CN103599788B - A kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application - Google Patents
A kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application Download PDFInfo
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- CN103599788B CN103599788B CN201310529488.2A CN201310529488A CN103599788B CN 103599788 B CN103599788 B CN 103599788B CN 201310529488 A CN201310529488 A CN 201310529488A CN 103599788 B CN103599788 B CN 103599788B
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Abstract
The present invention discloses a kind of catalyst for CO hydrogenation, and described catalyst is made up of the composite metal oxide and metal promoter with perovskite structure, and the complex metal formula with perovskite structure is ABO
3-y, wherein, A is rare earth metal, and B is the transition metal at least comprising cobalt, and the mol ratio of cobalt and all the other transition metal is not less than 3:1, is preferably not less than 4:1, and y is the molal quantity of the Lacking oxygen existed in composite oxides; With the weighing scale of catalyst, metal promoter simple substance content is 1-15%, preferred 5%-10%.This catalyst can improve the ratio of diesel oil distillate in liquid hydrocarbon product, the selective of reduction methane.
Description
Technical field
The present invention relates to a kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application, relating in particular to a kind of is raw material with synthesis gas, prepares concentrated CO hydrogenation Co based Fischer-Tropsch synthesis catalyst of carbon atom distribution and its preparation method and application.
Background technology
Liquid fuel is that modern society relies the blood of running, and it mainly to be produced by crude refining, processing.In recent years, owing to causing liquid fuel price continuous rise to the worry of crude supply prospect, a large amount of uses of liquid fuel simultaneously also bring serious problem of environmental pollution, and setting up continuable clean fuel liquid production method is the effective means solving above-mentioned two problems.Fischer-tropsch synthesis process refers to and coal, natural gas, living beings etc. is first converted into synthesis gas (CO and H containing carbon resource
2mixture), then synthesis gas is polymerized on a catalyst the process of gaseous state, liquid state and solid hydrocarbons, synthesis gas polymerization process is below called as Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis).Liquid hydrocarbon prepared by F-T synthesis, after hydrogenation upgrading, has the character identical with the liquid fuel that petroleum refining is produced.Because the known reserves of coal, natural gas verify reserves much larger than oil, living beings are a kind of reproducible resources, therefore fischer-tropsch synthesis process can, for society provides the sufficient liquid fuel being representative with gasoline and diesel oil etc. within the longer time, be the technology of desirable production petroleum replacing fuel.
Fischer-tropsch reaction carries out on a catalyst, and the catalyst (high activity, high selectivity, high stability) with excellent properties is the technical guarantee realizing efficient fischer-tropsch synthesis process.Catalyst activity is high, can improve the specific productivity of reaction unit, and selective height can improve the utilization rate of reaction raw materials, and stability is high is conducive to the running at full capacity, the minimizing non-normal stop that maintain reaction unit.Finding in the studying for a long period of time of fischer-tropsch reaction: nickel, ruthenium, iron and cobalt have fischer-tropsch reaction activity.Nickel-base catalyst, under fischer-tropsch reaction condition, can produce too many methane, self is easy to generate volatile carbonyl nickel and run off from reactor simultaneously, is difficult to realize commercial Application.Ruthenium is the most active known fischer-tropsch reaction catalyst, but its high price and limited reserves hinder its use on industrial Fischer Tropsch Facility, and it is generally add in iron-based and cobalt-base catalyst with auxiliary agent form, improve their reactivity worth.Iron-based and cobalt-base catalyst is only had to be used successfully in F-T synthesis industry.Ferrum-based catalyst and cobalt-base catalyst have bigger difference in reactivity worth.
Ferrum-based catalyst can have very high reactivity, but research [Fuel 76 (1997) 273.] finds that the CO reacted is converted into CO with higher ratio along with CO conversion ratio raises
2instead of hydrocarbon, namely generate selective the rising along with CO conversion ratio of hydrocarbon and decline.In order to obtain higher Auditory steady-state responses, ferrum-based catalyst is considered to suitable to lower CO conversion per pass work, CO total conversion (synthesis gas utilization rate) that secondary response mode reaches high and high hydrocarbon-selective is carried out by reaction end gas circulation, but this working method adds workload and the corresponding energy consumption such as tail gas separation, gas circulation compression, and the gross efficiency limiting fischer-tropsch synthesis process improves.
Forming what contrast with ferrum-based catalyst reactivity worth is cobalt-base catalyst, and its performance is less by generating water mitigation in fischer-tropsch reaction, and because its water-gas shift activity is very weak, the CO in synthesis gas is mainly converted into hydrocarbon.So, use the fischer-tropsch synthesis process of cobalt-base catalyst can to work in high conversion per pass mode, the operation to reaction end gas compression cycle can be save, shorten technological process, be conducive to the gross efficiency improving fischer-tropsch synthesis process.
US6765026B2 discloses and a kind ofly applies the Fischer-Tropsch synthesis method that special catalyst carries out catalysis.The catalyst precursor that the method adopts is the soluble compounds of a kind of iron group (especially cobalt) metal or the soluble compounds of salt and platinum or salt.The solution of presoma with hydroxyhy-drocarbyl amines or ammonium hydroxide is contacted, obtains a kind of special catalyst, make C
5 +hydrocarbon selective reaches 58% ~ 80%.
CN101224430A reports a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, and noble metal and cobalt load on silica supports, then carries out organically-modified.Wherein when noble metal adopts Pt, catalyst system 15%Co0.8%Pt/SiO
2, organically-modified reagent adopts dimethyldiethoxysilane modification, and on pressurization static bed, reaction condition is 230 DEG C, 1.0MPa, 1000h
-1(V/V), H
2the conversion ratio of/CO=3/1, CO is 72.7%.
CN200810039490.0 discloses a kind of precipitated ferrum-cobalt catalyst for F-T synthesis, the composition of this catalyst comprises: elemental iron, element cobalt 2 ~ 50g/100gFe, Element Potassium 1 ~ 10g/100gFe and the siliceous oxygen species 5 ~ 100g/100gFe with silica weight.Preparation method is mixed solution precipitating reagent being added iron-containing liquor and cobalt-carrying solution, after aging 24h to be precipitated, washing and filtering, obtain the co-precipitation filter cake of iron content cobalt, deionized water is added in filter cake, making beating makes it even, SiO 2 powder and potassium carbonate powder is added under constantly at the uniform velocity stirring, or add SiO 2 powder and potassium silicate colloid, mix, obtained catalyst pulp is dry, roasting, namely obtain described precipitated ferrum-cobalt catalyst, its weight ratio consists of Fe: Co: K: SiO
2=100: 2 ~ 50: 1 ~ 10: 5 ~ 100.The sintering temperature of described catalyst pulp is 400 ~ 500 DEG C, roasting time is 2 ~ 6 hours.The method has higher gas conversions equally.
In sum, Co based Fischer-Tropsch synthesis catalyst compares ferrum-based catalyst and so, synthesis gas conversion ratio and reduce carbon dioxide selective on there is obvious advantage, but while high conversion, also there is liquid hydrocarbon product distribution compare dispersion, the long paraffinic components of carbochain is on the high side, the problems such as the selective height of methane; Be unfavorable for follow-up processing and utilization, the solution of these problems can improve application and the popularization of Co based Fischer-Tropsch synthesis catalyst further.
Summary of the invention
For the deficiencies in the prior art, the present invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst for CO hydrogenation and its preparation method and application.This catalyst can improve the ratio of diesel oil distillate in liquid hydrocarbon product, the selective of reduction methane.
For a catalyst for CO hydrogenation, described catalyst is made up of the composite metal oxide and metal promoter with perovskite structure, and the complex metal formula with perovskite structure is ABO
3-y, wherein, A is rare earth metal, and B is the transition metal at least comprising cobalt, and the mol ratio of cobalt and all the other transition metal is not less than 3:1, is preferably not less than 4:1, and y is the molal quantity of the Lacking oxygen existed in composite oxides; With the weighing scale of catalyst, metal promoter simple substance content is 1-15%, preferred 5%-10%.
The present invention is used in the catalyst of CO hydrogenation, and described rare earth metal comprises one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium.Described transition metal comprises one or more in iron, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium except cobalt.Described auxiliary agent is various auxiliary agents used in existing F-T synthesis technology, as one or more in zirconium, potassium, ruthenium, platinum, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
The present invention is used in the catalyst of CO hydrogenation, the composite metal oxide NdTi with perovskite structure that described catalyst is made up of rare earth metal neodymium and transition metals Ti and iron
1-xco
xo
3-y, wherein 0.8<x< 0.95 and auxiliary agent zinc composition.Composite metal oxide containing neodymium perovskite structure can produce to act synergistically with auxiliary agent zinc and improve diesel oil distillate in liquid hydrocarbon product further.
For a preparation method for the catalyst of CO hydrogenation, comprise preparation and the metal promoter loading process of the composite metal oxide with perovskite structure.
In the inventive method, the described preparation with the composite metal oxide of perovskite structure adopts complexometry, but is not limited to the method.Described complexometry comprises following process: first the metering rare earth metal of ratio and the transition metal precursor of iron content stirred with complexing agent mixing wiring solution-forming, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, the obtained composite metal oxide with perovskite structure after roasting.There is with preparation the composite metal oxide NdTi of perovskite structure
1-xco
xo
3-ywherein 0.8<x< 0.95 is example, specifically comprise following content: with neodymium nitrate, Titanium Nitrate, nickel nitrate for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, the sample after roasting is the catalyst for CO hydrogenation.
Above-mentioned complexometry preparation has in the composite metal oxide of perovskite structure, and complexing agent and metal ion mol ratio are 1:1 ~ 8:1, are preferably 1:1 ~ 4:1.Preparation and agitating solution, at 20 ~ 90 DEG C, carry out at being preferably 50 ~ 70 DEG C.Stir speed (S.S.) is 200 ~ 500rpm, is preferably 300 ~ 400rpm.Mixing time is 3 ~ 8 hours, is preferably 4 ~ 6 hours.Baking temperature is 60 ~ 200 DEG C, is preferably 80 ~ 150 DEG C.Drying time is 1 ~ 36 hour, is preferably 8 ~ 24 hours.Sintering temperature is 600 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours, is preferably roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
In the inventive method, described metal promoter loading process adopts infusion process, incipient impregnation or excessively volume impregnation.Can single-steeping be carried out according to actual conditions or repeatedly flood.Such as there is the composite metal oxide NdTi of perovskite structure
1-xco
xo
3-y(0.8<x< 0.95) is upper adopts equi-volume impregnating carried metal auxiliary agent Zn.
For a method of reducing for the catalyst of CO hydrogenation, reduction temperature is 400 ~ 1000 DEG C, preferred 500-700 DEG C, and the recovery time is 1-5h, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3, preferred the latter.Adopt the CO hydrogenation catalyst of low-carbon alkanes reduction while reduction, suitable modification can be carried out to catalyst, reduce the selective of methane.
The present invention adopts B position containing the composite metal oxide with perovskite structure of cobalt as fischer-tropsch synthetic catalyst, the content of diesel oil distillate in liquid hydrocarbon product is improve while keeping high conversion, reduce the selective of methane, solve the high and problem that distribution is wide, methane selectively is higher of the ubiquitous liquid hydrocarbon product of Co based Fischer-Tropsch synthesis catalyst in prior art carbon number.The present invention has in the preparation process of the composite metal oxide of perovskite structure, and the change of preparation condition can have a strong impact on generation and the purity of perovskite structure.In all conditions control, choosing of sintering temperature is vital, although some catalyst composition of the prior art is more close with the present invention, because the crystalline structure of constituent content and inherence is obviously different, so do not have the premium properties of catalyst of the present invention.
Accompanying drawing explanation
Fig. 1 is the complex metal compound LaCoO with perovskite structure prepared by embodiment 1
3-yxRD figure.
Detailed description of the invention
Further illustrate process and the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.
Embodiment 1
Preparation contains the mixed aqueous solution of cobalt nitrate and lanthanum nitrate, is that 1.2:1 takes appropriate citric acid, in mixed aqueous solution, adds citric acid slowly by metal ion total amount mol ratio in citric acid and mixed aqueous solution, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 4 hours at 800 DEG C, obtain the composite metal oxide LaCoO with perovskite structure
3-y, adopt infusion process at composite metal oxide LaCoO
3-yupper load weight content is the auxiliary agent potassium of 5%, and 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C, obtained catalyst was designated as C-1, and evaluation result is in table 1.
Embodiment 2
The mixed aqueous solution of preparation containing cobalt nitrate, cerous nitrate and Titanium Nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 DEG C, obtain the composite metal oxide CeCo with perovskite structure
0.9ti
0.1o
3-y, adopt infusion process at composite metal oxide CeCo
0.9ti
0.1o
3-yupper load weight content is the zinc of 10%, and obtained catalyst is designated as C-2, and evaluation result is in table 1.
Embodiment 3
The mixed aqueous solution of preparation containing neodymium nitrate, cobalt nitrate and Titanium Nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 DEG C, obtain the composite metal oxide NdCo with perovskite structure
0.9ti
0.1o
3-y, adopt infusion process at composite metal oxide NdCo
0.9ti
0.1o
3-yupper load weight content is the zinc of 10%, and obtained catalyst is designated as C-3, and evaluation result is in table 1.
Embodiment 4
The mixed aqueous solution of preparation containing neodymium nitrate, cobalt nitrate and Titanium Nitrate, is that 4:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 8 hours at 600 DEG C, obtain the composite metal oxide NdTi with perovskite structure
0.15co
0.85o
3-y, adopt infusion process at composite metal oxide NdTi
0.15co
0.85o
3-yupper load weight content is the auxiliary agent zinc of 5%, and 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C, obtained catalyst C-4, evaluation result was in table 1.
Embodiment 5
The mixed aqueous solution of preparation containing cobalt nitrate, cerous nitrate, is that 3:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 5 hours at 1000 DEG C, obtain the composite metal oxide CeCoO with perovskite structure
3-y, adopt infusion process at composite metal oxide CeCoO
3-yupper load weight content is the auxiliary agent manganese of 8%, and obtained catalyst is designated as C-5, and evaluation result is in table 1.
Comparative example 1
Adopt conventional coprecipitation to obtain cobalt, the lanthanum composite metal oxide of non-perovskite structure, sintering temperature is 450 DEG C, then impregnation aids potassium, and obtained catalyst is designated as B1, and in oxide, the weight content of lanthanum, cobalt, potassium is with embodiment 1, and evaluation result is in table 1.
Carry out activity rating to catalyst prepared by above-described embodiment and comparative example, evaluation test is carried out in high pressure CSTR, using paraffin as solvent.First carry out reduction 5 hours to catalyst, reduction temperature is 650 DEG C, and wherein embodiment 3 adopts methane gas to reduce, and all the other adopt hydrogen reducing.After reduction, catalyst is put into reactor and carry out Fischer-Tropsch synthesis, reaction actual conditions is 200 DEG C, 1000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).The operation result of 200h is in table 1, and the conversion ratio of CO is conversion per pass.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
Claims (9)
1. for a fischer-tropsch synthetic catalyst for CO hydrogenation, it is characterized in that: the composite metal oxide NdTi with perovskite structure that described catalyst is made up of rare earth metal neodymium and transition metals Ti and cobalt
1-xco
xo
3-ywith auxiliary agent zinc composition, wherein composite metal oxide NdTi
1-xco
xo
3-ymiddle 0.8<x< 0.95, with the weighing scale of catalyst, auxiliary agent zinc simple substance content is 5-10%.
2. the preparation method of catalyst described in claim 1, is characterized in that: comprise the composite metal oxide NdTi with perovskite structure
1-xco
xo
3-ypreparation and the loading process of auxiliary agent zinc.
3. method according to claim 2, it is characterized in that: with neodymium nitrate, cobalt nitrate, Titanium Nitrate for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, prepares the composite metal oxide NdTi with perovskite structure after roasting
1-xco
xo
3-y, wherein 0.8<x< 0.95.
4. method according to claim 3, is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 8:1; Preparation and agitating solution are at 20 ~ 90 DEG C; Stir speed (S.S.) is 200 ~ 500rpm; Mixing time is 3 ~ 8 hours; Baking temperature is 60 ~ 200 DEG C; Drying time is 1 ~ 36 hour; Sintering temperature is 600 ~ 1000 DEG C, and roasting time is 2 ~ 15 hours.
5. method according to claim 4, is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 4:1; Preparation and agitating solution carry out at 50 ~ 70 DEG C; Stir speed (S.S.) is 300 ~ 400rpm; Mixing time is 4 ~ 6 hours; Baking temperature is 80 ~ 150 DEG C; Drying time is 8 ~ 24 hours; Sintering temperature is 700 ~ 900 DEG C, roasting time 3 ~ 8 hours.
6. method according to claim 2, is characterized in that: described auxiliary agent zinc loading process adopts infusion process.
7. method according to claim 6, is characterized in that: have the composite metal oxide NdTi of perovskite structure
1-xco
xo
3-yupper employing equi-volume impregnating carried metal auxiliary agent Zn, wherein 0.8<x< 0.95.
8. the method for reducing of catalyst described in claim 1, is characterized in that: reduction temperature is 400 ~ 1000 DEG C, and the recovery time is 1-5h, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3.
9. method of reducing according to claim 8, is characterized in that: reduction temperature is 500-700 DEG C, and reducing atmosphere is the low-carbon alkanes of C1-C3.
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| CN109225234B (en) * | 2018-09-19 | 2021-07-20 | 石河子大学 | Composition for preparing methane by carbon catalytic hydrogenation |
| CN110876943B (en) * | 2019-11-19 | 2022-11-04 | 天津大学 | Oxide-modified Pt-Co bimetallic catalyst, preparation method and application thereof to CO oxidation |
| CN112169817B (en) * | 2020-10-19 | 2022-10-04 | 宁夏大学 | Perovskite type composite oxygen carrier and application |
| CN112121814B (en) * | 2020-10-19 | 2021-10-29 | 宁夏大学 | Preparation method and application of perovskite catalyst |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN112403491B (en) * | 2020-11-26 | 2021-12-28 | 厦门大学 | Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof |
| CN114558586A (en) * | 2022-02-28 | 2022-05-31 | 中国科学技术大学 | KCoMnMoOxCatalyst, preparation method and application thereof |
| CN114700081B (en) * | 2022-03-18 | 2023-06-20 | 南京大学 | Preparation and application of perovskite type metal cerium salt with transition metal ion regulation and control performance |
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