CN102309967B - Catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation and preparation method thereof - Google Patents
Catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation, and the catalyst comprises Fe2O3 used as a substrate, SiO2 used as a structure auxiliary agent, and Zn, Cu and K as chemical auxiliary agents; based on the mass of Fe2O3, the mass contents of the Zn, Cu and K chemical auxiliary agents and the SiO2 structure auxiliary agent are respectively: 1-10% of Zn, 1-10% of Cu, 0.3-7% of K, 3-25% of SiO2; The catalyst of the invention has high reactive activity for CO2 hydrogenation and hydrocarbon generation and high C2+ hydrocarbon selectivity at a low reaction temperature; and with the great reduction of the reaction temperature, the catalyst facilitates the prolongation of the service life of the reaction device.
Description
(1) technical field
The present invention relates to a kind of chemical catalyst, particularly a kind of CO
2Synthetic hydrocarbon catalyst of catalytic hydrogenation and preparation method thereof.
(2) background technology
Hydrocarbon is a kind of organic compound that only is comprised of carbon and two kinds of elements of hydrogen, is called again hydrocarbon, and carbon atom is connected to each other the molecular skeleton that forms carbochain or carbocyclic ring shape in hydrocarbon molecule, and the hydrogen atom of some is connected on carbon atom.Hydrocarbon is important industrial chemicals and energy resources, as industrial chemicals, is the synthesis material of various plastics and chemical fibre as ethene and propylene; As the energy, gasoline, diesel oil, liquefied gas etc. are the necessitys of daily life and production.At present, hydrocarbon can be produced by natural gas separation, petroleum refining and coal carbonization, and wherein crude refining is main production ways.In recent years, due to former oil measure adopt than decline, the worry of crude supply prospect has been caused the crude oil price continuous rise, increased the cost of hydrocarbon manufacturing enterprise, have influence on the stable development of down-stream enterprise, need to set up new hydrocarbon production line.
Carbon dioxide (CO
2) be the end product after carbon and carbon compound combustion oxidation, have aboundresources, characteristics cheap and easy to get, exist natural CO
2The gas field, many industrial process also produce a large amount of CO
2CO
2Maximum carbon resource storehouse, at occurring in nature with CO
2The carbon content that form exists is about 10
16Ton, its phosphorus content are 10 times [Zhejiang Educational College's journal, 2005 (3) 53.] of oil, coal, natural gas three large energy phosphorus content.If with abundant CO
2As the raw material of hydrocarbon processed, not only can satisfying the market to the very big demand of hydrocarbon, can also effectively reduce CO
2Discharge capacity, be conducive to reduce the CO in atmosphere
2Concentration is controlled greenhouse effects to the adverse effect of weather.
Studies show that and pass through CO
2Catalytic hydrogenation can be realized the synthetic of hydrocarbon.Rope palm bosom waits [Journal of Molecular Catalysis, 15 (2001) 91.] with Al
2O
3, TiO
2, ZrO
2For carrier, the preparation of employing infusion process support iron catalyst, the reaction result under 350 ℃ shows that the M-O key of carrier is longer, and surperficial Fe-O atomic distance is also longer, and the best reduction temperature of catalyst is lower, thereby catalytic activity is better, CO
2Conversion ratio is higher, C
2-C
5Hydrocarbon selectively higher, and CO and CH
4Selectively lower; Think Zero-valent Iron and the undersaturated Fe of coordination that the surface exists
2+/ Fe
3+The synergy of species is that it shows highly active essence, Fe
2+/ Fe
3+Species are to CO
2It is essential that hydrogenation generates CO, and is conducive to CH
4Or C
2+ 0Generation, the having of Zero-valent Iron is beneficial to the CO hydrogenation and generates low-carbon alkene.Han Yizhuo etc. [coal conversion, 29 (2006) 79.] find for CO under the reaction temperature of 340 ℃
2Hydrogenation reaction, the Fe-Zn-Zr that adopts the coprecipitation preparation is during as catalyst, and the hydro carbons of generation is mainly methane; Utilize the physical mixture of Fe-Zn-Zr/HY molecular sieve as catalyst, the selectively significantly reduction of methane, C
2 +Selectively significantly improving of hydrocarbon, especially isomery C
4, C
5Hydrocarbon selectively risen to 58.75% by 0.5%.Ando[Catal.Today, 45 (1998) 229.] etc. utilize co-precipitation Fe-Cu catalyst to carry out CO under 400 ℃
2Hydropyrolysis experiment, C
2 +The productive rate of hydrocarbon is higher than CH
4
Above-mentioned CO
2The synthetic hydrocarbon of catalytic hydrogenation is all to carry out CO at higher temperature
2Hydrogenation reaction, reason is high temperature is conducive to vapour transformationreation against the current on thermodynamics carrying out (shown in (1)) [J.M.Smith, H.C.van Ness, Introduction to Chemical Engineering Thermodynamics, 3rd ed., McGraw Hill, Tokyo, 1975, P390.], the CO that generates again with H
2React and acquisition hydrocarbon [J.Catal.104 (1987) 339.Nature 327 (1987) 506.Appl.Catal.58 (1990) 255.J.Phys.Chem.95 (1991) 6341.Catal.Lett.9 (1991) 415.].
CO
2+ H
2→ CO+H
2O formula (1)
In order to develop the CO of excellent performance
2The Hydrogenation hydrocarbon catalyst, catalyst reaction performance evaluation is carried out in the present invention's selection (230 ℃) at low temperatures, under this condition, to CO
2Activation and the hydrogenation reaction reactivity worth that mainly depends on catalyst self, be conducive to determine that suitable catalyst forms, then, then the optimization by reaction condition, can realize CO
2Efficient Conversion to hydrocarbon.
(3) summary of the invention
The object of the invention is to provide a kind of CO
2Synthetic hydrocarbon catalyst of catalytic hydrogenation and preparation method thereof, catalyst reaction good stability of the present invention, C
2+ hydrocarbon-selective is high, and method for preparing catalyst is easy to carry out large-scale production.
The technical solution used in the present invention is:
A kind of CO
2Catalytic hydrogenation synthesizes hydrocarbon catalyst, and described catalyst is with Fe
2O
3Be matrix, with SiO
2Be structural promoter, form take Zn, Cu and K as chemical assistant; Based on described Fe
2O
3Quality, described Zn, Cu and K chemical assistant and SiO
2The structural promoter mass content is respectively: Zn is 1～10%, Cu is 1～10%, K is 0.3～7%, SiO
2Be 3～25%.
Further, described CO
2The synthetic hydrocarbon catalyst of catalytic hydrogenation is based on described Fe
2O
3Quality, preferred described Zn, Cu and K chemical assistant and SiO
2The structural promoter mass content is respectively: Zn is 6～9%, Cu is 2～8%, K is 1～5%, SiO
2Be 5～20%.
A kind ofly prepare CO of the present invention
2The method of the synthetic hydrocarbon catalyst of catalytic hydrogenation is: (1) mixes ferric nitrate and potassium silicate, obtains mixed liquor; The mass ratio that feeds intake of described ferric nitrate and potassium silicate is 1: 0.025～0.212; Described ferric nitrate adds with the form of mass concentration 20～40% iron nitrate aqueous solutions, and described potassium silicate adds with the form of mass concentration 5～55% potassium silicate aqueous solutions; (2) mixed liquor and mass concentration 20～45% ammonium carbonate solutions with step (1) preparation pump into sedimentation basin simultaneously, co-precipitation 0.5～1.5h under 40～70 ℃, pH=6～8 conditions, precipitation finishes to precipitate with the distilled water washing, filters, and discards filtrate and obtains filter cake; In described 20～45% ammonium carbonate solutions, ammonium carbonate and ferric nitrate mass ratio are 1: 2.1～2.4; (3) nitrate and/or the carbonate mixed aqueous solution with zinc, copper and potassium joins in the filter cake of step (2) acquisition, stir dipping 30～60min, obtain slurries, with slurries in 120 ℃ of dryings or 200～250 ℃ of spray-dryings, at 400 ℃ of roasting 12～20h, obtain CO again
2Catalytic hydrogenation synthesizes hydrocarbon catalyst; The nitrate of described zinc, copper and potassium and/or the mass concentration of carbonate aqueous solution are independently 0.1～50% separately; The nitrate of described ferric nitrate and zinc, copper and potassium and/or the carbonate mass ratio that feeds intake is 1: 0.006～0.096: 0.006～0.098: 0.002～0.06.
Further, in described step (1) mass ratio that feeds intake of ferric nitrate and potassium silicate be preferably 1: 0.032～0.17.
Further, in described step (2) in 20～45% ammonium carbonate solutions ammonium carbonate and ferric nitrate mass ratio be preferably 1: 2.2～2.3.
Further, in described step (3) nitrate of ferric nitrate and zinc, copper and potassium and/or carbonate feed intake mass ratio be preferably 1: 0.038～0.086: 0.013～0.078: 0.006～0.043.
SiO of the present invention
2Be structural promoter, be used for improving Fe
2O
3Decentralization and mechanical strength, be used for improving catalyst activity take Zn, Cu and K as chemical assistant.
CO of the present invention
2The preparation method of the synthetic hydrocarbon catalyst of catalytic hydrogenation drops into the Fe (NO of 1 unit mass
3)
39H
2O can obtain the Fe of 0.2 unit mass
2O
3, drop into the potassium silicate water glass of 1 unit mass, can obtain the SiO of 0.31 unit mass
2, drop into the Zn (NO of 1 unit mass
3)
26H
2O can obtain the Zn of 0.22 unit mass, drops into the Cu (NO of 1 unit mass
3)
23H
2O can obtain the Cu of 0.26 unit mass, drops into the KNO of 1 unit mass
3Or K
2CO
3, can obtain the K of 0.39 or 0.14 unit mass.
Compared with prior art, catalyst of the present invention has high CO than under low reaction temperatures
2Be hydrogenated into the reactivity of hydrocarbon and high C
2+ hydrocarbon-selective, the significantly reduction of simultaneous reactions temperature is conducive to extend service life of reaction unit.
(4) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1
(1) with 8.34kg Fe (NO
3)
39H
2O is dissolved in 15L distilled water, and the 0.529kg potassium silicate water glass is dissolved in 2L distilled water, then is merged into mixed liquor;
(2) with 3.78kg (NH
4)
2CO
3Be dissolved in 14L distilled water, the mixed liquor of ammonium carbonate solution and step (1) preparation is pumped into sedimentation basin simultaneously, co-precipitation 1h, precipitation temperature are 45 ± 1 ℃, and the pH value is controlled at 6.3 ± 0.2; Precipitation finishes, and the gained precipitation discards filtrate with distilled water washing, filtration, obtains filter cake 20.0kg;
(3) with 0.605kg Zn (NO
3)
36H
2O, 0.374kg Cu (NO
3)
23H
2O and 0.129kg KNO
3Mixing is dissolved in 1.5L distilled water, obtains the nitrate mixed liquor of zinc, copper and potassium; The nitrate mixed liquor of above-mentioned zinc, copper and potassium is joined in the filter cake of step (2) acquisition, stirred dipping 60 minutes, obtain slurries, slurries are put into baking oven in 120 ℃ of dryings, then obtain catalyst 2.15kg, called after catalyst 1 at 400 ℃ of roasting 15h
#, this catalyst Z n, Cu and K chemical assistant and SiO
2Structural promoter is with respect to Fe
2O
3Mass content be: Zn:8%, Cu:6%, K:3%, SiO
2: 10%.
(4) activity rating: catalyst that step (3) is prepared with desktop electric tablet press machine (DY-30, Tianjin device high and new technology company of section) compressing tablet, be broken into again the particle of particle diameter 80～150 μ m with agate mortar, get 1.0g catalyst 1
#Particle is put into fixed bed reactors (ZJGD-XJ2009-041, Tianjin roc Xiang Science and Technology Ltd.) and is carried out activity rating by following reaction condition, reaction temperature: 230 ℃, and reaction pressure: 1.6MPa, reacting gas forms: H
2/ CO
2=2, reaction gas flow: 6.0Lh
-1G-cat.
-1, the results are shown in Table 1.
Embodiment 2
(1) with 8.34kg Fe (NO
3)
39H
2O is dissolved in 20L distilled water, and the 0.528kg potassium silicate water glass is dissolved in 3.9L distilled water, then is merged into mixed liquor;
(2) with 3.78kg (NH
4)
2CO
3Be dissolved in 14L distilled water, the mixed liquor of ammonium carbonate solution and step (1) preparation is pumped into sedimentation basin simultaneously, co-precipitation 0.8h, precipitation temperature are 50 ± 1 ℃, and the pH value is controlled at 6.8 ± 0.2; Precipitation finishes, and the gained precipitation discards filtrate with distilled water washing, filtration, obtains filter cake 13.2kg;
(3) with 0.453kg Zn (NO
3)
36H
2O, 0.498kg Cu (NO
3)
23H
2O and 0.172kg KNO
3Mixing is dissolved in 3L distilled water, obtains the nitrate mixed liquor of zinc, copper and potassium; The nitrate mixed liquor of above-mentioned zinc, copper and potassium is joined in the filter cake of step (2) acquisition, stirred dipping 50 minutes, obtain slurries, slurries are put into baking oven in 120 ℃ of dryings, then obtain catalyst 2.12kg, called after catalyst 2 at 400 ℃ of roasting 20h
#, this catalyst Z n, Cu and K chemical assistant and SiO
2Structural promoter is with respect to Fe
2O
3Mass content be: Zn:6%, Cu:8%, K:4%, SiO
2: 10%.
(4) activity rating: the activity rating condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
(1) with 15.2kg Fe (NO
3)
39H
2O is dissolved in 35L distilled water, and the 1.45kg potassium silicate water glass is dissolved in 15L distilled water, then is merged into mixed liquor;
(2) with 6.85kg (NH
4)
2CO
3Be dissolved in 25L distilled water, the mixed liquor of ammonium carbonate solution and step (1) preparation is pumped into sedimentation basin simultaneously, co-precipitation 1.5h, precipitation temperature are 55 ± 1 ℃, and the pH value is controlled at 7.1 ± 0.2; Precipitation finishes, and the gained precipitation discards filtrate with distilled water washing, filtration, obtains filter cake 37.6kg;
(3) with 0.824kg Zn (NO
3)
36H
2O, 0.227kg Cu (NO
3)
23H
2O and 0.156kg KNO
3Mixing is dissolved in 60L distilled water, obtains the nitrate mixed liquor of zinc, copper and potassium; The nitrate mixed liquor of zinc, copper and potassium is joined in the filter cake of step (2) acquisition, stirred dipping 30 minutes, obtain slurries, the recycling spray dryer is in 200 ℃ of dryings, then at 400 ℃ of roasting 12h acquisition catalyst 4.2kg, called after catalyst 3
#, this catalyst Z n, Cu and K chemical assistant and SiO
2Structural promoter is with respect to Fe
2O
3Mass content be: Zn:6%, Cu:2%, K:2%, SiO
2: 15%.
(4) activity rating: the activity rating condition the results are shown in Table 1 with embodiment 1.
Embodiment 4
(1) with 8.34kg Fe (NO
3)
39H
2O is dissolved in 20L distilled water, and the 0.264kg potassium silicate water glass is dissolved in 2L distilled water, then is merged into mixed liquor;
(2) with 3.78kg (NH
4)
2CO
3Be dissolved in 14L distilled water, the mixed liquor of ammonium carbonate solution and step (1) preparation is pumped into sedimentation basin simultaneously, co-precipitation 0.8h, precipitation temperature are 60 ± 1 ℃, and the pH value is controlled at 7.7 ± 0.2; Precipitation finishes, and the gained precipitation discards filtrate with distilled water washing, filtration, obtains filter cake 15kg;
(3) with 0.302kg Zn (NO
3)
36H
2O, 0.249kg Cu (NO
3)
23H
2O and 0.043kg KNO
3Mixing is dissolved in 1L distilled water, obtains the nitrate mixed liquor of zinc, copper and potassium; The nitrate mixed liquor of zinc, copper and potassium is joined in the filter cake of step (2) acquisition, stirred dipping 60 minutes, obtain slurries, slurries are put into baking oven in 120 ℃ of dryings, then obtain catalyst 1.9kg, called after catalyst 4 at 400 ℃ of roasting 20h
#, this catalyst Z n, Cu and K chemical assistant and SiO
2Structural promoter is with respect to Fe
2O
3Mass content be: Zn:4%, Cu:4%, K:1%, SiO
2: 5%.
(4) activity rating: the activity rating condition the results are shown in Table 1 with embodiment 1.
Embodiment 5
(1) with 15.2kg Fe (NO
3)
39H
2O is dissolved in 35L distilled water, and the 1.92kg potassium silicate water glass is dissolved in 5L distilled water, then is merged into mixed liquor;
(2) with 6.85kg (NH
4)
2CO
3Be dissolved in 25L distilled water, the mixed liquor of ammonium carbonate solution and step (1) preparation is pumped into sedimentation basin simultaneously, co-precipitation 0.5h, precipitation temperature are 65 ± 1 ℃, and the pH value is controlled at 7.4 ± 0.2; Precipitation finishes, and the gained precipitation discards filtrate with distilled water washing, filtration, obtains filter cake 25.3kg;
(3) with 1.1kg Zn (NO
3)
36H
2O, 0.453kg Cu (NO
3)
23H
2O and 0.39kg KNO
3Mixing is dissolved in 80L distilled water, obtains the nitrate mixed liquor of zinc, copper and potassium; The nitrate mixed liquor of zinc, copper and potassium is joined in the filter cake of step (2) acquisition, stirred dipping 40 minutes, obtain slurries, the recycling spray dryer is in 230 ℃ of dryings, then at 400 ℃ of roasting 16h acquisition catalyst 4.5kg, called after catalyst 5
#, this catalyst Z n, Cu and K chemical assistant and SiO
2Structural promoter is with respect to Fe
2O
3Mass content be: Zn:8%, Cu:4%, K:5%, SiO
2: 20%.
(4) activity rating: the activity rating condition the results are shown in Table 1 with embodiment 1.
Catalyst reaction performance in table 1 embodiment
Claims (4)
1. CO
2Catalytic hydrogenation synthesizes hydrocarbon catalyst, it is characterized in that described catalyst is with Fe
2O
3Be matrix, with SiO
2Be structural promoter, form take Zn, Cu and K as chemical assistant; Based on described Fe
2O
3Quality, described Zn, Cu and K chemical assistant and SiO
2The structural promoter mass content is respectively: Zn is 6 ~ 9%, Cu is 2 ~ 8%, K is 1 ~ 5%, SiO
2Be 5 ~ 20%.
2. CO as claimed in claim 1
2The preparation method of the synthetic hydrocarbon catalyst of catalytic hydrogenation is characterized in that described method is: (1) mixes ferric nitrate and potassium silicate, obtains mixed liquor; The mass ratio that feeds intake of described ferric nitrate and potassium silicate is 1:0.025 ~ 0.212; Described ferric nitrate adds with the form of mass concentration 20 ~ 40% iron nitrate aqueous solutions, and described potassium silicate adds with the form of mass concentration 5 ~ 55% potassium silicate aqueous solutions; (2) mixed liquor and mass concentration 20 ~ 45% ammonium carbonate solutions with step (1) preparation pump into sedimentation basin simultaneously, co-precipitation 0.5 ~ 1.5 h under 40 ~ 70 ℃, pH=6 ~ 8 conditions, precipitation finishes to precipitate with the distilled water washing, filters, and discards filtrate and obtains filter cake; In described 20 ~ 45% ammonium carbonate solutions, ammonium carbonate and ferric nitrate mass ratio are 1:2.1 ~ 2.4; (3) nitrate and/or the carbonate mixed aqueous solution with zinc, copper and potassium joins in the filter cake of step (2) acquisition, stir dipping 30 ~ 60min, obtain slurries, with slurries in 120 ℃ of dryings or 200 ~ 250 ℃ of spray-dryings, at 400 ℃ of roasting 12 ~ 20h, obtain CO again
2Catalytic hydrogenation synthesizes hydrocarbon catalyst; The nitrate of described zinc, copper and potassium and/or the mass concentration of carbonate aqueous solution are independently 0.1 ~ 50% separately; The nitrate of described ferric nitrate and zinc, copper and potassium and/or the carbonate mass ratio that feeds intake is 1:0.038 ~ 0.086:0.013 ~ 0.078:0.006 ~ 0.043.
3. CO as claimed in claim 2
2The preparation method of the synthetic hydrocarbon catalyst of catalytic hydrogenation is characterized in that the mass ratio that feeds intake of the middle ferric nitrate of described step (1) and potassium silicate is 1:0.032 ~ 0.17.
4. CO as claimed in claim 2
2The preparation method of the synthetic hydrocarbon catalyst of catalytic hydrogenation is characterized in that in described step (2) that in 20 ~ 45% ammonium carbonate solutions, ammonium carbonate and ferric nitrate mass ratio are 1:2.2 ~ 2.3.
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| WO2015007230A1 (en) | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | Iron-based hydrogenation catalyst and applications thereof |
| CN105833874A (en) * | 2016-04-20 | 2016-08-10 | 北京石油化工学院 | Loaded type magnetic carrier Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN107497437B (en) * | 2017-09-11 | 2020-05-08 | 华东理工大学 | For CO2Iron-based catalyst for preparing low-carbon olefin by hydrogenation and application thereof |
| CN108421547B (en) * | 2018-01-30 | 2020-12-01 | 浙江工业大学 | Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof |
| CN113117683A (en) * | 2021-04-16 | 2021-07-16 | 郑州大学 | Supported catalyst and preparation method thereof |
| CN113318744A (en) * | 2021-06-23 | 2021-08-31 | 浙江工业大学 | Iron-based catalyst with high hydrocarbon selectivity and preparation method and application thereof |
| CN115845859A (en) * | 2022-11-25 | 2023-03-28 | 金宏气体股份有限公司 | Modified iron-based catalyst for synthesizing alpha-olefin by carbon dioxide hydrogenation and preparation method thereof |
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| CN1562471A (en) * | 2004-03-29 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Iron base catalyzer through Fischer-Tropsch synthesis and preparation method |
| CN1714933A (en) * | 2004-06-28 | 2006-01-04 | 华东理工大学 | Process for preparing synthetic hydrocarbon catalyst of synthetic gas |
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| CN1562471A (en) * | 2004-03-29 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Iron base catalyzer through Fischer-Tropsch synthesis and preparation method |
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