CN102698797A - Method for preparing mesoporous solid acid catalyst - Google Patents

Method for preparing mesoporous solid acid catalyst Download PDF

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CN102698797A
CN102698797A CN2012102098611A CN201210209861A CN102698797A CN 102698797 A CN102698797 A CN 102698797A CN 2012102098611 A CN2012102098611 A CN 2012102098611A CN 201210209861 A CN201210209861 A CN 201210209861A CN 102698797 A CN102698797 A CN 102698797A
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acid
catalyst
mesoporous
mesoporous solid
esterification
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杨松
王瑞
薛伟
吴志兵
罗家凤
宋宝安
胡德禹
谭道养
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Guizhou University
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Guizhou University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

The invention discloses a method for preparing mesoporous solid acid catalyst used in esterification deacidification catalytic reaction. The method is characterized in that metal salt belonging to groups of IV B, V B and VI B is taken as raw materials; C12 to C22 fatty acid is taken as modifier; a fatty acid compound is formed through simple heating and stirring; and the catalyst with uniform mesoporouses and a larger surface area is formed through roasting. The method has the advantages of simplicity, low cost and high maneuverability, and can obtain the catalyst with uniform pore diameters. Compared with a catalyst obtained according to the conventional method (direct roasting), the catalyst obtained according to the method has higher catalytic performance, and the catalytic efficiency can be improved by more than 30 percent under the same condition.

Description

A kind of method for preparing the mesoporous solid acid catalyst
Technical field
The present invention relates to the preparation method of the mesoporous solid acid catalyst of a kind of low cost, easy preparation, and catalyst prepares the application of the esterification acid reduction reaction of biodiesel at the high acid value oil plant.
 
Background technology
Be used for the production biodiesel (Fatty acid methyl esters, in raw material FAME), without accurately machined crude oil contain usually certain mass free fatty (Free fatty acid, FFA).And the existence of FFA has limited the use of base catalyst, but FFA can generate FAME through esterification with methyl alcohol under the effect of acidic catalyst.Though FFA and methyl alcohol can be converted into FAME through homogeneous acids such as sulfuric acid, hydrochloric acid under normal pressure, the environmental issue that the equipment corrosion that homogeneous acid caused such as sulfuric acid, hydrochloric acid and follow-up a large amount of wash waters cause can not be ignored.
FFA in the oil plant and methyl alcohol also can generate FAME through catalytic reaction.Therefore, high acid value oil plant and methyl alcohol not only can be made FAME through the catalyzing esterification reaction, also can play the purpose that reduces acid value of oil and fat.Under such technical background, highly active solid acid catalyst has obtained extensive concern.Can find out that through domestic and international reported pertinent literature the high-performance solid acid catalyst that is used for high acid value oil plant catalysis for preparing biodiesel oil should have following characteristic: the acid strength that (1) is high; (2) active sites is stable in reaction system, solubility is little, loss is few; (3) to heat endurance; (4) have the grease of high density, intensity, the active sites that methanol molecules is easy to touch, and do not have mass transfer limit.Therefore; Of the present invention use itself has acidity and solubility is little in methyl alcohol transition metal oxide is catalyst precursor, prepares highly active mesoporous out-phase solid acid catalyst and is used for esterification, the ester exchange reaction of high acid value oil plant through simple chemical property modification approach.
2010, Domen K. seminar of Tokyo Univ Japan reported the solid acid catalyst of two novelties in succession: mesoporous Nb 3W 7Oxide, mesoporous Ta 3W 7The preparation of oxide, sign and application [1,2]Result of study shows: (1) can obtain having the metal oxide of the meso-hole structure of high-specific surface area, pore-size distribution homogeneous under the effect of P-123 structure directing agent; (2) as the W of high valence state + 6Nb with lower valency + 5, Ta + 5Isomorphous substitution takes place, and the surface area that not only contains the W oxide increases, and the increase of active sites density, and generates stronger bronsted acid position; (3) mesoporous Nb 3W 7Oxide, mesoporous Ta 3W 7Oxide in Fu Ke-alkylation, hydrolysis, esterification than niobic acid (Nb 2O 5H 2O), Amberlyst-15, H-ZSM5, Nafion SAC-13 show better catalytic performance; The optimum mole ratio of Nb/W, Ta/W is 3:7 in (4) two kinds of metal oxides.Though more than two catalyst show high catalytic performance, have following drawback: (1) template used dose of P-123 costs an arm and a leg; (2) the catalyst precursor needs after 10 ~ 14 days, just can form mesoporous Nb through roasting 40 ℃ of placements 3W 7Oxide, mesoporous Ta 3W 7Oxide.
Summary of the invention
The objective of the invention is to: prepare the drawback that mesoporous solid acid catalyst cost of material is high, the time is long to the structure directing agent approach; Cost through cheapness and simple approach prepare the mesoporous solid acid catalyst of high catalytic activity; Gained catalyst aperture is evenly distributed; Show high catalytic activity being used for the esterification acid reduction reaction that the high acid value oil plant prepares biodiesel, and it is little to run off.
The present invention relates to a kind of preparation method who is used for the mesoporous solid acid catalyst; Gained catalyst aperture homogeneous; Be particularly useful for the catalyst that the high acid value oil plant prepares esterification acid reduction in the biodiesel processes, it is characterized in that with IV B, V B, VI B family slaine be raw material, through C12 ~ C22 aliphatic acid press mass ratio 1:1 ~ 6 mixed, in 100 ~ 300 ℃ of heated and stirred 0.2 ~ 3h; Be transferred in the crucible while hot then; In 300 ~ 800 ℃ of roasting 1 ~ 10h, cool off, be ground to 100 ~ 200 orders, promptly get mesoporous solid acid catalyst with large surface area.
Relating to IV B, V B, VI B family slaine in the invention is: a kind of, two or more mixtures in titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum, the tungsten slaine; Relate to C in the invention 12~ C 22Aliphatic acid is one or more mixtures in laurate, lauroleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, arachidic acid, peanut monoenoic acid, the erucic acid; Relating to calcination atmosphere in the invention is air stream, nitrogen stream.
Product mesoporous solid acid catalyst of the present invention is mainly used in the esterification acid reduction reaction that the high acid value oil plant prepares biodiesel.
The present invention's scope of asking for protection also relates to the prepared mesoporous solid acid catalyst product of the inventive method, is called for short mesopore oxide.
Be the solid acid catalyst of IV B, V B, the slaine preparation of VI B family equally, through C 12~ C 22Aliphatic acid handles by the inventive method and without fatty acid treatment, its character differs greatly, and the inventor prepares Ta without fatty acid treatment 2O 5-WO 3, Nb 2O 5-WO 3With the present invention through the mesoporous Ta of the acid-treated mesoporous solid acid catalyst of tristearin 3W 7The mesoporous Nb of oxide (preparation method sees embodiment 1) 3W 7Oxide (preparation method sees embodiment 2) is through SEM scanning, Ta 2O 5-WO 3, Nb 2O 5-WO 3Be big bulk, mesoporous Ta 2W 7Oxide, mesoporous Nb 3W 7Oxide particle obviously diminishes (seeing accompanying drawing 1), and is visible, mesoporous Ta 3W 7Fine and close loose structure (seeing accompanying drawing 2) appears in oxide surface
Prepare Ta without fatty acid treatment 2O 5-WO 3, Nb 2O 5-WO 3The preparation method of solid catalyst: the Ta that takes by weighing 0.01 mol 2O 5Or Nb 2O 5(NH with 0.0039mol 4) 10H 2(W 2O 7) 6XH 2O is dissolved in the 36 mL secondary water and stirs and regulate pH5 through oxalic acid, and 80 ℃ of vigorous stirring are spent the night.Mixture places drying box to spend the night for interior 100 ℃ after decompression distillation dewaters.The gained pressed powder is in 500 ℃ of roasting 300 min (still air, 1 ℃/min), obtain Ta 2O 5-WO 3And Nb 2O 5-WO 3Solid catalyst
Ta 2O 5-WO 3, Nb 2O 5-WO 3With mesoporous Ta 2W 7Oxide, mesoporous Nb 3W 7Oxide not only SEM characterizes difference, and N 2The adsorption-desorption characterization result shows, Nb 2O 5-WO 3, Ta 2O 5-WO 3Specific area only be respectively 0.35 and 0.81 m 2/ g, and mesoporous Ta 3W 7Oxide (stearic acid, 1 ℃/min) and mesoporous Nb 3W 7(specific area of stearic acid, 1 ℃/min) is respectively 107.49 m to oxide 2/ g and 66.12m 2/ g.Visible by Fig. 3, mesoporous Ta 3W 7Oxide (stearic acid, 1 ℃/min) and mesoporous Nb 3W 7Oxide (the even aperture distribution of stearic acid, 1 ℃/min).
Above-mentioned four catalyst: Ta 2O 5-WO 3, Nb 2O 5-WO 3, mesoporous Ta 3W 7Oxide (stearic acid, 1 ℃/min) and mesoporous Nb 3W 7(stearic acid, 1 ℃/min) are under equal catalytic condition (under catalyst amount 5 wt.%, the molar ratio of methanol to oil 8:1 condition respectively at 65 ℃, 180 ℃ reaction 1 h) for oxide; To acid number is that the Jatropha curcas oil of 22.17 mg KOH/g carries out esterification acid reduction, and the conversion ratio of four catalyst is respectively 36.76%, 33.56%, 66.49%, 70.38%.
It is above-mentioned that (stearic acid is meant through the acid-treated mesoporous solid acid catalyst of tristearin the 1 ℃/min of programming rate during processing in the bracket of stearic acid, 1 ℃/min).
Description of drawings:
Fig. 1, Ta 2O 5-WO 3, Nb 2O 5-WO 3, mesoporous Ta 3W 7Oxide, mesoporous Nb 3W 7The flying-spot microscope figure of oxide can know from figure, without the Ta of fatty acid treatment 2O 5-WO 3Solid catalyst (upper left) and the stearic acid-treated mesoporous Ta of warp 3W 7Oxide (left side down) reaches the Nb without fatty acid treatment 2O 5-WO 3Solid catalyst (upper right) and the stearic acid-treated mesoporous Nb of warp 3W 7Oxide (bottom right) compares, through stearic acid-treated mesoporous Ta 2W 7Oxide, mesoporous Nb 3W 7Oxide particle obviously diminishes.
Fig. 2 is mesoporous Ta 3W 7The oxide transmission electron microscope picture can be known mesoporous Ta from figure 3W 7Fine and close loose structure appears in oxide surface.
Fig. 3 is mesoporous Nb 3W 7Oxide (stearic acid, 1 ℃/min), mesoporous Ta 3W 7(the BJH graph of pore diameter distribution of stearic acid, 1 ℃/min) can be known mesoporous Ta from figure to oxide 3W 7Oxide and mesoporous Nb 3W 7Oxide aperture is evenly distributed.
The specific embodiment
Embodiment one: mesoporous Ta 3W 7The preparation of oxide and the catalysis of high acid value oil plant fall acid application
Take by weighing 0.3 mol TaCl 5With 0.7mol WCl 6Mix (TaCl with 358.65 g stearic acid 5, WCl 6Be respectively 1:5,1:6 with the stearic acid mol ratio; Two kinds of metal salt mixture and stearic acid mass ratio are 1:1), stir 3 h in 100 ℃, while hot the gained mixture is poured in the porcelain boat; The cooling back is that 40 L/h, 1 ℃/min are warming up to 600 ℃ as for the inherent air mass flow of tube furnace; When temperature rises to 600 ℃, stop bubbling air, and at 600 ℃ of insulation 300 min.Above-mentioned oxide is taken out while hot, be enclosed within the drier, cooling is ground, and is subsequent use, the mesoporous Ta of gained 3W 7Oxide flying-spot microscope figure such as Fig. 1 left side figure below.The gained specific surface area of catalyst is 167.49 m 2/ g.
With the 20g acid number is that the Jatropha curcas oil of 9.34 mg KOH/g is raw material, at catalyst amount 5 wt.%, and alcohol/molar equivalent: 10:1, the conditions of 180 ℃ of reaction 2 h think that catalytic conversion is 77.62%.The acid of high acid value Jatropha curcas oil is reduced to 2.09 mgKOH/g by value under this catalytic reaction condition.
Will through the Jatropha curcas grease of preparatory esterification treatment through filter, drying under reduced pressure; With methanol mixed (mol ratio 1:8); Through 5%CaO catalytic reaction (65 ℃, 2h); Products therefrom through suction filtration, recovered under reduced pressure methyl alcohol, cool off, leave standstill, separation of glycerin, gained biodiesel FAME content is 96.93%, biodiesel production rate is 89.14% in the whole technology.
Embodiment two: mesoporous Nb 3W 7The preparation of oxide and in the application of biodiesel catalytic preparation
Take by weighing 0.6 mol NbCl 5With 1.4 mol WCl 6Mix (NbCl with 162.36 g stearic acid 5, WCl 6Be respectively 1:1,1:6 with the stearic acid mol ratio); Stir 0.2 h in 200 ℃; While hot the gained mixture is poured in the porcelain boat, the cooling back is that 40 L/h, 4 ℃/min are warming up to 800 ℃ as for the inherent air mass flow of tube furnace, when temperature rises to 800 ℃; Stop bubbling air, and at 800 ℃ of insulation 1 h.Above-mentioned oxide is taken out while hot, be enclosed within the drier, cooling is ground, and is subsequent use, the mesoporous Nb of gained 3W 7Oxide flying-spot microscope figure such as Fig. 1 bottom-right graph.The gained specific surface area of catalyst is 66.12m 2/ g.
With the 20g acid number is that the Euphorbia lathyris oil of 9.17 mg KOH/g is raw material, at catalyst amount 5 wt.%, and alcohol/molar equivalent: 10:1, the conditions of 180 ℃ of reaction 2 h think that catalytic conversion is 81.34%.The acid of high acid value Jatropha curcas oil is reduced to 1.73 mgKOH/g by value under this catalytic reaction condition.
Will through the Euphorbia lathyris grease of preparatory esterification treatment through filter, drying under reduced pressure; With methanol mixed (mol ratio 1:8); Through 5%CaO catalytic reaction (65 ℃, 2h); Products therefrom through suction filtration, recovered under reduced pressure methyl alcohol, cool off, leave standstill, separation of glycerin, gained biodiesel FAME content is 97.11%, whole process yield is 87.21%.
Embodiment three: mesoporous MoO 3Preparation and in the application of biodiesel catalytic preparation
Take by weighing 1 mol (NH 4) 6Mo 7O 244H 2O mixes ((NH with 206 g laurate 4) 6Mo 7O 244H 2O and laurate mol ratio are respectively 1:1); Stir 0.2 h in 200 ℃; While hot the gained mixture is poured in the porcelain boat, the cooling back is that 40 L/h, 4 ℃/min are warming up to 500 ℃ as for the inherent air mass flow of tube furnace, when temperature rises to 500 ℃; Stop bubbling air, and at 500 ℃ of insulation 10 h.Above-mentioned oxide is taken out while hot, be enclosed within the drier, cooling is ground, and is subsequent use.
With the 20g acid number is that the Chinese tallow of 4.89 mg KOH/g is a raw material, at catalyst amount 5 wt.%, and alcohol/molar equivalent: 10:1, the conditions of 180 ℃ of reaction 2 h think that catalytic conversion is 81.34%.The acid of high acid value Chinese tallow is reduced to 1.08 mgKOH/g by value under this catalytic reaction condition.
Will through the Chinese tallow tree grease of preparatory esterification treatment through filter, drying under reduced pressure; With methanol mixed (mol ratio 1:8); Through 5%CaO catalytic reaction (65 ℃, 2h); Products therefrom through suction filtration, recovered under reduced pressure methyl alcohol, cool off, leave standstill, separation of glycerin, gained biodiesel FAME content is 98.76%, whole process yield is 86.20%.
Embodiment four: the preparation of mesoporous Mo/Ti/W oxide and in the application of biodiesel catalytic preparation
Take by weighing MoS 2, Ti (NO 3) 4, WCl 6Each 50g; Each 50g mixes with oleic acid/linoleic acid/erucic acid/palmitic acid, in 260 ℃ of stirring 0.2 h, while hot the gained mixture is poured in the porcelain boat; The cooling back is that 40 L/h, 10 ℃/min are warming up to 700 ℃ as for the inherent air mass flow of tube furnace; When temperature rises to 700 ℃, stop bubbling air, and at 700 ℃ of insulation 10 h.Above-mentioned oxide is taken out while hot, be enclosed within the drier, cooling is ground, and is subsequent use.
With the 20g acid number is that the Euphorbia lathyris oil of 9.17 mg KOH/g is raw material, at catalyst amount 5 wt.%, and alcohol/molar equivalent: 10:1, the conditions of 180 ℃ of reaction 2 h think that catalytic conversion is 82.81%.The acid of high acid value Jatropha curcas oil is reduced to 1.44 mgKOH/g by value under this catalytic reaction condition.
Will through the Euphorbia lathyris grease of preparatory esterification treatment through filter, drying under reduced pressure; With methanol mixed (mol ratio 1:8); Through 5%CaO catalytic reaction (65 ℃, 2h); Products therefrom through suction filtration, recovered under reduced pressure methyl alcohol, cool off, leave standstill, separation of glycerin, gained biodiesel FAME content is 96.16%, whole process yield is 87.60%.
List of references:
[1]?Tagusagawa,?C.;?Takagaki,?A.;?Iguchi,?A.;?Takanabe,?K.;?Kondo,?J.?N.;?Ebitani,?K.;?Tatsumi,?T.;?Domen,?K.?Synthesis?and?Characterization?of?Mesoporous?Ta-W?Oxides?as?Strong?Solid?Acid?Catalysts?[J].? Chem.?Mater.,? 2010,?22(10):?3072-3078.
[2]?Tagusagawa,?C.;?Takagaki,?A.;?Iguchi,?A.;?Takanabe,?K.;?Kondo,?J.?N.;?Ebitani,?K.;?Hayashi,?S.;?Tatsumi,?T.;?Domen,?K.?Highly?Active?Mesoporous?Nb–W?Oxide?Solid-
Acid?Catalyst?[J].? Angew?Chem.?Int.?Edit.,? 2010,?49(6):?1128-1132.

Claims (6)

1. preparation method who is used for the mesoporous solid acid catalyst of catalyzing esterification; It is characterized in that with IV B, V B, VI B family slaine be raw material, through C12 ~ C22 aliphatic acid press mass ratio 1:1 ~ 1:6 mixed, in 100 ~ 260 ℃ of heated and stirred 0.2 ~ 3h, be transferred in the crucible while hot then; In 500 ~ 800 ℃ of roasting 1 ~ 10h; Cool off, be ground to 100 ~ 200 orders, promptly get mesoporous solid acid catalyst, be called for short mesopore oxide with large surface area.
2. according to right 1 described a kind of preparation method who is used for the mesoporous solid acid catalyst of catalyzing esterification, it is characterized in that IV B, V B, VI B family slaine are: a kind of, two or more mixture in the powder of nitrate, hydrochloride, sulfate, ammonium salt.
3. according to right 1 described a kind of preparation method who is used for the mesoporous solid acid catalyst of catalyzing esterification, it is characterized in that C 12~ C 22Aliphatic acid is a kind of, two or more fatty acid mixeds in laurate, lauroleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, arachidic acid, peanut monoenoic acid, the erucic acid.
4. according to right 1 described a kind of preparation method who is used for the mesoporous solid acid catalyst of catalyzing esterification, the atmosphere that it is characterized in that roasting is air stream, nitrogen stream.
5. according to right 1 described a kind of application that is used for the mesoporous solid acid catalyst of catalyzing esterification, its characteristic is being used for the esterification acid reduction reaction that the high acid value oil plant prepares biodiesel.
6. the preparation method of a kind of mesoporous solid acid catalyst that is used for catalyzing esterification as claimed in claim 1 is prepared, is used for the mesoporous solid acid catalyst that the high acid value oil plant prepares the esterification acid reduction reaction of biodiesel.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102850303A (en) * 2012-10-16 2013-01-02 贵州大学 New application and using method of mesoporous solid acid catalyst
CN103990449A (en) * 2014-05-30 2014-08-20 贵州大学 Preparation of mesoporous Ti-Mo solid acid catalyst and application of catalyst

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CAIO TAGUSAGAWA ET AL.: "Highly Active Mesoporous Nb–W Oxide Solid-Acid Catalyst", 《ANGEW. CHEM.》 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102850303A (en) * 2012-10-16 2013-01-02 贵州大学 New application and using method of mesoporous solid acid catalyst
CN102850303B (en) * 2012-10-16 2014-07-09 贵州大学 New application and using method of mesoporous solid acid catalyst
CN103990449A (en) * 2014-05-30 2014-08-20 贵州大学 Preparation of mesoporous Ti-Mo solid acid catalyst and application of catalyst

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Application publication date: 20121003