CN1962824A - Process for preparing supported solid catalyst for use in production of bio-diesel oil - Google Patents
Process for preparing supported solid catalyst for use in production of bio-diesel oil Download PDFInfo
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- CN1962824A CN1962824A CNA2006101367992A CN200610136799A CN1962824A CN 1962824 A CN1962824 A CN 1962824A CN A2006101367992 A CNA2006101367992 A CN A2006101367992A CN 200610136799 A CN200610136799 A CN 200610136799A CN 1962824 A CN1962824 A CN 1962824A
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- biofuel
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- hydrotalcite
- solid catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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 discloses a preparing method of load alkaline catalyst to manufacture biological diesel, which comprises the following steps: allocating the material with at least one hydrotalcite or hydrotalcite load KF, CaF2, ZnF2, NaF or K2CO3 with density at 3-20%; sintering at 400-800 Deg C for 2-10h; grinding. The invention makes the production rate by over 94%, which recycles residual carbinol to avoid huge waste of difficult separation of by-product and carbinol.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for the production biofuel.
Background technology
Diesel oil occupies higher share as a kind of important refining of petroleum product in various countries' fuel structure, become important power fuel.The raising of exhausted day by day and people's environmental consciousness of petroleum resources, people begin to pay close attention to oil-fired substitute.Biofuel is to be the renewable energy source of raw material production with vegetables oil or animal grease, can be used as fine petroleum diesel surrogate.
Biofuel, be to prepare at present mostly by the homogeneous catalysis ester-interchange method, basic catalyst is mainly sodium hydroxide, potassium hydroxide, sodium methylate etc., consumption is about about 1% (oil is heavy), speed of response is fast, transformation efficiency height (more than 95%), but it is many also to exist the three wastes simultaneously, environmental pollution is serious, problems such as aftertreatment complexity.In the existing document, Wu Guoying etc., vegetables oil prepares biofuel, the Jiangsu Petrochemical Engineering College journal, 2002,14 (13): 8～11, use liquid alkali catalyst.Also there is the people under the condition that liquid acid catalyst exists, to prepare biofuel.CN 13282762A adopts sulfuric acid or Phenylsulfonic acid to make catalyzer, and CN1412278A adopts sulfuric acid to make catalyzer, but serious to equipment corrosion with the liquid acid as catalyst, and product is difficult to separate the aftertreatment complexity.Therefore, solid base catalyst is competitively studied in countries in the world.The patent No. be US2006069274 U.S. Patent Publication a kind of " biofuel serialization production process ", it is a heterogeneous catalysis process, catalyst system therefor is the mixture of CaO and MgO; The patent No. is that the European patent of WO2006002087 discloses a kind of " method for producing biodiesel ", for heterogeneous transesterify catalytic process, has very high transformation efficiency, and its catalyzer is non-public, only knows it is solid catalyst.The patent No. be CN 1664072A Chinese patent application " adopt solid alkali legal system be equipped with method of bio-diesel oil ", catalyzer is alkali or alkaline earth metal oxide, loading type alkali metal and oxyhydroxide, and it comprises: alkalimetal oxide Rb2O, alkaline earth metal oxide and oxyhydroxide MgO, CaO, SrO, BaO, MgO-NaOH, MgO-Na, Mg-Al composite oxides, loading type alkali metal and oxyhydroxide γ-Al
2O
3-NaOH-Na, γ-Al
2O
3-KOH-K; Chinese patent CN 1680514A has applied for " a kind of solid base catalyst and preparation method and application ", it relates to a kind of multi-phase solid base catalyst that uses in the transesterification reaction of preparation biofuel, this solid base catalyst is made up of alkaline-earth metal and alkali-metal oxide compound, described alkaline-earth metal is one or more among Mg, Ca, Sr and the Ba, described basic metal is one or more among Li, Na, K and the Rb, wherein alkaline-earth metal and alkali-metal mol ratio are not more than 2/3, and the yield of its biofuel can reach more than 85%; The Chinese patent of patent No. CN 1580190A has then adopted solid acid, alkaline catalysts to prepare biofuel.Above-mentioned catalyzer is existing raising the aspect the production biofuel, but stable not enough, transformation efficiency does not yet reach the stage that can popularize in an all-round way.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the load type solid body base catalyst of production biofuel.
The objective of the invention is to realize in the following way: a kind of preparation method who is used for the supported solid catalyst of production biofuel is characterized in that: with hydrotalcite or houghite dip loading concentration is KF, the CaF of 3-20%
2, ZnF
2, NaF, K
2CO
3In at least a, 400～800 ℃ of calcinings 2-10 hour, pulverize then.
Also hydrotalcite or houghite can be calcined 4-12 hour at 400～800 ℃, dip loading concentration is KF, the CaF of 3-20% then
2, ZnF
2, NaF, K
2CO
3In at least a, 400～800 ℃ of calcinings 2-10 hour, pulverize then.
The present invention has following beneficial effect, and 1, the productive rate that adopts present method to prepare biofuel can reach more than 97%, and every performance index of product meet German diesel quality index (DINV51606); 2, Preparation of Catalyst is simple, and excellent catalytic effect is reusable, and makes the production of biodiesel technical process simple, mild condition, and last handling process is simplified greatly, and the no three wastes produce, environmental friendliness; 3, byproduct glycerine is easy to separate and purifies, and reacts remaining methyl alcohol and can be recycled, and has avoided because byproduct is difficult to separate the huge waste that causes with methyl alcohol.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1:
Taking by weighing 57.8g magnesium nitrate and 21.8g aluminum nitrate is dissolved in 250 milliliters of redistilled waters, and then adding 120g urea, put into 110 ℃ of oily territories, stir reaction times 10h, static crystallization 20h in 95 ℃ of thermostat containers again, suction filtration then, wash to PH be about 7, filter cake is dry in 100 ℃ of vacuum drying ovens, obtains the Mg/Al atomic ratio and be 4: 1 magnesium aluminum-hydrotalcite.
Prepare MgO-ZnO, CaO-ZnO, MgO-γ-Al with the same manner
2O
3, houghites such as MgO-TiO, MgO-SrO.
Get 100ml concentration and be 3% Potassium monofluoride and be carried on 100 gram hydrotalcites, static 8h, vacuum-drying then, at 500 ℃ of calcining and activating 4h, the loaded article solid base catalyst, be used for the production of biofuel.
Get 100ml concentration equally and be 3% Potassium monofluoride and be carried on 100 gram houghites, static 8h, vacuum-drying then, at 500 ℃ of calcining and activating 4h, the loaded article solid base catalyst, be used for the preparation of biofuel.
In kind with the CaF of 3-20% concentration
2, ZnF
2, NaF or K
2CO
3Be carried on the hydrotalcite, get different loaded article solid catalysts.
In kind with the CaF of 3-20% concentration
2, ZnF
2, NaF or K
2CO
3Be carried on the houghite, obtain respective negative loading solid catalyst.
Embodiment 2:
Taking by weighing 57.8g magnesium nitrate and 21.8g aluminum nitrate is dissolved in the 250ml redistilled water, and then add 120g urea and 10g gelatin, and put into 105 ℃ of oily territories, stir, reaction times 12h, static crystallization 20h in 95 ℃ of thermostat containers again, suction filtration then, wash to PH be about 7, filter cake is dry in 100 ℃ of vacuum drying ovens, obtain the Mg/Al atomic ratio and be 4: 1 magnesium aluminum-hydrotalcite, the above-mentioned hydrotalcite that obtains 500 ℃ of calcinings 6 hours down, is just obtained the Mg-Al complex metal oxides.
Prepare MgO-ZnO, CaO-ZnO, MgO-γ-Al with the same manner
2O
3, houghites such as MgO-TiO, MgO-SrO, the above-mentioned houghite that obtains 500 ℃ of down calcinings 6 hours, is obtained corresponding complex metal oxides.
Get 100ml concentration and be 3% Potassium monofluoride and be carried on 100 gram Mg-Al complex metal oxidess, static 8h, vacuum-drying then, at 500 ℃ of calcining and activating 4h, the loaded article solid base catalyst, be used for the preparation of biofuel.
Get 100ml concentration equally and be the complex metal oxides that 3% Potassium monofluoride is carried on 100 gram houghites, static 8h, vacuum-drying then, at 500 ℃ of calcining and activating 4h, the loaded article solid base catalyst, be used for the preparation of biofuel.
In kind with the CaF of 3-20% concentration
2, ZnF
2, NaF or K
2CO
3Be carried on the complex metal oxides of hydrotalcite through obtaining after the calcining, get different loaded article solid catalysts.
In kind with the CaF of 3-20% concentration
2, ZnF
2, NaF or K
2CO
3Be carried on the complex metal oxides of houghite through obtaining after the calcining, obtain respective negative loading solid catalyst.
Specific embodiments 3:
With 50g soybean oil (density 0.92g/cm
3) and 11.03g (density 0.792g/cm
3) methyl alcohol puts into three mouthfuls of round-bottomed flasks of 250ml, adds the prepared load type solid body base catalyst of 1g, is heated to 65 ℃, violent stirring, reaction 4h, reacting liquor while hot is filtered, and isolates catalyzer, then filtrate is poured into the separating funnel standing demix.The upper strata product is a biofuel, and lower floor is a byproduct glycerine.
With the biofuel product chromatography of gases analysis that makes, chromatographic condition: stainless steel packed column (3mm * 2m Silar-9cp); Fid detector, temperature of vaporization chamber are 250 ℃; Adopt programmed temperature method,, keep 2min, rise to 215 ℃, keep 10min with 1.5 ℃/min since 160 ℃; Carrier gas is a high pure nitrogen, 19.0ml/min; Hydrogen, 40ml/min; Air, 400ml/min; Sample size 0.5 μ l.
The biofuel quality standard that meets Germany according to the quality standard of analyzing biofuel.
Biofuel quality index analytical results and comparison
| Performance perameter | Self-control | German standard (DINV51606) |
| Density (g/cm 3, 15 ℃) and (40 ℃/m of viscosity 2，s -1) open flash point, (℃) sulphur content, (%) cetane value ash content, (%) moisture, (mg/kg) neutralization value KOH/mg.kg -1The total glycerine (%) of methanol content (%) free glycerol (%) | ?0.8841 ?3.89 ?186 ?0.0028 ?57 ?0.023 ?215 ?0.155 ?0.0049 ?0.0019 ?0.2157 | ?0.875～0.900 ?3.5～5.0 ?≥110 ?≤0.01 ?≥49 ?≤0.03 ?≤300 ?≤0.5 ?≤0.03 ?≤0.02 ?≤0.25 |
Claims (2)
1, a kind of preparation method who is used for the supported solid catalyst of production biofuel is characterized in that: with hydrotalcite or houghite dip loading concentration is KF, the CaF of 3-20%
2, ZnF
2, NaF or K
2CO
3At least a, 400～800 ℃ of calcinings 2-10 hour, pulverize then.
2, the preparation method who is used for the supported solid catalyst of production biofuel according to claim 1 is characterized in that: hydrotalcite or houghite were calcined 4-12 hour at 400～800 ℃, and dip loading concentration is KF, the CaF of 3-20% then
2, ZnF
2, NaF or K
2CO
3At least a, 400～800 ℃ of calcinings 2-10 hour, pulverize then.
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|---|---|---|---|
| CNB2006101367992A CN100497527C (en) | 2006-12-01 | 2006-12-01 | Process for preparing supported solid catalyst for use in production of bio-diesel oil |
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|---|---|---|---|
| CNB2006101367992A CN100497527C (en) | 2006-12-01 | 2006-12-01 | Process for preparing supported solid catalyst for use in production of bio-diesel oil |
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| CN1962824A true CN1962824A (en) | 2007-05-16 |
| CN100497527C CN100497527C (en) | 2009-06-10 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039202A (en) * | 2010-12-15 | 2011-05-04 | 东南大学 | Solid-base monolithic catalyst with regular porous channels and preparation method of solid-base monolithic catalyst |
| CN101195759B (en) * | 2007-12-19 | 2011-07-20 | 贵州大学 | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst catalysis |
| CN102161933A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Method for preparing biodiesel by one step based on lepra fruits as raw material |
| CN106693941A (en) * | 2015-07-29 | 2017-05-24 | 上海华谊（集团）公司 | Catalyst for preparing methyl acrylate and acrylic acid, and preparation method and application thereof |
| CN107115874A (en) * | 2017-06-13 | 2017-09-01 | 贵州大学 | A kind of preparation method of the difunctional modified fluorinated zinc solid catalyst of soda acid |
| CN107541234A (en) * | 2017-09-02 | 2018-01-05 | 湘潭大学 | A kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite |
| CN108795578A (en) * | 2018-07-06 | 2018-11-13 | 扬州工业职业技术学院 | A method of utilizing catalyzed by solid base preparing biodiesel by ester exchange |
| CN108927218A (en) * | 2018-07-06 | 2018-12-04 | 扬州工业职业技术学院 | A kind of polyaniline-coated biology carbon material and its preparing the application in solid base |
| CN108927217A (en) * | 2018-07-06 | 2018-12-04 | 扬州工业职业技术学院 | A kind of solid base catalyst based on polyaniline-coated carbon material and its application in preparation biodiesel |
| CN109046417A (en) * | 2018-08-17 | 2018-12-21 | 湘潭大学 | A kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis |
| CN111468149A (en) * | 2020-05-15 | 2020-07-31 | 淮阴工学院 | Novel biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof |
| CN115999528A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof |
-
2006
- 2006-12-01 CN CNB2006101367992A patent/CN100497527C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195759B (en) * | 2007-12-19 | 2011-07-20 | 贵州大学 | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst catalysis |
| CN102039202B (en) * | 2010-12-15 | 2012-09-19 | 东南大学 | Solid-base monolithic catalyst with regular porous channels and preparation method of solid-base monolithic catalyst |
| CN102039202A (en) * | 2010-12-15 | 2011-05-04 | 东南大学 | Solid-base monolithic catalyst with regular porous channels and preparation method of solid-base monolithic catalyst |
| CN102161933A (en) * | 2011-03-10 | 2011-08-24 | 四川大学 | Method for preparing biodiesel by one step based on lepra fruits as raw material |
| CN106693941A (en) * | 2015-07-29 | 2017-05-24 | 上海华谊（集团）公司 | Catalyst for preparing methyl acrylate and acrylic acid, and preparation method and application thereof |
| CN107115874B (en) * | 2017-06-13 | 2019-09-27 | 贵州大学 | A kind of preparation method of the difunctional modified fluorinated zinc solid catalyst of soda acid |
| CN107115874A (en) * | 2017-06-13 | 2017-09-01 | 贵州大学 | A kind of preparation method of the difunctional modified fluorinated zinc solid catalyst of soda acid |
| CN107541234A (en) * | 2017-09-02 | 2018-01-05 | 湘潭大学 | A kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite |
| CN108927218A (en) * | 2018-07-06 | 2018-12-04 | 扬州工业职业技术学院 | A kind of polyaniline-coated biology carbon material and its preparing the application in solid base |
| CN108927217A (en) * | 2018-07-06 | 2018-12-04 | 扬州工业职业技术学院 | A kind of solid base catalyst based on polyaniline-coated carbon material and its application in preparation biodiesel |
| CN108795578A (en) * | 2018-07-06 | 2018-11-13 | 扬州工业职业技术学院 | A method of utilizing catalyzed by solid base preparing biodiesel by ester exchange |
| CN109046417A (en) * | 2018-08-17 | 2018-12-21 | 湘潭大学 | A kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis |
| CN111468149A (en) * | 2020-05-15 | 2020-07-31 | 淮阴工学院 | Novel biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof |
| CN111468149B (en) * | 2020-05-15 | 2023-08-22 | 淮阴工学院 | Biodiesel solid catalyst KF/Ca-Mg-Al-O and preparation method and application thereof |
| CN115999528A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof |
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| Publication number | Publication date |
|---|---|
| CN100497527C (en) | 2009-06-10 |
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Granted publication date: 20090610 Termination date: 20100104 |