0.65g potassium nitrate, with 20ml butanol and 40ml water Mixed liquor one water acetic acid copper and potassium nitrate are dissolved, add the polyacrylic acid PAA of 3.6g, 35 DEG C of supersound process 15min, after adding 15.15g nine water ferric nitrate, continue super at 50 DEG C Sound 20min, prepares dipping mother solution, then weighs the ZSM-5 of 6g, will impregnate mother solution dropwise Joining on ZSM-5 carrier, after dropping, supersound process 60min, during impregnation process Between 10h, under 120 DEG C of vacuum conditions be dried 24h, the most in atmosphere, roasting at 450 DEG C 5h, the catalyst of gained is designated as 35%Fe100Cu5.0K12.0/ZSM-5。
Embodiment 6
Weigh 0.74g nitrate trihydrate copper, 0.52g potassium nitrate, with 20ml ethanol and 30ml water Mixed liquor nitrate trihydrate copper and potassium nitrate are dissolved, add polyvinyl alcohol and the 2.1g of 2.1g Polyethylene Glycol, 40 DEG C of supersound process 15min, after adding 16.02g nine water ferric nitrate, Continue ultrasonic 15min at 50 DEG C, prepare dipping mother solution, then weigh the Al of 6g2O3, will Dipping mother solution is added dropwise to Al2O3On carrier, after dropping, microwave treatment 60min, Impregnation process time 20h, dry 20h under 125 DEG C of vacuum conditions, the most in atmosphere, Roasting 5h at 450 DEG C, the catalyst of gained is designated as 37%Fe100Cu7.0K9.0/Al2O3。
Embodiment 7
Weigh 0.69g mono-water acetic acid copper, 0.25g potassium nitrate, with 30ml methanol and 30ml water Mixed liquor one water acetic acid copper and potassium nitrate are dissolved, add polyvinyl alcohol and the 2.1g of 2.1g Polyethylene Glycol, 30 DEG C of supersound process 15min, after adding 9.99g iron acetate, 50 DEG C continue ultrasonic 25min, prepare dipping mother solution, then weigh the Al of 6g2O3, will dipping mother Liquid is added dropwise to Al2O3On carrier, after dropping, supersound process 30min, at microwave Reason 30min, impregnation process time 20h, be dried 20h under 125 DEG C of vacuum conditions, then exist In air, roasting 5h at 450 DEG C, the catalyst of gained is designated as 40%Fe100Cu10.0K4.0/Al2O3。
Comparative example 1
Weigh 9.99g iron acetate, 0.69g mono-water acetic acid copper, 0.93g potassium nitrate, use 30ml Methanol is dissolved with the mixture of 30ml water, at 50 DEG C of constant temperature 30min, then weighs 6g Activated carbon, dipping mother solution is added dropwise on carrier, impregnation process time 12h, 130 12h, then 500 DEG C of roasting 4h, gained under nitrogen atmosphere is protected it is dried under DEG C vacuum condition Catalyst be designated as 40%Fe100Cu10.0K15.0/AC-IWI。
Anti-by carrying out F-T synthesis after embodiment 1～7 and the activation of catalyst for preparing of comparative example 1 Should, wherein, activation condition is as follows: activation temperature: 450 DEG C, reducing atmosphere: H2, reduction Time: 16h；The reaction condition of Fischer-Tropsch synthesis is as follows: reactor fixed bed reactors are anti- The temperature is answered to be: 280 DEG C, reaction pressure is: 3.0MPa, H2/ CO is: 1.7, and reactor is empty Speed (GHSV): 3.0SL/g h.
Embodiment 1～7 and the catalyst for preparing of comparative example 1 run the Activity evaluation of 100h See table 1:
Table 1
Catalyst CO conversion ratio CH4Selectivity C2～C4Selectivity C5+Selectivity
Embodiment 1 85.4 4.9 15.9 79.2
Embodiment 2 87.9 4.7 13.4 81.9
Embodiment 3 89.6 4.5 12.4 83.1
Embodiment 4 93.5 4.4 16.9 78.7
Embodiment 5 84.7 7.1 13.8 79.1
Embodiment 6 91.4 5.2 13.4 81.4
Embodiment 7 95.4 4.8 15.6 79.6
Comparative example 1 70.2 7.6 37.3 55.1
Embodiment 1～7 and the catalyst for preparing of comparative example 1 run the Activity evaluation of 500h See table 2:
Table 2
Catalyst CO conversion ratio CH4Selectivity C2～C4Selectivity C5+Selectivity
Embodiment 1 60.4 5.9 16.9 77.2
Embodiment 2 61.9 6.0 15.1 78.9
Embodiment 3 63.6 5.5 16.4 78.1
Embodiment 4 62.5 6.4 17.9 75.7
Embodiment 5 58.7 6.3 20.6 73.1
Embodiment 6 61.4 6.4 19.2 74.4
Embodiment 7 60.4 6.4 20.0 73.6
Comparative example 1 40.7 8.6 44.3 47.1
Catalyst performance embodiment 1～7 prepared is carried out with the catalyst performance of comparative example 1 Relatively, from table 1, data can be seen that catalyst activity prepared by the inventive method substantially carries In height, and product, the selectivity of methane substantially reduces, C5+The selectivity of product is significantly carried High.It addition, comparing embodiment 1～7 and the catalyst for preparing of comparative example 1 run 100h and 500h Evaluation result, can be seen that from Tables 1 and 2 data and use the catalysis prepared of the inventive method The stability of agent be improved significantly, run after 500h and still keep preferable reactivity and product Thing selectivity, the CO conversion ratio of comparative example 1 is then reduced to 40.7%, C5+The choosing of product Selecting property is down to 47.1.Therefore, use support type Fe base catalyst prepared by the inventive method, Clearly enhance Cu, K component strong promotor action to Fe component, thus improve catalysis The activity and selectivity of agent, extends its service life, reduces the cost of unit synthetic oil, This is significant for the Fe base catalyst that exploitation is new and effective.

Claims (18)

1., for a load-type iron-based catalyst for Fischer-Tropsch synthesis, including carrier, live Property component Fe, auxiliary agent Cu and auxiliary agent K, it is characterised in that: described active component Fe and institute The mass ratio stating carrier is 20～60%, described active component Fe and described auxiliary agent Cu and described The mass ratio of auxiliary agent K is: 100: 5～10: 4～12；And described auxiliary agent Cu and described auxiliary agent K is uniformly distributed on the surface of catalyst.
The most according to claim 1 for the load-type iron-based catalyst of Fischer-Tropsch synthesis, It is characterized in that: described active component Fe and described auxiliary agent Cu and the quality of described auxiliary agent K Ratio is: 100: 6～10: 8～12.
The most according to claim 1 for the load-type iron-based catalyst of Fischer-Tropsch synthesis, It is characterized in that: described active component Fe is 30～40% with the mass ratio of described carrier.
4. for the load-type iron-based catalyst of Fischer-Tropsch synthesis described in a claim 1 Preparation method, it is characterised in that: comprise the following steps:
1) by water with alcohol be by volume 1～3: 1 proportions become mixed liquor, then press The mass ratio of Cu: K be 5: 2～12 ratio weigh soluble Cu salt and solubility K salt stirs Mix and be dissolved in described mixed liquor, join to obtain mixed solution；
2) add solvable in described mixed solution in the ratio that mass concentration is 20～100g/L Nonionic surfactant, join to obtain presoma mother solution；
3) in the ratio that the mass ratio of Fe: Cu: K is 100: 5～10: 4～12 before described Drive addition Dissolvable Fe salt in body mother solution, join to obtain dipping mother solution, Fe in described dipping mother solution Concentration is 25～100g/L；
4) described load is weighed in the ratio of 20 that the load capacity of Fe is described carrier quality～60% Body, by described mother solution thorough impregnation to described carrier, uses supersonic vibration in dipping process Or microwave treatment, then carry out vacuum drying treatment, obtain sample；
5) described sample is carried out calcination process, i.e. can get described catalyst.
The most according to claim 4 for the load-type iron-based catalyst of Fischer-Tropsch synthesis Preparation method, it is characterised in that: described step 4) in, dip time is 8～48h, In dipping process, supersonic vibration or microwave treatment time are 0.5～1.0h；Vacuum drying temperature is 100～180 DEG C, the vacuum drying time is 8～36h.
6. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 4) in, dip time is 11～20h, In dipping process, ultrasonic or microwave vibrations processes the time is 0.8～1.0h；Vacuum drying temperature is 120～130 DEG C, the vacuum drying time is 12～24h.
7. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 5) in, sintering temperature is 300～600 DEG C, roasting time is 2～8h.
8. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 5) in, sintering temperature is 400～500 DEG C, roasting time is 4～6h.
9. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 2) in, by mass concentration it is The ratio of 60～90g/L adds solvable nonionic surfactant in described mixed solution.
10. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 2) in, it is heated to 30～50 DEG C and to use microwave or ultrasonic vibration treatment, process time be 10～30min.
11. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 3) in, continue to be heated to 30～50 DEG C, and to use microwave or ultrasonic vibration treatment, process time be 10～30min.
12. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 1) in, described soluble Cu salt For one or both the mixing in copper nitrate hydrate or acetate hydrate.
13. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 1) in, described solubility K salt is One or both mixing in potassium nitrate or potassium acetate.
14. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 1) in, described alcohol is methanol, second The mixing of one or more in alcohol or butanol.
15. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 2) in, described non-ionic surface Activating agent is polyacrylic acid PAA, PVAC polyvinylalcohol, Polyethylene Glycol PEG, polycyclic oxygen second The mixing of one or more in alkane PEO or tween 80.
16. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 3) in, described Dissolvable Fe salt For one or both in ferric nitrate hydrate or iron acetate hydrate.
17. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 4) in, by the load capacity of Fe it is The 30 of described carrier quality～the ratio of 40% weigh described carrier.
18. urge for the load-type iron-based of Fischer-Tropsch synthesis according to described in claim 4 or 5 The preparation method of agent, it is characterised in that: described step 4) in, described carrier is titanium dioxide The mixing of one or more in silicon, aluminium oxide, activated carbon or ZSM-5.
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