CN101492603B - Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof - Google Patents

Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof Download PDF

Info

Publication number
CN101492603B
CN101492603B CN2008100467545A CN200810046754A CN101492603B CN 101492603 B CN101492603 B CN 101492603B CN 2008100467545 A CN2008100467545 A CN 2008100467545A CN 200810046754 A CN200810046754 A CN 200810046754A CN 101492603 B CN101492603 B CN 101492603B
Authority
CN
China
Prior art keywords
reaction
catalyzer
catalyst
oil
biofuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2008100467545A
Other languages
Chinese (zh)
Other versions
CN101492603A (en
Inventor
韩鹤友
王运
胡圣扬
文利柏
关燕萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong Agricultural University
Original Assignee
Huazhong Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong Agricultural University filed Critical Huazhong Agricultural University
Priority to CN2008100467545A priority Critical patent/CN101492603B/en
Publication of CN101492603A publication Critical patent/CN101492603A/en
Application granted granted Critical
Publication of CN101492603B publication Critical patent/CN101492603B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Landscapes

  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the biodiesel preparation technical field, in particular to a method for producing the biodiesel by tallow seed oil and a special magnetic nanometer difunctional solid catalyst suitable for the method. The invention is characterized in that: the tallow seed oil and a low-carbon alcohol are put in a reaction system and react under the catalysis of the catalyst; wherein the catalyst is magnetic nanometer solid acid or/and alkali with the particle size of 30-200nm, the low-carbon alcohol is methyl alcohol, and the reaction is esterification and/or ester exchange reaction; the usage of the catalyst is 1-8% of the weight of the tallow seed oil, the alcohol/oil mol ratio is maintained to be 5-45:1, and the reaction temperature is 60-180 DEG C; the reaction lasts 1-10h at normal pressure, glycerol is separated, the methyl alcohol is evaporated out, so that the prepared biodiesel is neutral. With the invention adopted, the magnetic nanometer difunctional solid catalyst having the advantages of high activity, good intensity, long service life and good regenerability is obtained; in addition, the post process of biodiesel production is simple, the yield is high, thus meeting the production requirement of environmental protection.

Description

Utilize tallowseed oil production method of bio-diesel oil and special solid catalyst
Technical field
The invention belongs to technical field of biodiesel preparation, be specifically related to a kind of tallowseed oil production method of bio-diesel oil and special solid catalyst of utilizing, this catalyzer belongs to a kind of magnetic nanometer difunctional.
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 oil and fat 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, corrosive equipment, 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.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 broad research in the association area of preparation biodiesel catalyst both at home and abroad, at present, the related patent U.S. Patent No. report is more both at home and abroad; As application number be 200610019245.4, publication number is patent documentations such as CN1664072A, US5908946, EP0985654; 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; Although external relevant patent report is more, also not about the report of the magnetic nanometer difunctional that is used to prepare biofuel.It is that 200610019245.4 (denomination of invention prepares method of bio-diesel oil for adopting nano solid acid or base catalysis) documents and application number are 200510082922.2 (production technology of preparing biodiesel by solid magnetic catalyst) document that portion and closely-related patent documentation of the present invention such as application number are arranged in existing publication document.Application number is that to disclose a kind of it is said be solid acid or the solid alkali as a catalyst that utilizes nano level (the nanoparticle footpath is in the 1-100nm scope) for 200610019245.4 patent documentation; 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 is 40-100 ℃; Reaction back is centrifugal to go out thick methyl esters and glycerine mutually, and then thick methyl esters is distilled out low-carbon alcohol respectively mutually with glycerine, obtains neutral biofuel and glycerine at last.But its specification sheets does not fully disclose the concrete preparation method of said 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; Illustrative has not adopted its catalytic activity of nanocatalyst and the variation tendency thereof that invention is claimed; Be used for preparing the problems such as saponification that biofuel can't overcome the biodiesel manufacture process by its said nano solid base; The protection domain of claims request of this patented claim can not get the support (like critical technical parameters such as the nanometer range of nanocatalyst, adding proportion, mol ratios) of specification sheets, and the technology contents public who provides according to this specification sheets can't reproduce the effect shown in this invention book.Number of patent application is that 200510082922.2 to disclose a kind of it is said be to utilize solid magnetic catalyst, and the catalyzer add-on is the 1-10% of vegetable and animals oils weight, the mol ratio 3-40 of low-carbon alcohol and vegetable and animals oils: 1, and 40-100 ℃ of reaction 1-5 hour down.But its specification sheets does not carry out magnetic characterization to said catalyzer.
Magnetic nanometer difunctional is the important development direction of preparation biofuel, because this type of catalyzer had both had the characteristics of nanocatalysts such as high-ratio surface, high catalytic activity, makes catalyzer be easy to separate with reaction product again.Difunctional magnetic nano-catalyst has not only overcome liquid acid alkaline catalysts environmental pollution problems; Common solid acid and the insufficient problem of solid alkali part have been solved again; Like nanoparticle and product separation difficulty, can cause in the product mechanical impurity too high, influence the use of product.Therefore, researching and developing the magnetic Nano solid 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; Develop a kind of tallowseed oil production method of bio-diesel oil and special solid catalyst of utilizing; This catalyzer belongs to a kind of magnetic nanometer difunctional; Utilize this catalyst can significantly improve the transformation efficiency of biofuel, overcoming the agglomeration traits of nano particle in the existing catalyzer, and saponification in preparation biofuel process and catalyzer a gordian technique difficult problem such as separate.Task of the present invention comprises that also the magnetic nanometer difunctional with the present invention's preparation is applied in the preparation of biofuel; Through enforcement of the present invention; Obtain the magnetic nanometer difunctional of outstanding advantages such as a kind of activity is high, intensity is big, the life-span is long, regenerability is good; It is simple to be used in preparation biofuel aftertreatment technology, and the product yield is high, meets the environmental protection production requirement.
Solving technical scheme of the present invention is:
A kind of tallowseed oil production method of bio-diesel oil of utilizing places a reaction system with tallowseed oil and low-carbon alcohol, under the catalysis of catalyzer, reacts; Described catalyzer be particle diameter be the nano-scale magnetic nano solid acid of 30-200nm or/and alkali, described low-carbon alcohol is a methyl alcohol, described reaction is esterification and/or transesterification reaction; Said catalyst levels is the 1%-8% (preferably, catalyst levels is the 2%-6% of tallowseed oil weight) of tallowseed oil weight, and maintenance alcohol/molar equivalent is 5-45: 1 (preferably; Alcohol/molar equivalent is 8-30: 1), temperature of reaction is 60-180 ℃ (preferably, temperature of reaction is 75-150 ℃); The following reaction times of normal pressure is that (preferably, the reaction times is 2～8h) to 1-10h, 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 95%, and the use that can repeat and regenerate of the difunctional solid acid of described magnetic Nano, alkaline catalysts.
As preferred version, single reaction times with transesterify wherein is preferably 2-8h, and reaction time of esterification is 1-3h in esterification and the transesterification reaction coupling technology, and the transesterification reaction time is 2-6h.
Raw oil of the present invention can be Chinese tallow tree seed crude oil, also can be Chinese tallow tree seed Clean products.
According to the production needs, the applicant has prepared a kind of magnetic nano solid acid or/and alkaline catalysts, and solid acid catalyst wherein is selected from sulfuric acid/ZIRCONIUM DIOXIDE 99.5-titanium oxide/Z 250 (SO 4 2-/ ZrO 2-TiO 2/ Fe 3O 4), sulfuric acid/γ-aluminium sesquioxide-silicon-dioxide/Z 250 (SO 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4), sulfuric acid/alumina-zirconia/Z 250 (SO 4 2-/ Al 2O 3-ZrO 2/ Fe 3O 4), sulfuric acid/ZIRCONIUM DIOXIDE 99.5/Z 250 (SO 4 2-/ ZrO 2/ Fe 3O 4), ammonium persulfate/titanium oxide-ZIRCONIUM DIOXIDE 99.5/Z 250 S 2O 8 2-/ TiO 2-ZrO 2/ Fe 3O 4Wherein a kind of or its combination.Its detailed preparation method is said referring to embodiment 1.
The difunctional solid base catalyst of magnetic Nano is selected from Potassium monofluoride/alkaline earth metal oxide/Z 250 (KF/MO/Fe 3O 4) (M=Mg, Ca, Sr, Ba), Potassium monofluoride/calcium aluminium/Z 250 (KF/CaAl (O)/Fe 3O 4), saltpetre/magnalium/Z 250 (KNO 3/ MgAl (O)/Fe 3O 4) wherein a kind of or its combination.Its detailed preparation method is said referring to embodiment 1.
The detailed preparation method of the difunctional solid acid of magnetic Nano of the present invention, alkaline catalysts is referring to " embodiment " of the present invention, and promptly embodiment 1 is said.
For embodiment of the present invention better; When adopting Chinese tallow tree seed crude oil; In reaction system, add the difunctional solid acid catalyst of above-mentioned magnetic Nano earlier and carry out esterification (reaction times is 1-3h), carry out transesterification reaction (reaction times is 2-6h) with nano-magnetic nano double function solid base catalyst again.If Chinese tallow tree seed Clean products; Only need in reaction system of the present invention, add the difunctional solid base catalyst of magnetic Nano carries out transesterification reaction (reaction times is 2-8h); Just can obtain the biofuel and the glycerine of ON-LINE SEPARATION of the present invention, thereby accomplish the present invention smoothly.
The invention has the beneficial effects as follows:
1. adopt rational preparation method to obtain the difunctional solid acid of magnetic Nano, the alkaline catalysts of 30～200nm, the type catalyzer has active height, intensity is big, the life-span is long and be easy to isolating characteristics.Like patent publication No. is that the nanocatalyst of CN1858160A preparation need carry out spinning when being used to prepare biofuel; Product and catalyst separating difficulty are big; And the magnetic nanometer difunctional of the present invention's preparation; Under the effect of externally-applied magnetic field, catalyzer and product sharp separation have been realized.Like the difunctional solid base catalyst KF/CaO/Fe of magnetic Nano 3O 4Magnetic intensity is seen Figure 13.From Figure 13, can know catalyzer KF/CaO/Fe 3O 4Be to have certain magnetic, magnetic intensity is 0.16emu/g; And number of patent application is 200510082922.2 and for the catalyzer magnetic intensity is characterized.
2. utilizing the difunctional solid acid of magnetic Nano, alkaline catalysts is that feedstock production biofuel transformation efficiency reaches more than 95% with the tallowseed oil; 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 oil motor fully.
With the difunctional solid acid of magnetic Nano, the alkaline catalysts coupling prepares biofuel that tallowseed oil raw oil is not had selectivity, the tallowseed oil that is suitable for different acid numbers prepares biofuel.Patent publication No. is the scope of application of the undeclared catalyzer of CN1858160A, needs to make catalyzer with the difunctional solid acid of magnetic Nano for the high acid value crude oil, or carries out transesterify with the difunctional solid alkali of magnetic Nano again with the preparatory esterification of the difunctional solid acid of magnetic Nano.The present invention uses these two kinds of catalyzer coupling techniques to overcome the harsh requirement to the raw oil material moity.
4. utilize the difunctional solid acid of magnetic Nano, alkaline catalysts to prepare biofuel and traditional liquid acid, the meliority that alkali is bigger than having; Production technique is simple, and product need not neutralization, washing, environment is not produced and pollutes; 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 30～200nm scope, the disposable successive reaction transformation efficiency of preparation biofuel reaches more than 95%.
5. this biodiesel consumption uses 1～10h generally at 1%～8% of weight of oil at every turn, can use 16～82 activity constant basically continuously, and this catalyzer can also be regenerated, and activity and live catalyst after the regeneration are suitable.Like catalyst S O 4 2-/ ZrO 2-TiO 2/ Fe 3O 4With tallowseed oil, methyl alcohol is that the feedstock production biodiesel catalyst uses and the following Fig. 1 of the result of use of regenerating, Fig. 2 continuously.Reaction conditions: temperature of reaction is 150 ℃, and molar ratio of methanol to oil is 12: 1, and catalyst levels is 5% (wt) of oil, and the reaction times is 6h.
Fig. 1 has shown the catalyst S O of the present invention's preparation 4 2-/ ZrO 2-TiO 2/ Fe 3O 4The relation of access times and esterification yield, Fig. 2 has then shown catalyst S O of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4The relation of regeneration access times and esterification yield.
From Fig. 1 and Fig. 2, can find out the difunctional solid acid catalyst SO of magnetic Nano of the present invention's preparation 4 2-/ ZrO 2-TiO 2/ Fe 3O 4Use continuously and the back of regenerating uses its catalytic performance fluctuation less; Basically do not influence catalytic effect; With patent publication No. be that the CN1858160A document relatively has more superior catalytic performance, and the relation of the access times of CN1858160A document and undeclared catalyzer, regeneration access times and esterification yield.
Description of drawings
Fig. 1 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4The relation of access times and esterification yield;
Fig. 2 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4The relation of regeneration access times and esterification yield;
Fig. 3 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4Temperature is to the influence of esterification yield;
Fig. 4 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4Reaction times is to the influence of esterification yield;
Fig. 5 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4Molar ratio of methanol to oil influences esterification yield;
Fig. 6 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4Catalyst levels influences esterification yield;
Fig. 7 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4Charge capacity is to the influence of esterification yield;
Fig. 8 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4Calcining temperature is to the influence of esterification yield;
Fig. 9 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4Calcination time is to the influence of esterification yield;
Figure 10 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4Transmission electron microscope picture, Figure 10 a are the general views of Figure 10; Figure 10 b is that amplify the part of Figure 10, has shown one of them particulate enlarged image of Figure 10;
Figure 11 is the difunctional solid acid SO of magnetic Nano of the present invention 4 2-/ ZrO 2-TiO 2/ Fe 3O 4Transmission electron microscope picture;
Figure 12 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4The XRD diffractogram;
Figure 13 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4Magnetic hysteresis loop;
Figure 14 is magnetic substrate Fe of the present invention 3O 4The XRD powder diagram;
Figure 15 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4The graph of a relation of the recovery and magneticstrength;
Figure 16 is the difunctional solid alkali KF/CaO/Fe of magnetic Nano of the present invention 3O 4The recovery and time relation figure.
Embodiment
The preparation of the difunctional solid acid of embodiment 1 magnetic Nano, alkaline catalysts
One, the difunctional solid acid catalyst of magnetic Nano is selected from the following compounds preparation: sulfuric acid/ZIRCONIUM DIOXIDE 99.5-titanium oxide/Z 250 (SO 4 2-/ ZrO 2-TiO 2/ Fe 3O 4), sulfuric acid/γ-aluminium sesquioxide-silicon-dioxide/Z 250 (SO 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4), sulfuric acid/alumina-zirconia/Z 250 (SO 4 2-/ Al 2O 3-ZrO 2/ Fe 3O 4), ammonium persulfate/titanium oxide-ZIRCONIUM DIOXIDE 99.5/Z 250 S 2O 8 2-/ TiO 2-ZrO 2/ Fe 3O 4Wherein a kind of or its combination.
Concrete preparation technology's division is following:
(1) magnetic substrate Fe 3O 4Preparation press amount of substance and calculate, with FeCl 26H 2O and FeCl 34H 2O [n (Fe 3+): n (Fe 2+)=2: 1] mixing solutions pack in the three-necked bottle, be positioned in 65 ℃ the water bath with thermostatic control, stirring and dripping 1: 1 ammoniacal liquor of concentration simultaneously is pH=12 until solution.Continue constant temperature and stir ageing 30min, magnetic separate and subside thing is washed to neutral repeatedly with zero(ppm) water in the cooling back, preserves subsequent use or filtration drying is subsequent use with suspended state.That Figure 14 shows is magnetic substrate Fe 3O 4The XRD diffractogram, as can be seen from Figure 14, the Fe that the present invention is prepared 3O 4Has superparamagnetism preferably.
(2) sulfuric acid/ZIRCONIUM DIOXIDE 99.5-titanium oxide/Z 250 (SO 4 2-/ ZrO 2-TiO 2/ Fe 3O 4) the preparation concrete steps be: get 50ml magnetcisuspension supernatant liquid in three-necked flask, press amount of substance again and calculate TiCl 4And ZrOCl 28H 2O [n (Ti 4+): n (Zr 4+)=6: 1] the aqueous solution add in the three-necked flask, stir and drip 28% ammoniacal liquor down, obtain a large amount of flockss, uses the pH detection paper to be 9-10, deposition room temperature ageing 24h, filtration, and be washed till no Cl with zero(ppm) water to pH -, porphyrize behind 110 ℃ of dry 2h is used 0.5molL again -1H 2SO 4Dipping 12h, behind the filtration drying, at 550 ℃ of calcinings of retort furnace 3h, cooling, porphyrize places moisture eliminator subsequent use.
Catalyzer TEM characterizes: as can be seen from Figure 11; The most of particle shape almost spherical of catalyzer; Particle diameter between 50～80nm, the globule size distribution uniform, and from figure passable finding out; Magnetic substrate (aterrimus) has the tangible dirt settling of one deck (light gray) all around, and it is middle to explain that magnetic substrate well is wrapped in by catalyzer.
(3) sulfuric acid/γ-aluminium sesquioxide-silicon-dioxide/Z 250 (SO 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4) the preparation concrete steps be: get 50ml magnetcisuspension supernatant liquid and in three-necked flask, calculate AlCl by amount of substance again 46H 2O and Na 2SiO 3[n (Al 3+): n (Si 4+)=1: 10] the aqueous solution join in the three-necked flask, stir drip 1: 1 down ammoniacal liquor to pH=8～9, be deposited in 65 ℃ and be stirred to the gel after-filtration, and be washed till no Cl with zero(ppm) water -, porphyrize behind 110 ℃ of dry 2h is used 0.5molL again -1H 2SO 4Dipping 12h, behind the filtration drying, at 550 ℃ of calcinings of retort furnace 3h, cooling, porphyrize places moisture eliminator subsequent use.
(4) sulfuric acid/alumina-zirconia/Z 250 (SO 4 2-/ Al 2O 3-ZrO 2/ Fe 3O 4) the preparation concrete steps be: get 50ml magnetcisuspension supernatant liquid in three-necked flask, press amount of substance again and calculate AlCl 46H 2O and ZrOCl 28H 2O [n (Al 3+): n (Zr 4+)=2: 1] the aqueous solution add in the three-necked flask, stir the ammoniacal liquor that dripped down 1: 1, be 9-10 to the pH detection paper to pH, precipitate 70 ℃ of ageing 12h, filtration, and be washed till no Cl with zero(ppm) water -, porphyrize behind 110 ℃ of dry 2h is used 0.5molL again -1H 2SO 4Dipping 12h, behind the filtration drying, at 550 ℃ of calcinings of retort furnace 3h, cooling, porphyrize places moisture eliminator subsequent use
(5) ammonium persulfate/titanium oxide-ZIRCONIUM DIOXIDE 99.5/Z 250 S 2O 8 2-/ TiO 2-ZrO 2/ Fe 3O 4The preparation concrete steps be: get 50ml magnetcisuspension supernatant liquid in three-necked flask, press amount of substance again and calculate TiCl 4And ZrOCl 28H 2O [n (Ti 4+): n (Zr 4+)=6: 1] the aqueous solution add in the three-necked flask, stir and drip 28% ammoniacal liquor down, obtain a large amount of flockss, uses the pH detection paper to be 9-10, deposition room temperature ageing 24h, filtration, and be washed till no Cl with zero(ppm) water to pH -, porphyrize behind 110 ℃ of dry 2h is used 0.5molL again -1(NH 4) S 2O 8Dipping 24h, behind the filtration drying, at 550 ℃ of calcinings of retort furnace 3h, cooling, porphyrize places moisture eliminator subsequent use.
Two, the difunctional solid base catalyst of magnetic Nano is selected from the following compounds preparation: Potassium monofluoride/alkaline earth metal oxide/Z 250 (KF/MO/Fe 3O 4) (M=Mg, Ca, Sr, Ba), Potassium monofluoride/calcium aluminium/Z 250 (KF/CaAl (O)/Fe 3O 4), saltpetre/magnalium/Z 250 (KNO 3/ MgAl (O)/Fe 3O 4) wherein a kind of or its combination.Concrete grammar is:
(1) Potassium monofluoride/quicklime/Z 250 (KF/CaO/Fe 3O 4) the preparation concrete steps be: take by weighing 23gFe respectively 3O 4Powder and 280g quicklime (CaO) mix, and its mixture was transferred on the ball mill ball milling 1 hour, dipping 20 minutes in isopyknic Potassium monofluoride (KF) aqueous solution then, and then calcining 4 hours in 600 ℃ of retort furnaces, subsequent use with the furnace temperature cool to room temperature.
Catalyzer (KF/CaO/Fe 3O 4) condition optimizing:
1) calcining temperature is that 12: 1, catalyst levels are that 3h, temperature of reaction are under 70 ℃ the condition for heavy 3% (ω), the reaction times of oil to the influence of esterification yield at molar ratio of methanol to oil, investigates the influence of calcining temperature to catalyst efficient.By shown in Figure 8: when (1) was lower than 600 ℃ when calcining temperature, along with the rising of calcining temperature, esterification yield improved gradually; The catalytic efficiency (that catalyzer is described is increasingly high, and this is because when calcining temperature is lower than 600 ℃, along with the rising of calcining temperature; The amount of the branch of KF improves gradually; Thereby the quantity of the basic center that is produced is also more and more, and the alkalescence of catalyzer is also more and more stronger, and catalytic efficiency (also improves naturally thereupon.(2) when calcining temperature is higher than 600 ℃, along with the rising of 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.So its optimum calcinating temperature is 600 ℃.
2) calcination time is to the influence of catalyst efficient
At molar ratio of methanol to oil is that 12: 1, catalyst levels are that 3h, temperature of reaction are under 70 ℃ the condition for heavy 3% (ω), the reaction times of oil, investigates the influence of calcination time to catalyst efficient.By shown in Figure 9: when calcination time was lower than 4h, along with the prolongation of calcination time, esterification yield improved gradually (1); The catalytic efficiency (that is catalyzer promotes rapidly along with the prolongation of calcination time; This is because when calcination time is lower than 4h, and along with the prolongation of calcination time, the quantity of the basic center that is produced is also more and more; The alkalescence of catalyzer is also more and more stronger, and catalytic efficiency (also improves naturally thereupon.(2) when calcination time during greater than 4h; Prolongation along with 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; 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.So its best calcination time is 4h.
3) catalyst loadings is to the influence of catalyst efficient
At molar ratio of methanol to oil is that 12: 1, catalyst levels are that 3h, temperature of reaction are under 70 ℃ the condition for heavy 3% (ω), the reaction times of oil, investigates the influence of catalyst proportion to catalytic efficiency (.By shown in Figure 7: KF/CaO/Fe is worked as in (1) 3O 4Proportioning is lower than at 25% o'clock, and along with the increase gradually of KF ratio, esterification yield increases gradually, explains that the catalytic efficiency (of catalyzer is increasingly high, and this is because work as KF/CaO/Fe 3O 4Proportioning is lower than at 25% o'clock, and the KF of carrier surface distributes more even, and eclipsing effect is little, and along with the increase gradually of KF ratio, catalytic efficiency (also improves thereupon.(2) work as KF/CaO/Fe 3O 4Proportioning is higher than at 50% o'clock, and along with the increase gradually of KF composition, esterification yield reduces gradually, explains that the catalytic efficiency (of catalyzer is more and more lower, and this is because work as KF/CaO/Fe 3O 43Proportioning is higher than at 50% o'clock, and it is inhomogeneous that the KF of carrier surface distributes, and eclipsing effect is big, along with the increase gradually of KF ratio, does not only make KF/CaO/Fe 3O 4Alkalescence strengthen and to make its reduction on the contrary, catalytic efficiency (also decreases.So its optimum load amount is 25%.
4) catalyzer tem analysis
Figure 10 a and Figure 10 b are the transmission electron microscope pictures of the catalyzer that under top condition, prepares; From Figure 10 a, can find out, most of particle shape almost spherical, particle diameter is between 40～80nm; There is certain sintering phenomenon in the globule size distribution uniform between the part particle; Can find out that from Figure 10 b catalyst surface is the micropore shape, show that this type of catalyzer just has bigger specific surface area, catalytic activity is higher.
5) catalyzer XRD analysis
Catalyzer KF/CaO/Fe 3O 4XRD analysis such as Figure 12, the catalyzer before a representes to calcine among Figure 12; B representes to calcine the preceding catalyzer of afterreaction; C representes to calcine the catalyzer behind the afterreaction.A can find out from Figure 12, and catalyzer mainly was made up of Ca (OH) 2 and CaO before calcining, and the alkalescence of alkalimetal oxide is better than its oxyhydroxide, and therefore, this stage does not produce more intense basic sites.B can find out from Figure 12; Through high-temperature calcination; Ca (OH) 2 diffraction peaks disappear, and have new KCaF3 diffraction peak to occur, and explain in the high-temperature calcination process; KF and support C aO take place to interact and have formed new crystalline phase, that is to say that high-temperature calcination has a very important role for the activation of catalyzer.B and c contrast can find out that after reaction, the diffraction peak of KCaF3 weakens to some extent from Figure 12, but the degree that weakens is little, and is also promptly better through the interaction of carrier and KF after the reaction.Can find out from Figure 12 a, b, c, Fe not occur in the whole XRD figure spectrum 3O 4Diffraction peak, Fe is described 3O 4What be wrapped is relatively good.
(2) Potassium monofluoride/calcium aluminium/Z 250 (KF/CaAl (O)/Fe 3O 4) concrete steps are; With CaCl 22H 2O and AlCl 36H 2O is made into mixed solution A (ratio with amount of substance is calculating in 3: 1), and 1: 1 ammoniacal liquor is that (amount of substance of ammoniacal liquor is AlCl to solution B 36H 24 times of O).Solution A and B are added drop-wise to prior scattered Fe simultaneously 3O 4There-necked flask in, drip the back mixed solution in 65 ℃ of water-baths aging 12 hours, filter, 80 degree obtained CaAl (O)/Fe in dry 10 hours 3O 4Catalyzer then adopts isopyknic KF solution impregnation, drying and 600 degree high-temperature calcinations, and is subsequent use with the furnace temperature cool to room temperature after accomplishing
(3) saltpetre/magnalium/Z 250 (KNO 3/ MgAl (O)/Fe 3O 4) concrete steps are: with MgCl 26H 2O and AlCl 36H 2O is made into mixed solution A (ratio with amount of substance is calculating in 3: 1), and 0.1mol/LNaOH is that (amount of substance with ammoniacal liquor is AlCl to solution B 36H 24 times of calculating of O).Solution A and B are added drop-wise to prior scattered Fe simultaneously 3O 4There-necked flask in, with mixed solution in 80 ℃ of water-baths aging 12 hours, filter, 80 ℃ of dryings obtained MgAl (O)/Fe in 12 hours after dripping 3O 4Catalyzer then adopts isopyknic KF solution impregnation, drying and 600 degree high-temperature calcinations, and is subsequent use with the furnace temperature cool to room temperature after accomplishing
Embodiment 2 catalyst separating methods
Get tallowseed oil (Clean products, acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 4kg, catalyzer are KF/CaO/Fe 3O 4(particle diameter of catalyzer is 50nm) 500g (catalyst levels be tallowseed oil weight 5%); Described tallowseed oil, catalyzer and methyl alcohol are placed a reaction kettle, and temperature of reaction is 60 ℃, after normal pressure reacts 3～4h down; Reaction kettle is placed on the electro-magnet; Energized, coming controlling magnetic field intensity through the size of regulating electric current is 0.1-0.8T (tesla), investigates the recovery of catalyzer and the relation of magneticstrength.The recovery of the catalyzer that Figure 15 shows and the relation of magneticstrength, Figure 16 demonstration be the recovery and the time relation of magneticstrength catalyzer when being 0.5T.As can beappreciated from fig. 15 when magneticstrength during greater than 0.3T, the recovery of catalyzer is 94.8%; When magneticstrength during greater than 0.5T, the recovery of catalyzer is more than 99.5%.As can beappreciated from fig. 16, when reaction kettle was placed 40s on electro-magnet, the recovery of catalysis base reached 98%.So the reaction kettle that will react after accomplishing is placed on the electro-magnet of a magneticstrength greater than 0.5T, storage period, catalyzer just separated with reaction product completely during greater than 1min.
Embodiment 3 utilizes tallowseed oil production biofuel embodiment 1
Get tallowseed oil (Clean products, acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 4kg, catalyzer are KF/CaO/Fe 3O 4(particle diameter of catalyzer is 50nm) 300g (catalyst levels be tallowseed oil weight 3%); Described tallowseed oil, catalyzer and methyl alcohol are placed a reaction kettle; Temperature of reaction is 60 ℃, and normal pressure is reaction 3～4h down, adopts the method separating catalyst of embodiment 2; Product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.In the present embodiment, the biofuel transformation efficiency reaches more than 97%, the use that can repeat and regenerate of production biofuel rear catalyst.The repetition and the regeneration tests of catalysis base are implemented as follows:
The repeated experiments of l, catalysis base: after accomplishing first set reaction, product is taken out and catalyzer is stayed in the reactor drum feed intake again (methyl alcohol and tallowseed oil) and carried out second time and react.After reaction is accomplished for the second time, repeat a step and react for the third time, so reaction repeated.
2, catalyst regeneration is tested: catalyzer carries out catalyst regeneration through repeatedly reacting when the back catalytic activity obviously reduces (low 50%), adopt Potassium monofluoride (KF) solution incipient impregnation, drying and the high-temperature calcination of 0.1mol/L after catalyzer process methanol wash, the drying.
Embodiment 4 utilizes Chinese tallow tree seed crude oil production biofuel embodiment 2
Get Chinese tallow tree seed crude oil (the calculation value is 76mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ ZrO 2-TiO 2/ Fe 3O 4(particle diameter of catalyzer is 60nm) 200g (catalyst levels be tallowseed oil weight 2%) is in reaction kettle; Temperature of reaction is 150 ℃, and normal pressure is reaction 8～10h down, isolates catalyzer by the method for embodiment 2; Product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency of present embodiment production reaches more than 98%, according to the method for embodiment 3 catalyzer is carried out repetition and uses with regeneration.
The preparation condition optimization of biofuel:
1) temperature of reaction is to the influence of esterification yield
The mol ratio of methyl alcohol and tallowseed oil is 12: 1, and catalyst levels is 5wt.%, during reaction times 6h, investigates the influence of differential responses temperature to the grease transformation efficiency, and the result sees Fig. 3.Fig. 3 shows that temperature is bigger to the influence of the transesterification reaction of solid acid catalysis grease and methyl alcohol, and reaction or transformation efficiency are very not low basically below 100 ℃; Along with temperature raises; Reaction rate accelerates, the esterification yield of tallowseed oil obviously increases, when 150 ℃ of left and right sides; The esterification yield of reaction is the highest, reaches more than 95%.When temperature continued to be increased to more than 150 ℃, esterification yield descended to some extent, and this is because too high temperature makes methyl alcohol excessive concentration in gas phase, make the molar ratio of methanol to oil reduction and cause esterification yield to descend, but influence is not very significantly.So its optimal reaction temperature is 150 ℃.
2) reaction times is to the influence of esterification yield
The mol ratio of methyl alcohol and tallowseed oil is 12: 1, and catalyst levels is 5wt.%, during 150 ℃ of temperature, investigates the influence of differential responses time to the grease transformation efficiency, and the result sees Fig. 4.Can be known that by Fig. 4 optimum reacting time is 6h, before 6h, along with the growth in reaction times, the transformation efficiency of reaction increases gradually.Surpass 6h, transformation efficiency reduces, and this possibly be owing to the increase along with the reaction times, and the possibility that side reaction takes place strengthens, and the reversed reaction degree of fatty acid methyl ester increases, thereby causes esterification yield to reduce.
3) catalyst levels is 5wt.%, and 150 ℃ of temperature during reaction times 6h, are investigated the influence of different alcohols molar equivalent to the grease transformation efficiency, and the result sees Fig. 5.Because the acid-catalyzed transesterification reaction is reversible balanced reaction; According to reaction equilibrium theory, before reaction arrived balance, the forward that the increase reactant concn helps reacting carried out; So reaction is carried out towards the direction that generates product, and molar ratio of methanol to oil is greater than 3: 1 of theoretical amount.From experiment, can find that along with the increase of molar ratio of methanol to oil, esterification yield raises gradually, the esterification yield to reaction when molar ratio of methanol to oil surpasses 12: 1 does not have any influence basically, because reaction is near balance with this understanding.So its best molar ratio of methanol to oil is 12: 1.
4) catalyst levels is to the influence of esterification yield
The mol ratio of methyl alcohol and tallowseed oil is 12: 1, and 150 ℃ of temperature during reaction times 6h, are investigated the influence of different catalysts consumption to the grease transformation efficiency, and the result sees Fig. 6.Can know by Fig. 6, when carrying out transesterification reaction, when catalyst consumption is 5% (wt.) left and right sides of tallowseed oil quality with solid acid catalyst; Esterification yield is maximum; Continue to increase catalyst consumption, the transformation efficiency of reaction slightly reduces, this possibly be because; The existence of excessive an acidic catalyst causes the increase of backward reaction degree, makes the partial fatty acid methyl esters of generation be hydrolyzed to lipid acid and methyl alcohol again.So being oil, its optimum catalyst consumption weighs 5%.
Embodiment 5 utilizes the embodiment 3 of tallowseed oil Clean products production biofuel
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 10kg, catalyzer KF/CaAl (O)/Fe 3O 4(particle diameter of catalyzer is 150nm) 400g (catalyst levels be tallowseed oil weight 4%) is in a reaction system (for example reaction kettle); Temperature of reaction is 85 ℃; Normal pressure is reaction 2～4h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 97.5% in the present embodiment, and the catalyzer of the method that adopts embodiment 3 after to the production biofuel carries out repetition to be used with regeneration.
Embodiment 6 utilizes the embodiment 4 of tallowseed oil Clean products production biofuel
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 10kg, catalyzer KF/CaAl (O)/Fe 3O 4(particle diameter of catalyzer is 90nm) 600g (catalyst levels be tallowseed oil weight 6%) is 90 ℃ in the reaction kettle for reaction temperature; Normal pressure is reaction 1～2h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 95% in the present embodiment.
Embodiment 7 utilizes tallowseed oil Clean products production biofuel embodiment 5
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 6kg, catalyzer KNO 3/ MgAl (O)/Fe 3O 4(particle diameter of catalyzer is 60nm) 200g (catalyst levels be tallowseed oil weight 2%) is in a reaction kettle; Temperature of reaction is 60 ℃; Normal pressure is reaction 3～5h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.Biofuel transformation efficiency in the present embodiment reaches more than 96.3%.
Embodiment 8 utilizes tallowseed oil Clean products production biofuel embodiment 6
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 6kg, catalyzer KNO 3/ MgAl (O)/Fe 3O 4(particle diameter of catalyzer is 30nm) 300g (catalyst levels be tallowseed oil weight 3%) is in a reaction kettle; Temperature of reaction is 75 ℃; Normal pressure is reaction 6～8h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency of present embodiment reaches more than 96.9%.
Embodiment 9 utilizes tallowseed oil Clean products production biofuel embodiment 7
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 10kg, catalyzer KF/CaAl (O)/Fe 3O 4(particle diameter of catalyzer is 200nm) 800g (catalyst levels be tallowseed oil weight 8%) is in a reaction kettle; Temperature of reaction is 85 ℃; Normal pressure is reaction 2～4h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 97.5% in the present embodiment.
Embodiment 10 utilizes tallowseed oil Clean products production biofuel embodiment 8
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 12kg, catalyzer KF/CaAl (O)/Fe 3O 4(particle diameter of catalyzer is 30nm) 600g (catalyst levels be tallowseed oil weight 6%) is in a reaction system (for example reaction kettle); Temperature of reaction is 90 ℃; Normal pressure is reaction 1～2h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 95% in the present embodiment.
Embodiment 11 utilizes tallowseed oil Clean products production biofuel embodiment 9
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 6kg, catalyzer KNO 3/ MgAl (O)/Fe 3O 4(particle diameter of catalyzer is 80nm) 200g (catalyst levels be tallowseed oil weight 2%) is in a reaction system (for example reaction kettle); Temperature of reaction is 60 ℃; Normal pressure is reaction 3～5h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.3% in the present embodiment.
Embodiment 12 utilizes tallowseed oil Clean products production biofuel embodiment 10
Get tallowseed oil Clean products (acid number is less than or equal to 1.5mgKOH/g) 10kg, methyl alcohol 6kg, catalyzer KNO 3/ MgAl (O)/Fe 3O 4(particle diameter of catalyzer is 200nm) 800g (catalyst levels be tallowseed oil weight 8%) is in a reaction kettle; Temperature of reaction is 75 ℃; Normal pressure is reaction 6～8h down; Adopt the method for embodiment 2 to isolate the catalyzer of generation, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency that utilizes the present invention to produce reaches more than 96.9%.
Embodiment 13 utilizes Chinese tallow tree seed crude oil production biofuel embodiment 11
Get Chinese tallow tree seed crude oil (acid number is 55mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S 2O 8 2-/ TiO 2-ZrO 2/ Fe 3O 4(particle diameter of catalyzer is 200nm) 800g (catalyst levels be Chinese tallow tree seed weight 8%) is in a reaction kettle; Temperature of reaction is 180 ℃; Normal pressure is reaction 8～10h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 95% in the present embodiment.
Embodiment 14 utilizes Chinese tallow tree seed crude oil production biofuel embodiment 12
Get Chinese tallow tree seed crude oil (acid number is 82mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S 2O 8 2-/ TiO 2-ZrO 2/ Fe 3O 4(particle diameter of catalyzer is 120nm) 400g (catalyst levels be Chinese tallow tree seed weight 4%) is in a reaction kettle; Temperature of reaction is 150 ℃; Normal pressure is reaction 6～8h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96% in the present embodiment.
Embodiment 15 production of biodiesel embodiment 13
Get Chinese tallow tree seed crude oil (acid number equals 100mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S 2O 8 2-/ TiO 2-ZrO 2/ Fe 3O 4(particle diameter of catalyzer is 30nm) 300g (catalyst levels be Chinese tallow tree seed weight 3%) is in a reaction system (for example reaction kettle); Temperature of reaction is 100 ℃; Normal pressure is reaction 6～8h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 95.8% in the present embodiment.
Embodiment 16 production of biodiesel embodiment 14
Get Chinese tallow tree seed crude oil (acid number is 76mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ Al 2O 3-ZrO 2/ Fe 3O 4(particle diameter of catalyzer is 100nm) 300g (catalyst levels be Chinese tallow tree seed weight 3%) is in a reaction kettle; Temperature of reaction is 150 ℃; Normal pressure is reaction 8～10h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 95% in the present embodiment.
Embodiment 17 production of biodiesel embodiment 15
Get Chinese tallow tree seed crude oil (acid number equals 90mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4(particle diameter of catalyzer is 130nm) 300g (catalyst levels be Chinese tallow tree seed weight 3%) is in a reaction kettle; Temperature of reaction is 180 ℃; Normal pressure is reaction 6～8h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.3% in the present embodiment.
Embodiment 18 production of biodiesel embodiment 16
Get Chinese tallow tree seed crude oil (acid number equals 78mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ Al 2O 3-ZrO 2/ Fe 3O 4(particle diameter of catalyzer is 160nm) 800g (catalyst levels be tallowseed oil weight 8%) is in a reaction kettle; Temperature of reaction is 160 ℃; Normal pressure is reaction 8～9h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 95% in the present embodiment.
Embodiment 19 production of biodiesel embodiment 17
Get Chinese tallow tree seed crude oil (acid number is 84mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ Al 2O 3-ZrO 2/ Fe 3O 4(particle diameter of catalyzer is 30nm) 400g (catalyst levels be tallowseed oil weight 4%) is in a reaction kettle; Temperature of reaction is 160 ℃; Normal pressure is reaction 5～7h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.8% in the present embodiment.
Embodiment 20 production of biodiesel embodiment 18
Get Chinese tallow tree seed crude oil (acid number is 65mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4(particle diameter of catalyzer is 180nm) 600g (catalyst levels be Chinese tallow tree seed weight 6%) is in a reaction kettle; Temperature of reaction is 180 ℃; Normal pressure is reaction 4～6h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.3% in the present embodiment.
Embodiment 21 production of biodiesel embodiment 19
Get Chinese tallow tree seed crude oil (acid number is for equaling 101mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4(particle diameter of catalyzer is 30nm) 200g (catalyst levels be Chinese tallow tree seed weight 2%) is in a reaction kettle; Temperature of reaction is 150 ℃; Normal pressure is reaction 6～7h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.3% in the present embodiment.
Embodiment 22 production of biodiesel embodiment 20
Get Chinese tallow tree seed crude oil (acid number equals 75mgKOH/g) 10kg, methyl alcohol 4kg, catalyst S O 4 2-/ γ-Al 2O 3-SiO 2/ Fe 3O 4(particle diameter of catalyzer is 80nm) 500g (catalyst levels be Chinese tallow tree seed weight 5%) is in a reaction kettle; Temperature of reaction is 120 ℃; Normal pressure is reaction 8～10h down; Adopt the method for embodiment 2 to isolate catalyzer, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.3% in the present embodiment.
Embodiment 23 utilizes Chinese tallow tree seed crude oil production biofuel embodiment 21
Take by weighing SO 4 2-/ ZrO 2-TiO 2/ Fe 3O 4(particle diameter of catalyzer is 600nm), KF/CaO/Fe 3O 4(particle diameter of catalyzer is 600nm) each 4.00g of catalyzer places the three-necked bottle of two 250mL respectively, 150mL Chinese tallow tree seed crude oil (for 110mgKOH/g), 46mL methyl alcohol is added earlier fill SO 4 2-/ ZrO 2-TiO 2/ Fe 3O 4In the three-necked bottle of (particle diameter of catalyzer is 600nm), about 105 ℃ of following pre-esterification reactor 3h, adopt the method separating catalyst of embodiment 2 simultaneously, the product of preparatory esterification is added dress KF/CaO/Fe again 3O 4Three-necked bottle in, continue down to adopt the method for embodiment 2 to isolate catalyzer simultaneously about reaction 1h at 68 ℃, product changes the separating funnel standing demix over to, promptly gets biofuel and by-product glycerin.The biofuel transformation efficiency reaches more than 96.8% in the present embodiment.

Claims (2)

1. one kind is utilized tallowseed oil production method of bio-diesel oil, and tallowseed oil and low-carbon alcohol are placed a reaction system, under the catalysis of catalyzer, reacts; It is characterized in that; Described catalyzer be particle diameter be the magnetic nano solid acid of 30-200nm or/and alkali, described low-carbon alcohol is a methyl alcohol, described reaction is esterification and/or transesterification reaction; Reaction time of esterification is 1-3h, and the transesterification reaction time is 2-6h;
Said catalyst levels is the 2%-6% of tallowseed oil weight, and keeping the mol ratio of alcohol/oil is 8-30: 1, and temperature of reaction is 75-90 ℃, and normal pressure is reaction 1-10h down, and separation of glycerin steams methyl alcohol, makes the biofuel of preparation be neutral;
Wherein:
Described magnetic nano solid acid catalyst is selected from wherein a kind of or its combination of sulfuric acid/ZIRCONIUM DIOXIDE 99.5-titanium oxide/Z 250, sulfuric acid/γ-aluminium sesquioxide-silicon-dioxide/Z 250 and ammonium persulfate/titanium oxide-ZIRCONIUM DIOXIDE 99.5/Z 250, and described magnetic Nano solid base catalyst is selected from Potassium monofluoride/quicklime/Z 250, Potassium monofluoride/calcium aluminium/Z 250, saltpetre/magnalium/Z 250 is wherein a kind of or its combination.
2. be applicable to the described special-purpose catalyst that utilizes tallowseed oil production biofuel method of claim 1; It is characterized in that; This catalyzer is that particle diameter is that the magnetic nano solid acid of 30-200nm is or/and alkali; Described magnetic nano solid acid catalyst is selected from wherein a kind of or its combination of sulfuric acid/ZIRCONIUM DIOXIDE 99.5-titanium oxide/Z 250, sulfuric acid/γ-aluminium sesquioxide-silicon-dioxide/Z 250 and ammonium persulfate/titanium oxide-ZIRCONIUM DIOXIDE 99.5/Z 250, and described magnetic Nano solid base catalyst is selected from Potassium monofluoride/quicklime/Z 250, Potassium monofluoride/calcium aluminium/Z 250 and saltpetre/magnalium/Z 250 is wherein a kind of or its combination.
CN2008100467545A 2008-01-23 2008-01-23 Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof Expired - Fee Related CN101492603B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100467545A CN101492603B (en) 2008-01-23 2008-01-23 Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100467545A CN101492603B (en) 2008-01-23 2008-01-23 Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof

Publications (2)

Publication Number Publication Date
CN101492603A CN101492603A (en) 2009-07-29
CN101492603B true CN101492603B (en) 2012-11-28

Family

ID=40923397

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100467545A Expired - Fee Related CN101492603B (en) 2008-01-23 2008-01-23 Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof

Country Status (1)

Country Link
CN (1) CN101492603B (en)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838591B (en) * 2010-05-07 2013-08-21 厦门大学 Catalytic esterification method of oil with high acid value
CN102302942B (en) * 2011-07-04 2012-12-05 中国科学院广州能源研究所 Nano-magnetic bifunctional solid alkali catalyst for transesterification reaction and preparation method thereof
CN102335607A (en) * 2011-07-20 2012-02-01 北京工业大学 Preparation method and application of magnetic solid base catalyst for synthesizing biodiesel
CN105032431A (en) * 2014-12-12 2015-11-11 北京恩泽福莱科技有限公司 Magnetic solid alkali catalyst and preparation method thereof
CN105419885B (en) * 2015-11-24 2017-05-10 华东理工大学 Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid
CN105524718A (en) * 2016-01-15 2016-04-27 广西阔能霸能源科技开发有限责任公司 Preparation method for biodiesel with Garcinia multiflora Champ as raw material
CN105695107A (en) * 2016-01-15 2016-06-22 广西阔能霸能源科技开发有限责任公司 Method for preparing biodiesel with euphorbia tirucalli as raw material
CN105542952A (en) * 2016-01-15 2016-05-04 广西阔能霸能源科技开发有限责任公司 Method for preparing biodiesel from malania oleifera oil
CN105524720A (en) * 2016-01-15 2016-04-27 广西阔能霸能源科技开发有限责任公司 Production method for biodiesel by utilizing Xanthoceras sorbifolia Bunge oil
CN105695106A (en) * 2016-01-15 2016-06-22 广西阔能霸能源科技开发有限责任公司 Preparation method for biodiesel
CN105542969A (en) * 2016-01-15 2016-05-04 广西阔能霸能源科技开发有限责任公司 Method for preparing biodiesel from pistacia chinensis bunge
CN105670805A (en) * 2016-01-15 2016-06-15 广西阔能霸能源科技开发有限责任公司 Production method of biodiesel using Aleurites moluccana fruits as raw materials
CN105524644B (en) * 2016-01-15 2017-08-25 广西阔能霸能源科技开发有限责任公司 A kind of synthetic method of biodiesel
CN105969419B (en) * 2016-01-15 2018-10-26 浙江海鸿工业产品设计有限公司 A kind of preparation method of high-quality biodiesel
CN105524719A (en) * 2016-01-15 2016-04-27 广西阔能霸能源科技开发有限责任公司 Production method for biodiesel
CN105670806A (en) * 2016-01-15 2016-06-15 广西阔能霸能源科技开发有限责任公司 Production method of Armeniaca sibirica biodiesel
CN105542954A (en) * 2016-01-15 2016-05-04 广西阔能霸能源科技开发有限责任公司 Method for preparing biodiesel with hodgsonia macrocarpa as raw material
CN105670801A (en) * 2016-01-15 2016-06-15 广西阔能霸能源科技开发有限责任公司 Method for improving yield of biodiesel
CN105542953A (en) * 2016-01-15 2016-05-04 广西阔能霸能源科技开发有限责任公司 Method for producing biodiesel through comprehensive utilization of chinaberry seeds
CN105670807A (en) * 2016-01-15 2016-06-15 广西阔能霸能源科技开发有限责任公司 Method for preparing biodiesel by using Jatropha carcas as raw material
CN105670802A (en) * 2016-01-15 2016-06-15 广西阔能霸能源科技开发有限责任公司 Method for producing biodiesel by using magnetic nanometer catalyst
CN108531295B (en) * 2018-04-19 2021-08-10 湘潭大学 Method for catalytically synthesizing biodiesel by KF/MgFeLaO solid base
CN110787801B (en) * 2019-11-05 2021-10-01 江南大学 Synthetic method and application of magnetic solid acid catalyst
CN114292689B (en) * 2021-12-07 2023-03-31 广州崃克保新材料科技有限公司 Release agent composition
CN117327537B (en) * 2023-11-27 2024-04-19 石家庄环腾能源科技有限公司 Environment-friendly treatment process of industrial mixed oil

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1290574A (en) * 2000-11-08 2001-04-11 哈尔滨工程大学 Magnetic solid super strong acid catalyst and its preparing method
CN1858160A (en) * 2006-06-02 2006-11-08 中国农业科学院油料作物研究所 Method for preparing biological diesel oil using nano solid acid or alkali catalyst
CN1891787A (en) * 2005-07-07 2007-01-10 南昌大学 Production technology for preparing biodiesel by solid magnetic catalyst
CN1891786A (en) * 2005-07-07 2007-01-10 南昌大学 Production technology for preparing biodiesel from tallowseed oil
CN1970692A (en) * 2006-12-07 2007-05-30 天津大学 Process for preparing biological diesel oil by using loop reactor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1290574A (en) * 2000-11-08 2001-04-11 哈尔滨工程大学 Magnetic solid super strong acid catalyst and its preparing method
CN1891787A (en) * 2005-07-07 2007-01-10 南昌大学 Production technology for preparing biodiesel by solid magnetic catalyst
CN1891786A (en) * 2005-07-07 2007-01-10 南昌大学 Production technology for preparing biodiesel from tallowseed oil
CN1858160A (en) * 2006-06-02 2006-11-08 中国农业科学院油料作物研究所 Method for preparing biological diesel oil using nano solid acid or alkali catalyst
CN1970692A (en) * 2006-12-07 2007-05-30 天津大学 Process for preparing biological diesel oil by using loop reactor

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
凌翠霞等."磁性纳米固体超强酸催化合成没食子酸正丁酯".《化工时刊》.2006,第20卷(第1期),第25-26页.
王君等."磁性固体超强酸SO42-/ZrO2-Al2O3-Fe3O4的制备与性能研究".《无机化学学报》.2007,第23卷(第7期),第1137-1142页.
陈文伟等."纳米磁性固体催化剂制备生物柴油".《太阳能学报》.2007,第28卷(第3期),第324-328页.
黎汉生等.磁性催化剂研究进展.《材料导报》.2005,第19卷(第8期),第5-12页. *

Also Published As

Publication number Publication date
CN101492603A (en) 2009-07-29

Similar Documents

Publication Publication Date Title
CN101492603B (en) Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof
Salimi et al. Study and optimization of conditions of biodiesel production from edible oils using ZnO/BiFeO3 nano magnetic catalyst
Guo et al. Process optimization of biodiesel production from waste cooking oil by esterification of free fatty acids using La3+/ZnO-TiO2 photocatalyst
Yadav et al. Methyl transesterification of waste cooking oil using a laboratory synthesized reusable heterogeneous base catalyst: Process optimization and homogeneity study of catalyst
Dehkordi et al. Transesterification of waste cooking oil to biodiesel using Ca and Zr mixed oxides as heterogeneous base catalysts
Yu et al. Transesterification of Pistacia chinensis oil for biodiesel catalyzed by CaO–CeO2 mixed oxides
Maleki et al. Transesterification of canola oil and methanol by lithium impregnated CaO–La2O3 mixed oxide for biodiesel synthesis
Kaur et al. Ethanolysis of waste cottonseed oil over lithium impregnated calcium oxide: Kinetics and reusability studies
Nasreen et al. Preparation of biodiesel from soybean oil using La/Mn oxide catalyst
CN103801282B (en) A kind of solid base catalyst and Synthesis and applications thereof
CN101294094A (en) Method for preparing biological diesel oil by using nano-solid heteropoly acid, heteropolybase catalyst
Dai et al. Applications of M2ZrO2 (M= Li, Na, K) composite as a catalyst for biodiesel production
CN111375431B (en) Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification
Ganesan et al. Esterification of free fatty acids using ammonium ferric sulphate-calcium silicate as a heterogeneous catalyst
Nasreen et al. Transesterification of soybean oil catalyzed by Sr-doped cinder
CN100475333C (en) Catalyst for synthesizing bio diesel oil and preparation method thereof
CN101293209B (en) Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof
WO2020022143A1 (en) Method for producing biofuel
CN101294093B (en) Integrated preparation method for biological diesel oil and isolated plant
CN102172521B (en) Solid basic catalyst and preparation method and application thereof
Kaur et al. An efficient and reusable Li/NiO heterogeneous catalyst for ethanolysis of waste cottonseed oil
CN100375780C (en) Production of biological diesel oil with solid alkali
Kumari et al. Greener synthesis of zirconium-based nanocatalyst for transesterification
Asri et al. Development of heterogeneous alumina supported base catalyst for biodiesel production
CN101130163A (en) Load type flyash solid base catalyst for producing biological diesel oil and method of producing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20121128

Termination date: 20140123