CN101294094A - Method for preparing biological diesel oil by using nano-solid heteropoly acid, heteropolybase catalyst - Google Patents

Method for preparing biological diesel oil by using nano-solid heteropoly acid, heteropolybase catalyst Download PDF

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CN101294094A
CN101294094A CNA2007100520650A CN200710052065A CN101294094A CN 101294094 A CN101294094 A CN 101294094A CN A2007100520650 A CNA2007100520650 A CN A2007100520650A CN 200710052065 A CN200710052065 A CN 200710052065A CN 101294094 A CN101294094 A CN 101294094A
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catalyst
catalyzer
reaction
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bio
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韩鹤友
郑新生
王运
文利柏
胡圣扬
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Huazhong Agricultural University
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Huazhong Agricultural 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The invention belongs to the field of bio-diesel preparation technology and discloses a novel method for producing bio-diesel by using nanosolid heteropolyacid and heteropolybase catalyst. The method comprises the following steps: adding raw material oil and methanol in a reaction system, and catalyzing with a catalyst with a diameter particle of 25 to 50 nm. The catalyst is selected from one or the combination of ammonium persulfate/zirconium dioxide-titanium dioxide, ammonium persulfate/gamma-aluminum oxide-silicon oxide, W-Si heteropolyacid, Mo-V-P heteropolyacid, Co-Mo-Al-Mg heteropolybase or potassium carbonate/gamma-aluminum oxide, potassium fluoride/calcium oxide, potassium fluoride/calcium oxide-magnesium oxide. The amount of the catalyst is 1 to 6% the weight of the raw material oil, the alcohol/oil molar ratio is (6 to 48):1, and the reaction is carried out at a temperature of 60 to 90 DEG C and under normal pressure for 1 to 10 h to obtain neutral bio-diesel after separating the glycerol and distilling the methanol. In the method, the remarkable advantages of the nanosolid catalyst are exerted fully, and the post-treatment process of the bio-diesel has simple operation and high yield and meets the requirement for green production.

Description

Utilize nano-solid heteropoly acid, heteropolybase catalyst production method of bio-diesel oil
Technical field
The invention belongs to technical field of biodiesel preparation, be specifically related to utilize the method for nano-solid heteropoly acid, heteropolybase catalyst catalyzed production biodiesel.
Background technology
Because fossil oil faces exhaustion, oil price is high, and diesel-fuel consumption enlarges day by day, is the important channel that solves oil shortage with production biofuel such as oil crops and animal grease therefore.Biofuel is not only a kind of renewable energy source as a kind of substitute energy, but also is a kind of environment amenable " green energy resource ".Decision production of biodiesel technology, operational path, production cost mainly be catalyzer.At present, the suitability for industrialized production biofuel is widely used is that liquid acid (vitriol oil), liquid caustic soda (KOH, NaOH) are made catalyzer.Use the acid catalyzed main drawback of liquid to be: speed of reaction is slow, and the acid consumption is big, and it is difficult to separate, and equipment is perishable, and product needed neutralization, washing produce a large amount of waste water.Use the catalytic main drawback of liquid caustic soda to be: the content requirement to free lipid acid and water in the raw material is higher, and because of in reaction process, free fatty acids can produce emulsion with alkali generation saponification reaction; Contained humidity then can cause the ester hydrolysis, and then saponification reaction takes place, and it also can weaken catalyst activity simultaneously; The generation emulsification because free fatty acids, water and alkaline catalysts react becomes glycerine mutually mutually and is difficult to separate, thereby makes the post-reaction treatment process become loaded down with trivial details with methyl esters; The product that obtains also needs a large amount of washings, produces a large amount of waste water.
The researchdevelopment trend of preparation biodiesel catalyst is to seek high efficiency solid catalyst to be used to transform grease, and purpose is when producing new forms of energy, must reduce production costs, enhance productivity, reduce environmental pollution.Therefore, competitively launch extensive studies in the association area of preparation biodiesel catalyst both at home and abroad, at present, relevant patent report is more both at home and abroad, as application number is that 200610019245.4 (publication number CN1580190A), publication number are as described in CN1664072A, US5908946, the EP0985654 etc., adopt solid acid, alkaline process to prepare biofuel, can overcome the part shortcoming of liquid acid, alkaline process, preparation technology is become simply, can reduce environmental pollution simultaneously.It was 200610019245.4 (denomination of invention prepares method of bio-diesel oil for adopting nano solid acid or base catalysis) that portion and closely-related patent documentation of the present invention such as number of patent application are arranged in existing publication document, disclosing a kind of it is said is solid acid or the solid alkali as a catalyst that utilizes nano level (the nanoparticle footpath is in the 1-100nm scope), the catalyzer add-on is the 1-20% of vegetable and animals oils weight, the mol ratio 3.5-40 of low-carbon alcohol such as methyl alcohol or ethanol and vegetable and animals oils: 1, the heated and stirred reaction, retort pressure is normal pressure-25Mp, temperature: 40-100 degree, reaction back is centrifugal to go out thick methyl esters and glycerine mutually, and then thick methyl esters distilled out low-carbon alcohol respectively mutually with glycerine, obtain neutral biofuel and glycerine at last.But its specification sheets does not fully disclose the concrete preparation method of described catalyzer, and whether be nano material, only used the nanometer notion if not characterizing listed catalyzer again.The nanometer unit of described catalyzer is not described in embodiment; lack the support of applying nano catalyzer implementation result and contrast experiment's data; its catalytic activity of nanocatalyst and the variation tendency thereof that have adopted invention to be claimed can not be described; be used for preparing the problems such as saponification that biofuel can't overcome the biodiesel manufacture process by its described nano solid base; this patent request scope of patent protection can not get the support of specification sheets (as the nanometer range of nanocatalyst; adding proportion; critical technical parameters such as mol ratio), the technology contents public who provides according to this specification sheets can't reproduce the effect shown in the invention book.This invention also will be carried out the centrifugal processing step of Denging to reacted primary products, makes whole preparation process can not realize integrated operation, and technology is succinct inadequately.
Nano solid acid, solid base catalyst are the important development directions of preparation biofuel, because the nano-solid catalyzer has high-ratio surface, high catalytic activity, therefore consumption is less, the catalytic efficiency height need not neutralization and washing, does not have environmental pollution substantially, but the fixing difficult problem of nano material ubiquity, as fixing improper then subsequent product separation difficulty, cause in the product mechanical impurity too high, influence the use of product.Therefore, researching and developing nano-solid heteropoly acid, heteropolybase catalyst with using value is the key of production biofuel.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, development utilizes the novel method of nano-solid heteropoly acid, heteropolybase catalyst catalytic preparation (production) biofuel, overcoming the agglomeration traits of nano particle in the existing catalyzer, and the gordian technique difficult problem such as fixing of saponification in preparation biofuel process and catalyzer.Task of the present invention also relates to nano-solid heteropoly acid, heteropolybase catalyst, by enforcement of the present invention, obtain the nano-solid catalyzer of outstanding advantages such as a kind of activity is high, intensity is big, the life-span is long, regenerability is good, make the aftertreatment technology of production biofuel simple, product yield height meets the green production requirement.
The present invention is achieved through the following technical solutions:
Utilize nano-solid heteropoly acid, the method of heteropolybase catalyst catalyzed production biodiesel, comprise the animals and plants crude oil of high acid value or concise vegetable and animals oils and low-carbon alcohol are placed a reaction system, under the catalysis of catalyzer, react, described catalyzer is that particle diameter is that the nanoscale solids heteropolyacid of 25～50nm is or/and heteropolybase, described low-carbon alcohol is a methyl alcohol, described reaction is esterification and/or transesterification reaction, described catalyst consumption is 1～6% of a vegetable and animals oils weight, keeping alcohol/molar equivalent is (to be preferably 9～24: 1) at 6～48: 1, temperature of reaction is 60～90 ℃ (being preferably 75-85 ℃), normal pressure is reaction 1～10h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98%, and the use that can repeat and regenerate of described nano-solid heteropoly acid, heteropolybase catalyst.
In the present invention, described nano-solid heteropoly acid catalyzer is selected from following compounds: ammonium persulfate/zirconium dioxide-titanium dioxide (S 2O 8 2-/ ZrO 2-TiO 2) or ammonium persulfate/γ-aluminium sesquioxide-silicon-dioxide (S 2O 8 2-/ γ-Al 2O 3-SiO 2), tungsten sila polyacid (H 4SiW 12O 40/ SiO 2), molybdenum vanadium phospha polyacid (H 4PMo11VO 40XH 2O) wherein a kind of or its combination.Its detailed preparation process is referring to embodiment 1.
Described nano-solid heteropolybase catalyst is selected from following compounds: salt of wormwood/γ-aluminium sesquioxide (K 2CO 3/ γ-Al 2O 3), Potassium monofluoride/calcium oxide (KF/CaO) or Potassium monofluoride/calcium oxide-magnesium oxide (KF/CaO-MgO), cobalt molybdenum magnalium heteropolybase (Co 2Mo/MgO 2Al 2O 3) wherein a kind of or its combination.The preparation method is described referring to embodiment 1 in detail.
The crude oil of lard, abendoned oil, rapeseed oil, Oleum Gossypii semen, soybean oil, plam oil and tallowseed oil etc. that described in the present invention vegetable and animals oils can be a high acid value also can be the Clean products that reduces the above-mentioned oil product of acid number.
In order to implement the present invention better, when adopting the crude oil such as lard, abendoned oil, rapeseed oil, Oleum Gossypii semen, soybean oil, plam oil, tallowseed oil of the high acid value of undressed processing, elder generation's above-mentioned nano-solid heteropoly acid catalyzer of adding in reaction system carries out esterification, and (in the reaction times 2～4h), (reaction times is 2～9h) to carry out transesterification reaction with the nano-solid heteropolybase catalyst again.If the Clean products of low acid number, only need add the nano-solid heteropolybase catalyst in reaction system of the present invention carries out transesterification reaction (reaction times is 2～6h), just can obtain the biofuel and the glycerine of ON-LINE SEPARATION of the present invention, thereby finish the present invention.
The invention has the beneficial effects as follows:
1. adopt rational preparation method to obtain solid heteropoly acid or the alkaline catalysts of 25～50nm, the type catalyzer has active height, intensity is big, the life-span is long and be easy to the fixed characteristics.As patent publication No. is that the nanocatalyst of CN1858160A preparation need carry out centrifugation when being used to prepare biofuel, product and catalyst separating difficulty are big, and the nanocatalyst of the present invention's preparation has found suitable fixing means, has realized that catalyzer separates automatically with product.
2. utilizing nano-solid heteropoly acid, heteropolybase catalyst is that feedstock production biofuel transformation efficiency reaches more than 98% with the vegetable and animals oils, technical target of the product meets U.S. ASTM D 6751-03 standard, need not do any processing and can directly supply with the use of all kinds diesel engine fully.
With nano-solid heteropoly acid, the heteropolybase catalyst coupling prepares biofuel that the vegetable and animals oils raw material is not had selectivity, is suitable for vegetable and animals oils (comprising abendoned oil) the preparation biofuel of any kind.Patent publication No. is the scope of application of the undeclared catalyzer of CN1858160A, need to make catalyzer for high-acid value grease (as abendoned oil) with nano-solid heteropoly acid, or carry out transesterify with solid alkali again with the pre-esterification of solid acid, when doing biodiesel, suitable nano solid acid also should use water trap, the water of separating reaction generation in time, otherwise primary first-order equation is difficult to reach the transformation efficiency more than 90%; And use solid base catalyst must strictly control greasy water-content and acid content, otherwise easily produce the carrying out of saponification influence reaction; As only making catalyzer with nano solid acid, then transesterification reaction is carried out slower, consuming time long.The present invention uses these two kinds of catalyzer coupling techniques to overcome harsh requirement to the raw oil material moiety.
4. utilize nano-solid heteropoly acid, heteropolybase catalyst to prepare biofuel and traditional liquid acid, the superiority that alkali is bigger than having, production technique is simple, product need not neutralization, washing, environment is not produced and pollute, glycerine reclaims easily, etching apparatus not, the product aftertreatment is simple, greatly reduces production cost.With patent publication No. be CN1858160A relatively, this catalyzer is owing to adopted multiple preparation technology simultaneously, the catalyst particle size that obtains is evenly distributed, through being characterized in 25～50nm scope, the disposable successive reaction transformation efficiency of preparation biofuel reaches more than 98%, and catalytic performance is the catalyzer (disposable successive reaction transformation efficiency is 97%) of CN1858160A preparation significantly better than publication number.
5. this biodiesel consumption uses 1～6h generally at 1～6% of weight of oil at every turn, can use 16～82 activity constant substantially continuously, and this catalyzer can also be regenerated, and activity and live catalyst after the regeneration are suitable.Is that the feedstock production biodiesel catalyst uses and the following Fig. 1 of the result of use of regenerating, Fig. 2 continuously as catalyzer KF/CaO-MgO with rapeseed oil, methyl alcohol.Reaction conditions, molar ratio of methanol to oil 12: 1,70 ℃ of temperature of reaction, reaction times 3h.
Fig. 4 has shown the catalyzer KF/CaO-MgO access times of the present invention's preparation and the relation of esterification yield, and Fig. 5 has then shown the relation of catalyzer KF/CaO-MgO regeneration access times of the present invention and esterification yield
From Fig. 4 and Fig. 5 as can be seen, nano-solid heteropolybase catalyst KF/CaO-MgO uses continuously and the back of regenerating uses its catalytic performance fluctuation less, substantially do not influence catalytic effect, with patent publication No. be that CN1858160A relatively has more superior catalytic performance, and the relation of the access times of CN1858160A and undeclared catalyzer, regeneration access times and esterification yield.
Description of drawings
Fig. 1 is a nano-solid heteropoly acid catalyst S of the present invention 2O 8 2-/ TiO 2-ZrO 2Transmission electron microscope picture; Catalyzer (the S that shows the present invention's preparation 2O 8 2-/ TiO 2-ZrO 2) median size is about 30nm.
Fig. 2 is the nano-solid heteropolybase catalyst KF/CaO transmission electron microscope picture that the present invention prepares; Catalyzer (KF/CaO) median size that shows the present invention's preparation is about 25nm.
Fig. 3 is the nano-solid heteropolybase catalyst KF/CaO-MgO transmission electron microscope picture that the present invention prepares; Catalyzer (KF/CaO-MgO) median size that shows the present invention's preparation is about 50nm
Fig. 4 is the catalyzer KF/CaO-MgO access times that prepare of the present invention and the relation of esterification yield
Fig. 5 is the catalyzer KF/CaO-MgO regeneration access times that prepare of the present invention and the relation of esterification yield
Fig. 6 is that the different mol ratio of n (Ti) and n (Zr) is to catalyst S 2O 8 2-/ TiO 2-ZrO 2The influence of esterification yield
Fig. 7 is (NH 4) 2S 2O 8Concentration is to catalyst S 2O 8 2-/ TiO 2-ZrO 2The influence of esterification yield
Fig. 8 is that the different dipping time of ammonium persulfate are to catalyst S 2O 8 2-/ TiO 2-ZrO 2The influence of esterification yield
Fig. 9 is a catalyst S 2O 8 2-/ TiO 2-ZrO 2Maturing temperature to influence to the catalyzer esterification yield
Figure 10 is a catalyst S 2O 8 2-/ TiO 2-ZrO 2Roasting time to influence to the catalyzer esterification yield
Figure 11 is that n (Al) and n (Si) different mol ratio are to catalyst S 2O 8 2-/ γ-Al 2O 3-SiO 2The influence of esterification yield
Figure 12 is (NH 4) 2S 2O 8Concentration is to catalyst S 2O 8 2-/ γ-Al 2O 3-SiO 2The influence of esterification yield
Figure 13 is that the different dipping time of ammonium persulfate are to catalyst S 2O 8 2-/ γ-Al 2O 3-SiO 2The influence of esterification yield
Figure 14 is the S of catalyzer 2O 8 2-/ γ-Al 2O 3-SiO 2Maturing temperature to the influence of esterification yield
Figure 15 is the S of catalyzer 2O 8 2-/ γ-Al 2O 3-SiO 2Roasting time to the influence of esterification yield
Figure 16 is K 2CO 3With γ-Al 2O 3Amount of substance is to the influence of esterification yield
Figure 17 is catalyzer K 2CO 3/ γ-Al 2O 3Calcining temperature is to the influence of esterification yield
Figure 18 is catalyzer K 2CO 3/ γ-Al 2O 3Calcination time is to the influence of esterification yield
Figure 19 is the influence to esterification yield of CaO and MgO mass ratio
Figure 20 is the influence of the pickup of catalyzer KF/CaO-MgO to esterification yield
Figure 21 is the influence of the quality of catalyzer KF/CaO-MgO soaker water to esterification yield
Figure 22 is the influence of catalyzer KF/CaO-MgO dipping time to esterification yield
Figure 23 is the influence of the calcining temperature of catalyzer KF/CaO-MgO to esterification yield
Figure 24 is the influence of the calcination time of catalyzer KF/CaO-MgO to esterification yield
Figure 25 is the influence of the consumption of the KF among the catalyzer KF/CaO-MgO to esterification yield
Figure 26 is the influence of methanol usage to esterification yield
Figure 27 is the influence to esterification yield of esterification and transesterification reaction temperature
Figure 28 is the influence to esterification yield of esterification and transesterification reaction time
Embodiment
The preparation of embodiment 1 nano-solid catalyzer heteropolyacid and heteropolybase
The nano-solid heteropoly acid catalyzer is selected from the following compounds preparation: ammonium persulfate/zirconium dioxide-titanium dioxide (S 2O 8 2-/ ZrO 2-TiO 2) or ammonium persulfate/γ-aluminium sesquioxide-silicon-dioxide (S2O82-/γ-Al2O3-SiO2), tungsten sila polyacid (H4SiW12O40/SiO2), molybdenum vanadium phospha polyacid (H4PMo11VO40xH2O).
Concrete preparation process:
(1) catalyst S 2O 8 2-/ ZrO 2-TiO 2Preparation: adopt chemical precipitation-high-temperature roasting method, its concrete preparation process is with reference to (golden auspicious sister-in-law .S 2O 8 2-/ ZrO 2-SiO 2Solid acid catalyst and catalysis synthesizing citric acid tri-n-butyl [J]. use chemical industry, 2005,34:32～35) method introduced carries out.Specifically: measure the 24ml titanium chloride, the 10ml zirconium oxychloride is soluble in water, makes precipitation agent with 25% ammoniacal liquor respectively, constantly stir, control titanium chloride and zirconyl chloride solution pH value be 8～10, static 2～6h.To generate titanium hydroxide and zirconium hydroxide thorough mixing then, and obtain A liquid, and with A liquid ageing 1～3h in 60～90 ℃ water-bath, filter, washing is to there not being chlorion (Cl -) exist, with silver nitrate solution (AgNO 3) (the A liquid that takes a morsel is to wherein adding 1～2 AgNO in check 3If, there is not muddy phenomenon, show with no Cl -).Dry by the fire 1～3h down at 110 ℃, with 0.1～2molL -1Ammonium persulfate solution dipping 1～3h, suction filtration, drying, roasting 3～6h in 450～650 ℃ of muffle furnaces can make the nano-solid heteropoly acid catalyst S 2O 3 2-/ TiO 2-ZrO 2This catalyzer transmission electron microscope picture is seen Fig. 1, and the catalyzer median size of preparation is about 30nm.
(2) catalyst S 2O 8 2-/ γ-Al 2O 3-SiO 2Preparation: adopt sol-gel-high-temperature roasting method, its concrete preparation process with reference to (Cao Yuping, Li Yuguo, Sun Qinjun. the preparation of bitter earth nano powder and sign [J]. Shandong Normal University is learned edition, 2007,22:69～70).Make Al during for 3-6 in the pH value 3+, SiO 3 2-Hydrolysis and polycondensation form Al 3+-(OH) n-Al 3+, Al 3+-(OH) n-Si 4+, Si 4+-(OH) n-Si 4+Colloidal sol naturally cools to room temperature, obtains γ-Al 2O 3-SiO 2Gel places the resistance furnace calcination with this gel, obtains γ-Al 2O 3-SiO 2Powder. use 0.1-2molL -1(NH 4) 2S 2O 8Handle, contain oxo bridge and the polycentric composite nano solid heteropoly acid of cystine linkage catalyzer after 400-700 ℃ of roasting promptly gets.The catalyst particle size of preparation is about 30nm.
(3) catalyzer H 4SiW 12O 40/ SiO 2Preparation: adopt sol-gel method, its concrete preparation process is with reference to (Sandipan Chatterjee, SudiptaChatterjeed et al.Clarification of fruitjuice with chitosan[J] .Process Biochemistry 2004, (39): 2229-2232.) at first utilize the extracted with diethyl ether legal system to be equipped with H4SiW12O40, prepare the compound phospho-wolframic acid of Nano type with sol-gel method then.According to tetraethyl silicate: the mass ratio of butanols: water: H4SiW12O40 is 10: 5: 4: 3.5 ratio, each raw material is added in the three-necked bottle, reflux and stir 2h, make silicate hydrolyzate generate vitreosol, colloidal sol is changed in the PVC mould over to water bath with thermostatic control 2h, obtain clear gel, 100 ℃ of oven dry, grind, can obtain Nano type H4SiW12O40/SiO2 (diameter of nanoparticle is about 50nm).
(4) catalyzer H4PMo11VO40xH2O.Preparation: its concrete preparation process is with reference to (opening rich people, Guo Maiping, Ge Hanqing. the novel method and the catalytic performance [J] thereof of synthetic molybdenum vanadium phospha polyacid. chemical industry progress, 2006,25:1171-1174) take by weighing MoO3 and V2O5 and be respectively 14.4g and 0.91g, be dissolved in the 250mL distilled water; Above-mentioned molten slurry reflux under vigorous stirring is slowly dripped the phosphoric acid of 1.15g 85% subsequently to 373K, dropwise the back and continue heating and keep 24h under this temperature, in this process, muddy molten slurry becomes the orange solution of clear gradually; Then in the electric vacunm drying case under the temperature of 327K, with the slow evaporate to dryness of moisture, obtain orange red solid; At last solid is dissolved in a small amount of distilled water, under 277K, slowly separates out, and recrystallization 3 times, H4PMo11VO40xH2O promptly got, (diameter of nanoparticle is about 40nm).
The preparation of nano-solid heteropolybase catalyst is selected from following compounds: salt of wormwood/γ-aluminium sesquioxide (K 2CO 3/ γ-Al 2O 3), Potassium monofluoride/calcium oxide (KF/CaO) or Potassium monofluoride/calcium oxide-magnesium oxide (KF/CaO-MgO), cobalt molybdenum magnalium heteropolybase (Co 2Mo/MgO 2Al 2O 3).
Concrete preparation process:
(1) catalyzer carbonic acid potassium/γ-aluminium sesquioxide (K 2CO 3/ γ-Al 2O 3) preparation: adopt incipient impregnation-high-temperature calcination.Its concrete preparation process with reference to (Meng Xin .KF/CaO Soybean Oil by Transesterification prepares biofuel [J]. petrochemical complex, 2005,34:282～285) method introduced carries out.With pickling process with a certain amount of K 2CO 3Be carried on a certain amount of γ-Al 2O 3[m (K on the powder 2CO 3)/m (γ-Al 2O 3) be 0.1～0.6], water is cooked immersion solvent, deposits 1-3h after stirring, and in 110 ℃ of baking 1～5h, at 600 ℃ of calcining 4h, promptly gets the nano-solid heteropolybase catalyst.This catalyzer median size is about 40nm.
(2) preparation of catalyzer Potassium monofluoride/calcium oxide (KF/CaO): adopt incipient impregnation-high-temperature calcination.Its concrete preparation process with reference to (Meng Xin .KF/CaO Soybean Oil by Transesterification prepares biofuel [J]. petrochemical complex, 2005,34:282～285) method introduced carries out.The lime powder (particle diameter 20～40 orders) that takes by weighing 100g places beaker, stirs in the KF solution of the 0.1mol/L that adding prepares in advance, moves in the chamber type electric resistance furnace after the placement room temperature, calcines 4 hours down at 873 ℃.Treat that it naturally cools to room temperature, kept dry promptly gets the nano-solid heteropolybase catalyst in the taking-up moisture eliminator.This catalyzer transmission electron microscope picture is seen Fig. 2, and the catalyzer median size that shows preparation is about 25nm.
(3) preparation of catalyzer Potassium monofluoride/calcium oxide-magnesium oxide (KF/CaO-MgO): adopt ball milling-hydro-thermal to synthesize-high-temperature calcination, its concrete preparation process is with reference to (Ma Hongxia, solid alkali MgO/Al 2O 3The performance of catalyzed oxidation mercaptan [J]. Nanjing University of Technology's journal, 2003,25:62～65) method introduced carries out.With 100g CaO, 20g MgO mixed grinding, the KF solution soaking 1～3h with 0.1mol/L stirs, and at 600 ℃ of calcining 5h, promptly gets the nano-solid heteropolybase catalyst.This catalyzer sem photograph is seen accompanying drawing 3, and the catalyzer median size of preparation is about 50nm.
(4) catalyst cobalt molybdenum magnalium heteropolybase (Co 2Mo/MgO 2Al 2O 3) preparation: adopt hybrid system, its concrete preparation process is with reference to (Zheng Quanxing, Wang Qi, Song Jianhua. XRD and TPR that hybrid system prepares the Co2Mo/MgO2Al2O3 transformation catalyst characterize [J]. Xiamen University's journal (natural science edition), 2004,11:820-823) make sodium aluminate solution with alumina trihydrate Al2O33H2O and 45%NaOH solution, under agitation splash into constant temperature and in 70～75 ℃ dilute nitric acid solution, carry out neutralization reaction, pH is controlled at 10.5, aging 1h, filter, washing, gained filter cake contain 15%Al2O3. the gel aluminium hydroxide HNO3 gel that makes, and add required MgO, (NH4) 6Mo7O244H2O and/or Co (NO3) 23H2O carries out mixed grind, drying, compression molding, 600 ℃ of calcinings make different catalyzer and the references of forming, and wherein the Co2Mo/MgO2Al2O3 catalyzer contains w (CoO)=3.5%, w (MoO3)=8%, w (MgO)=25%, (diameter of nanoparticle is about 50nm).
Embodiment 2 production of biodiesel embodiment 1
Get rapeseed oil (Clean products, acid number are less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 4kg, catalyzer K 2CO 3/ γ-Al 2O 3(particle diameter of catalyzer is 25nm) 200g (catalyst levels be rapeseed oil weight 2%) is in a reaction system (for example reactor), temperature of reaction is 60 ℃, and normal pressure is reaction 8～10h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 3 production of biodiesel embodiment 2
Get rapeseed oil (Clean products, acid number are less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 8kg, catalyzer K 2CO 3/ γ-Al 2O 3In in a reaction system (for example reactor), temperature of reaction is 75 ℃ to (particle diameter of catalyzer is 40nm) 300g (catalyst levels be rapeseed oil weight 3%), and normal pressure is reaction 6～8h down, and separation of glycerin steams methyl alcohol, makes the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 97.6%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 4 production of biodiesel embodiment 3
Get rapeseed oil (Clean products, acid number are less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, catalyzer K 2CO 3/ γ-Al 2O 3In in a reaction system (for example reactor), temperature of reaction is 85 ℃ to (particle diameter of catalyzer is 45nm) 400g (catalyst levels be rapeseed oil weight 4%), and normal pressure is reaction 2～4h down, and separation of glycerin steams methyl alcohol, makes the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98.5%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 5 production of biodiesel embodiment 4
Get rapeseed oil (Clean products, acid number are less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, catalyzer K 2CO 3/ γ-Al 2O 3In in a reaction system (for example reactor), temperature of reaction is 90 ℃ to (particle diameter of catalyzer is 50nm) 600g (catalyst levels be rapeseed oil weight 6%), and normal pressure is reaction 1～2h down, and separation of glycerin steams methyl alcohol, makes the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 97%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 6 production of biodiesel embodiment 5
Get rapeseed oil (Clean products, acid number is less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 4kg, catalyzer KF/CaO (particle diameter of catalyzer is 25nm) 200g (catalyst levels be rapeseed oil weight 2%) is in a reaction system (for example reactor), temperature of reaction is 60 ℃, and normal pressure is reaction 8～10h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 7 production of biodiesel embodiment 6
Get rapeseed oil (Clean products, acid number is less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 8kg, catalyzer KF/CaO (particle diameter of catalyzer is 30nm) 300g (catalyst levels be rapeseed oil weight 3%) is in a reaction system (for example reactor), temperature of reaction is 75 ℃, and normal pressure is reaction 6～8h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 97.6%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 8 production of biodiesel embodiment 7
Experiment material is a rapeseed oil (Clean products, acid number is less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, catalyzer KF/CaO (particle diameter of catalyzer is 45nm) 400g (catalyst levels be rapeseed oil weight 4%) is in a reaction system (for example reactor), temperature of reaction is 85 ℃, and normal pressure is reaction 2～4h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98.7%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 9 production of biodiesel embodiment 8
Get rapeseed oil (Clean products, acid number is less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, catalyzer KF/CaO (particle diameter of catalyzer is 50nm) 600g (catalyst levels be rapeseed oil weight 6%) is in a reaction system (for example reactor), temperature of reaction is 90 ℃, and normal pressure is reaction 1～2h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 97%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 10 production of biodiesel embodiment 9
Get rapeseed oil (Clean products, acid number are less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, CATALYST Co 2Mo/MgO 2Al 2O 3In in a reaction system (for example reactor), temperature of reaction is 90 ℃ to (particle diameter is 40nm) 600g (catalyst levels be rapeseed oil weight 6%), and normal pressure is reaction 1～2h down, and separation of glycerin steams methyl alcohol, makes the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98%, and the use that can repeat and regenerate of described catalyzer.
Embodiment 11 production of biodiesel embodiment 10
Get Oleum Gossypii semen (Clean products, acid number is less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, catalyzer H4SiW12O40/SiO2 (particle diameter is 50nm) 500g (catalyst levels be rapeseed oil weight 5%) is in a reaction system (for example reactor), temperature of reaction is 90 ℃, and normal pressure is reaction 1～2h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 98.5%, the catalyzer of the stating use that can repeat and regenerate.
Embodiment 12 production of biodiesel embodiment 11
Get Oleum Gossypii semen (Clean products, acid number are less than or equal to 1.5mg/g sodium hydroxide) 10kg, methyl alcohol 16kg, catalyzer H 4PMo 11VO40xH2O (particle diameter is 30nm) 600g (catalyst levels be rapeseed oil weight 6%) is in a reaction system (for example reactor), temperature of reaction is 90 ℃, and normal pressure is reaction 1～2h down, separation of glycerin, steam methyl alcohol, make the biofuel of preparation be neutral.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 97.5%, the catalyzer of the stating use that can repeat and regenerate
Embodiment 13: utilize the nano-solid heteropoly acid catalyst S 2O 8 2-/ ZrO 2-TiO 2Preparation and catalysis Chinese tallow tree seed crude oil prepare biofuel
In the present embodiment, the preparation of biofuel (production) technology is carried out with reference to embodiment 2 described technologies.
Nano-solid heteropoly acid catalyzer (S 2O 8 2-/ ZrO 2-TiO 2) the preparation raw material is TiCl 4, ZrOCl 2, NH 3H 2O, (NH 4) 2S 2O 8, its concrete preparation process is with reference to (Dong Guochen, nano solid supper corrosive acid SO 4 2-/ TiO 2-SiO 2[J]. Northeast Normal University newspaper natural science edition, 2004,36:27～31) method introduced carries out.
The main raw material of biodiesel manufacture and condition, the nano-solid heteropoly acid catalyst S 2O 8 2-/ ZrO 2-TiO 22.6g, cold rolling Chinese tallow tree seed crude oil 100mL (oneself make, its acid number is 87mg/g NaOH), commercially available methanol 36mL, 70 ℃ of temperature of reaction, reaction times 3h, esterification yield is with gas Chromatographic Determination (PE-500, fid detector, 2010 chromatographic working stations).
(1) different Ti: Zr is to the influence of catalyst activity
Get 10g ZrO 2And TiO 2Composite oxides, use 0.6molL -1(NH 4) 2S 2O 8Solution impregnation 3h, 600 ℃ of maturing temperatures, roasting 4h, investigate different n (Ti): n (Zr) sees Fig. 6 to the influence of catalyst activity.As seen from Figure 6, n (Ti): n (Zr) is very big to the activity of such catalysts influence, and n (Ti): n (Zr) is that 6～7 o'clock catalytic activitys are higher.
(2) (NH 4) 2S 2O 8The concentration of solution is to the influence of catalyst activity
N (Ti): n (Zr) is 7,600 ℃ of maturing temperatures, roasting 4h, dipping time are 3h, investigates (the NH of different concns 4) 2S 2O 8To the influence of catalyst activity, the condition of preparation biofuel is the same, and Fig. 7 is seen in its influence.As seen from Figure 7, ammonium persulphate concentration has very big influence to catalytic activity, and its concentration is too high or too low all unfavorable to catalytic activity, and the ammonium persulfate solution optimum concn is 0.6mol -1The time catalytic activity the best.
(3) the ammonium persulphate dipping time is to the influence of catalyst activity
N (Ti): n (Zr) is 7,600 ℃ of maturing temperatures, roasting 4h, ammonium persulfate solution concentration are 0.6molL -1, investigate of the influence of different dipping time to catalyst activity, the condition of preparation biofuel is the same, and Fig. 8 is seen in its influence.As seen from Figure 8, different dipping time catalyst activities have certain influence, catalytic activity the best when dipping 3h.
(4) maturing temperature is to the influence of catalyst activity
N (Ti): n (Zr) is 7, (NH 4) 2S 2O 8Concentration is 0.6molL -1, dipping time is 3h, roasting 4h, investigates the influence of different maturing temperatures to catalyst activity, the condition of preparation biofuel is the same, Fig. 9 is seen in its influence.As seen from Figure 9, the influence that maturing temperature is bigger to catalytic activity, optimum calcination temperature is 600 ℃.
(5) roasting time is to the influence of catalyst activity
N (Ti): n (Zr) is 7, (NH 4) 2S 2O 8Concentration is 0.6molL -1, dipping time is that 3h, maturing temperature are 600 ℃, investigates the influence of different roasting time to catalyst activity, the condition of preparation biofuel is the same, Figure 10 is seen in its influence.As seen from Figure 10, the influence that roasting time is bigger to catalytic activity, best roasting time is 4h.
Embodiment 14: the nano-solid heteropoly acid catalyst S 2O 8 2-/ γ-Al 2O 3-SiO 2Preparation and catalysis lard prepare biofuel
In the present embodiment, the preparation of biofuel (production) technology is carried out with reference to embodiment 2 described technologies.Catalyzer (S 2O 8 2-/ γ-Al 2O 3-SiO 2) preparation main raw material, AlCl 3, H 2SiO 3, HCl, NH 3H 2O, (NH 4) 2S 2O 8
The main raw material of biodiesel manufacture and condition, the nano-solid heteropoly acid catalyst S 2O 8 2-// γ-Al 2O 3-SiO 23.0g, lard 100g, methyl alcohol 36mL, 70 ℃ of temperature of reaction, reaction times 3h, the esterification yield gas Chromatographic Determination.
(1) influence of different al, Si comparison catalyst activity
To different al, Si than mixture gel 1molL -1Concentration (NH 4) 2S 2O 8Dipping, dipping time 2h at 550 ℃ of roasting 4h, investigates activity of such catalysts with the method for preparing biofuel and sees Figure 11.As seen from Figure 11, n (Al): n (Si) is 6 o'clock, and catalyst activity is the highest.
(2) different (NH 4) 2S 2O 8Dipping concentration is to the influence of catalyst activity
N (Al): n (Si) is 6,550 ℃ of maturing temperatures, roasting 4h, dipping time are 2h, investigates (the NH of different concns 4) 2S 2O 8To the influence of catalyst activity, the condition of preparation biofuel is the same, and Figure 12 is seen in its influence.As seen from Figure 12, ammonium persulphate concentration has very big influence to catalytic activity, and its concentration is too high or too low all unfavorable to catalytic activity, and the ammonium persulfate solution optimum concn is 1.0molL -1The time catalytic activity the best.
(3) the ammonium persulphate dipping time is to the influence of catalyst activity
N (Al): n (Si) is 6,550 ℃ of maturing temperatures, roasting 4h, (NH 4) 2S 2O 8Concentration is 1molL -1, investigate of the influence of dipping different time to catalyst activity, the condition of preparation biofuel is the same, and Figure 13 is seen in its influence.As seen from Figure 13, different dipping time have certain influence to catalyst activity, catalytic activity the best when dipping 1.5h.
(4) maturing temperature influences to catalyst activity that n (Al): n (Si) is 6, roasting 4h, (NH 4) 2S 2O 8Concentration is 1molL -1Dipping time is 2h, investigates the influence of different maturing temperatures to catalyst activity, and the condition of preparation biofuel is the same, and Figure 14 is seen in its influence.As seen from Figure 14, the influence that maturing temperature is bigger to catalytic activity, optimum calcination temperature is 550 ℃.
(5) roasting time is to the influence of catalyst activity
N (Al): n (Si) is 6, (NH 4) 2S 2O 8Concentration is 1molL -1Dipping time is 2h, and maturing temperature is 600 ℃, investigates the influence of different roasting time to catalyst activity, and the condition of preparation biofuel is the same, and Figure 15 is seen in its influence.As seen from Figure 15, the influence that roasting time is bigger to catalytic activity, best roasting time is 4.5h.
Embodiment 15: catalyzer K 2CO 3/ γ-Al 2O 3Preparation and catalysis rapeseed oil (Clean products) conversion biodiesel
In the present embodiment, the preparation of biofuel (production) technology is carried out with reference to embodiment 2 described technologies.
With pickling process with K 2CO 3Be carried on γ-Al 2O 3On the particle, water is cooked immersion solvent, and the back water-bath evaporation and dry by the fire 2h at 105 ℃ in baking oven of stirring is put into chamber type electric resistance furnace then and calcined, and treats that temperature reduces to about 100 ℃, catalyzer is taken out to put into preserve stand-by in dry device.Research load proportioning, calcining temperature, calcination time etc. are to the transesterify Effect on Performance.
In there-necked flask, add rapeseed oil 100mL, methyl alcohol 24mL, catalyzer (K 2CO 3/ γ-Al 2O 3) 2.6g, 70 ℃ of temperature of reaction,, reaction times 3h, reaction finishes and isolates glycerine and catalyzer, and evaporates unnecessary methyl alcohol and promptly obtain biofuel.
(1) catalyst proportion is to the influence of catalytic performance
As seen from Figure 16: 1. work as K 2CO 3/ γ-Al 2O 3Proportioning is lower than at 50% o'clock, along with K 2CO 3The increase gradually of ratio, esterification yield increases gradually, and the catalytic efficiency of catalyzer is more and more higher, and this is because work as K 2CO 3/ γ-Al 2O 3Proportioning is lower than at 50% o'clock, the K of carrier surface 2CO 3It is more even to distribute, heavily should be little, and along with K 2CO 3The increase gradually of ratio, K 2CO 3The quantity of the basic center that produces after the thermolysis also increases gradually, thereby makes K 2CO 3/ γ-Al 2O 3Property strengthens gradually, and then catalytic efficiency also improves thereupon; 2. work as K 2CO 3/ γ-Al 2O 3Proportioning is higher than at 50% o'clock, along with K 2CO 3The increase gradually of composition, ester reduces gradually, illustrates that the catalytic efficiency of catalyzer is more and more lower, and this is because work as K 2CO 3/ γ-Al 2O 3Proportioning is higher than at 50% o'clock, the K of carrier surface 2CO 3Branch is inhomogeneous, and eclipsing effect is big, along with K 2CO 3The increase gradually of ratio, K 2CO 3The basic center that produces after the thermolysis is also overlapping gradually, does not only make K 2CO 3/ γ-Al 2O 3Alkalescence strengthen and to make its reduction on the contrary, and then catalytic efficiency also decreases.
(2) change of calcining temperature is to the test of catalyst efficient
As seen from Figure 17: 1. when calcining temperature was lower than 600 ℃, along with the rising of calcining temperature, esterification yield improved gradually, illustrated that the catalytic efficiency of catalyzer is more and more higher, and this is because when calcining temperature is lower than 600 ℃, along with the rising of calcining temperature, K 2CO 3Rate of decomposition also improve gradually, thereby the quantity of the basic center that is produced is also more and more, the alkalescence of catalyzer is also more and more stronger, catalytic efficiency also improves naturally thereupon.2. when calcining temperature is higher than 600 ℃, rising along with calcining temperature, the variation of esterification yield is also not obvious, the catalytic efficiency that catalyzer is described changes not quite, and this is because temperature is too high, can form bigger gathering, produce sintering phenomenon, reduce specific surface, thereby the calcining temperature quantity that also can not make basic center that raises again increases, catalytic efficiency during with 600 ℃ the incinerating catalyzer compare and change and not obvious.
(3) change of calcination time is to the influence of catalyst efficient
As seen from Figure 18: 1. when calcination time is lower than 4h, along with the prolongation of calcination time, esterification yield improves gradually, and promptly the catalytic efficiency of catalyzer is along with the prolongation of calcination time promotes rapidly, this is because when calcination time is lower than 4h, along with the prolongation K of calcination time 2CO 3Rate of decomposition also improve gradually, thereby the quantity of the basic center that is produced is also more and more, the alkalescence of catalyzer is also more and more stronger, catalytic efficiency also improves naturally thereupon.2. when calcination time during greater than 4h, along with the prolongation of calcination time, esterification yield changes little, and promptly the catalytic efficiency of catalyzer changes along with the prolongation of calcination time and be not obvious, and this is because when calcination time during greater than 4h, along with the prolongation K of calcination time 2CO 3Rate of decomposition again can't improve, thereby calcination time prolongs the quantity that also can not make basic center again and increases, its catalytic efficiency during with 4h the incinerating catalyzer compare and change and not obvious.
Embodiment 16: the preparation of catalyzer KF/CaO and the test of catalysis rapeseed oil conversion biodiesel
Take by weighing the 100g lime powder and place furnace pot, 0.1mol/LKF solution is added and stir, the KF/CaO catalyzer that makes is put into chamber type electric resistance furnace, temperature is transferred to 873 ℃, calcining a few hours 4h.Treat that it naturally cools to room temperature, put it into wide-necked bottle and kept dry.
Taking by weighing the 2.8gKF/CaO catalyzer, to place 36mL methyl alcohol to be dipped to wet, puts into the there-necked flask of 250mL with the 100mL rapeseed oil, and bath temperature is 65 ℃, under the continuous electronic stirring condition, refluxes 2 hours.Decompress filter is isolated the KF/CaO catalyzer while hot, uses the separating funnel standing demix then, promptly gets biofuel and by-product glycerin.
(1) Preparation of catalysts test
According to principle of orthogonal test, determine the concrete scheme of orthogonal test, as following table.
Table 1 factor level
Figure A20071005206500121
Table 2 Preparation of Catalyst orthogonal experiments
Figure A20071005206500131
By R value in the table 2 as can be seen, the principal element that influences the biofuel transformation efficiency is KF and CaO mass ratio, and each factor influences size order and is: A＞B＞D＞C, and by K iBe worth as can be known, the optimization processing condition that the catalysis rapeseed oil prepares the nano-solid heteropolybase catalyst KF/CaO preparation of biofuel are A 2B 3D 3C 3
The stability test of catalyst optimization processing condition:
According to optimizing 5 groups of catalyzer of the parallel preparation of processing condition and preparing biofuel with rapeseed oil under the same conditions, with the gas Chromatographic Determination esterification yield, the results are shown in following table 3 under the same terms.
The catalyzer (KF/CaO) of table 3 the present invention preparation is optimized the stable process conditions test
Figure A20071005206500132
Table 3 data declaration, the result of test is in the error allowed band, and the catalytic performance of this catalyzer has stability preferably.
Embodiment 17: the preparation of nano-solid heteropolybase catalyst KF/CaO-MgO and the test of catalysis soybean oil conversion biodiesel
In the present embodiment, the preparation of biofuel (production) technology is carried out with reference to embodiment 2 described technologies.
Ball milling-hydro-thermal is synthetic-and high-temperature calcination prepares KF/CaO-MgO.With 100g CaO, 20gMgO mixed grinding, soak 1～3h with the 0.1mol/LKF body lotion, under 105 ℃ of conditions, dry, at 400～800 ℃ of calcining 2～6h, promptly get nano-solid heteropolybase KF/CaO-MgO catalyzer then.
Taking by weighing the 3.00gKF/CaO-MgO catalyzer, to place 24mL methyl alcohol to be dipped to wet, puts into the there-necked flask of 250mL with the 100mL rapeseed oil, and bath temperature is 68 ℃, under the continuous electronic stirring condition, refluxes 2 hours.Product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.
(1) CaO and MgO mass ratio are to the influence of catalytic activity
Take by weighing well-mixed CaO of 100g and MgO, add the aqueous solution 150mL that contains 25gKF, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining 5h, be the feedstock production biofuel with the soybean oil, investigate CaO and MgO mass ratio Figure 19 is seen in the influence of catalytic activity.As shown in Figure 19, m (CaO)/m (MgO) is 5 o'clock, and catalytic activity is the highest.
(2) relation of the pickup of KF and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5], the aqueous solution 150mL that adds 10-25gKF, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining 5h, with the soybean oil is the feedstock production biofuel, investigates the pickup of KF Figure 20 is seen in the influence of catalytic activity.As shown in Figure 20, the pickup of KF is 25% o'clock of CaO/MgO quality, and catalytic activity is the highest.
(3) relation of the quality of soaker water and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5], add 25g KF and 100-150g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining 5h, with the soybean oil is the feedstock production biofuel, investigates the quality of soaker water Figure 21 is seen in the influence of catalytic activity.As shown in Figure 21, the quality of soaker water is 130% o'clock of CaO/MgO quality, and catalytic activity is the highest.
(4) relation of dipping time and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5], add 25g KF and 130g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and the immersion certain hour, at 600 ℃ of calcining 5h, with the soybean oil is the feedstock production biofuel, investigates dipping time Figure 22 is seen in the influence of catalytic activity.As shown in Figure 22, dipping time is 1h, and catalytic activity is the highest.
(5) relation of calcining temperature and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5], add 25g KF and 130g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, calcine 5h down at 400-900 ℃, with the soybean oil is the feedstock production biofuel, investigates calcining temperature Figure 23 is seen in the influence of catalytic activity.As shown in Figure 23, during 600 ℃ of calcining temperatures, catalytic activity is the highest.
(6) relation of calcination time and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5], add 25g KF and 130g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining certain hours, with the soybean oil is the feedstock production biofuel, investigates calcination time Figure 24 is seen in the influence of catalytic activity.As shown in Figure 24, calcination time is 5h, and catalytic activity is the highest.
Embodiment 18: nano-solid heteropoly acid, alkaline catalysts (S 2O 8 2-/ ZrO 2-TiO 2And KF/CaO-MgO) coupling prepares the biofuel test with abendoned oil
In the present embodiment, the preparation of biofuel (production) technology is carried out with reference to embodiment 2 described technologies.
Abendoned oil contains certain water gaging (about 5%) and lipid acid (about 50%) usually, and it is obviously not all right only to make catalyzer with the nano-solid heteropolybase, can produce stronger saponification phenomenon, and product can't separate, and reaction also is difficult to carry out fully; It is very fast only to make the catalyzer Esterification Stage with nano-solid heteropoly acid, but too slow when carrying out transesterification reaction, and must in time isolate the water that reaction produces in the reaction process, otherwise is difficult to reach the ideal transformation efficiency, and it is longer to finish reaction time consumption.Therefore, take nano-solid heteropoly acid, alkaline catalysts coupling technique can overcome the problems referred to above preferably, can obtain optimized result high-acid value grease.
Take by weighing S 2O 8 2-/ ZrO 2-TiO 2, each 3.00g of KF/CaO-MgO catalyzer places the three-necked bottle of two 250mL respectively, the adding earlier of 100mL abendoned oil (dewatering), 36mL methyl alcohol is filled in the three-necked bottle of nano-solid heteropoly acid, react about 3h down at 68 ℃, isolate the water and the catalyzer of generation simultaneously, the product of pre-esterification added again accommodate in meter three-necked bottle of solid heteropolybase, continue down about reaction 3h at 68 ℃, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.
(1) catalyst levels is to the influence of esterification yield
By above-mentioned reaction conditions, keep other factors constant, change catalyst levels and investigate its influence esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, acid number is pressed GB/T 5530-1998 and is measured, and reaches below the 1mgKOH/g, carries out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and two stage esterification yields and catalyst levels relation are seen Figure 25.Know by Figure 25, Esterification Stage, the nano-solid heteropoly acid consumption reaches specified acid number during for 3.5g, this moment the esterification yield maximum, in the transesterify stage, nano-solid heteropolybase consumption is a 2.8g ester interchange conversion rate maximum.
(2) methanol usage is to the influence of esterification yield
By above-mentioned reaction conditions, the nano-solid heteropoly acid consumption is that 3.5g, nano-solid heteropolybase consumption are 2.8g, keep other factors constant, change methanol usage and investigate its influence to esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, and acid number is pressed GB/T 5530-1998 and measured, reach below the 1mgKOH/g, carry out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and the esterification yield in two stages and catalyst levels relation are seen Figure 26.Know that by Figure 26 when methanol usage was 48mL during acid catalysis, when methanol usage was 36mL during base catalysis, it is maximum that esterification yield reaches, suitable when taking all factors into consideration the disposable add-on of methyl alcohol and being 48mL.
(3) esterification and transesterification reaction temperature are to the influence of esterification yield
By above-mentioned reaction conditions, the nano-solid heteropoly acid consumption is that 3.5g, nano-solid heteropolybase consumption are 2.8g, methanol usage 48mL keeps other factors constant, changes temperature of reaction and investigates its influence to esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, acid number is pressed GB/T5530-1998 and is measured, and reaches below the 1mgKOH/g, carries out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and the esterification yield in two stages and catalyst levels relation are seen Figure 27.Known that by Figure 27 temperature of reaction is at 65～70 ℃ during base catalysis, temperature of reaction is at 70 ℃ during acid catalysis, and it is maximum that esterification yield reaches, and takes all factors into consideration, and temperature of reaction is set in 70 ℃ during acid catalysis, and temperature of reaction is set in 68 ℃ during base catalysis.
(4) esterification and transesterification reaction time are to the influence of esterification yield
By above-mentioned reaction conditions, the nano-solid heteropoly acid consumption is that 3.5g, nano-solid heteropolybase consumption are 2.8g, methanol usage 48mL keeps other factors constant, changes the reaction times and investigates its influence to esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, acid number is pressed GB/T5530-1998 and is measured, and reaches below the 1mgKOH/g, carries out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and the esterification yield in two stages and catalyst levels relation are seen Figure 28.As shown in Figure 28, the base catalysis the reaction time is 3h, and temperature of reaction is 3.5h during acid catalysis, and it is maximum that esterification yield reaches.

Claims (9)

1, utilize nano-solid heteropoly acid, the method of heteropolybase catalyst catalyzed production biodiesel, comprise the animals and plants crude oil of high acid value or concise vegetable and animals oils and low-carbon alcohol are placed a reaction system, under the catalysis of catalyzer, react, it is characterized in that, described catalyzer is that particle diameter is that the nanoscale solids heteropolyacid of 25～50nm is or/and heteropolybase, described low-carbon alcohol is a methyl alcohol, described reaction is esterification and/or transesterification reaction, described catalyst consumption is 1%～6% of a vegetable and animals oils weight, keeping the mol ratio of alcohol/oil is 6～48: 1, temperature of reaction is 60～90 ℃, normal pressure is reaction 1～10h down, separation of glycerin steams methyl alcohol, makes the biofuel of preparation be neutral.
2, production method of bio-diesel oil according to claim 1 is characterized in that described nano-solid heteropoly acid catalyzer is selected from S 2O 8 2-/ ZrO 2-TiO 2, S 2O 8 2-/ γ-Al 2O 3-SiO 2, H 4SiW 12O 40/ SiO 2, H 4PMo11VO 40XH 2Wherein a kind of or its combination of O.
3, production method of bio-diesel oil according to claim 1 is characterized in that described nano-solid heteropolybase catalyst is selected from K 2CO 3/ γ-Al 2O, KF/CaO, KF/CaO-MgO, Co 2Mo/MgO 2Al 2O 3Wherein a kind of or its combination.
4, production method of bio-diesel oil according to claim 3 is characterized in that preparing biofuel with the described method production of claim 3 with the animals and plants Clean products.
5,, it is characterized in that preparing biofuel with high acid value animals and plants crude oil with claim 2 and 3 described method productions according to claim 1,2 or 3 described production method of bio-diesel oil.
6, according to claim 1 or 4 described production method of bio-diesel oil, wherein the transesterification reaction time is 2～9h.
7, production method of bio-diesel oil according to claim 1 or 5, wherein reaction time of esterification is 1～3h, the transesterification reaction time is 2～4h.
8, production method of bio-diesel oil according to claim 1, alcohol/molar equivalent wherein is 9～24: 1.
9, production method of bio-diesel oil according to claim 1, temperature of reaction wherein is 75～85 ℃.
CNA2007100520650A 2007-04-29 2007-04-29 Method for preparing biological diesel oil by using nano-solid heteropoly acid, heteropolybase catalyst Pending CN101294094A (en)

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CN102061224A (en) * 2010-10-11 2011-05-18 西安石油大学 Method for preparing biodiesel by catalysis of modified calcium oxide
CN102274750A (en) * 2011-06-20 2011-12-14 安徽济民医药科技有限公司 Mesoporous molecular sieve supported solid acid catalyst used for santene essential-oil isomerous esterification reaction
CN102335632A (en) * 2011-07-20 2012-02-01 北京工业大学 Method for preparing solid base catalyst with porous SiO2 material as carrier and application of solid base catalyst
WO2012111023A1 (en) 2011-02-14 2012-08-23 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
TWI507519B (en) * 2013-09-26 2015-11-11 Univ Tatung Manufacture process of simultaneous synthesis of gasoline octane booster and diesel from glycerol with tert-butyl alcohol or isobutylene
CN105754718A (en) * 2016-04-26 2016-07-13 上海应用技术学院 Method for preparing biodiesel
US20180057786A1 (en) * 2009-06-30 2018-03-01 Anita Goel Nano Biofuel Production Processes: Using Nantechnology to Enhance Produciton fo Biofuels
CN109851498A (en) * 2019-01-28 2019-06-07 湖州新奥特医药化工有限公司 A kind of New Type of Ethylene ketone ester is combined to the preparation method of IPA
CN112126528A (en) * 2020-09-23 2020-12-25 上海应用技术大学 Preparation method of biodiesel

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180057786A1 (en) * 2009-06-30 2018-03-01 Anita Goel Nano Biofuel Production Processes: Using Nantechnology to Enhance Produciton fo Biofuels
CN102061224A (en) * 2010-10-11 2011-05-18 西安石油大学 Method for preparing biodiesel by catalysis of modified calcium oxide
WO2012111023A1 (en) 2011-02-14 2012-08-23 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
US9029583B2 (en) 2011-02-14 2015-05-12 Council Of Scientific & Industrial Research Process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
CN102274750A (en) * 2011-06-20 2011-12-14 安徽济民医药科技有限公司 Mesoporous molecular sieve supported solid acid catalyst used for santene essential-oil isomerous esterification reaction
CN102335632A (en) * 2011-07-20 2012-02-01 北京工业大学 Method for preparing solid base catalyst with porous SiO2 material as carrier and application of solid base catalyst
TWI507519B (en) * 2013-09-26 2015-11-11 Univ Tatung Manufacture process of simultaneous synthesis of gasoline octane booster and diesel from glycerol with tert-butyl alcohol or isobutylene
CN105754718A (en) * 2016-04-26 2016-07-13 上海应用技术学院 Method for preparing biodiesel
CN109851498A (en) * 2019-01-28 2019-06-07 湖州新奥特医药化工有限公司 A kind of New Type of Ethylene ketone ester is combined to the preparation method of IPA
CN112126528A (en) * 2020-09-23 2020-12-25 上海应用技术大学 Preparation method of biodiesel

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