CN1966142A - Catalyst for synthesizing bio diesel oil and its preparation method - Google Patents
Catalyst for synthesizing bio diesel oil and its preparation method Download PDFInfo
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- CN1966142A CN1966142A CNA2006101250777A CN200610125077A CN1966142A CN 1966142 A CN1966142 A CN 1966142A CN A2006101250777 A CNA2006101250777 A CN A2006101250777A CN 200610125077 A CN200610125077 A CN 200610125077A CN 1966142 A CN1966142 A CN 1966142A
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- lanthanum
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- nitrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention relates to a method for using ester exchange method to synthesize the catalyst of biological diesel, wherein said catalyst is formed by lanthanum oxide or lanthanum composite metal oxide (La2O3-MOx); said M is one of Zn, Mg, Zr, Al, and Ca. And its preparation comprises that: dissolving lanthanum nitrate and zinc salt into distilled water, to prepare 7-20% solution; and dissolving sodium carbonate or caustic soda into 10%-25% solution; then mixing the two solutions, drying and breaking the deposit, to obtain the catalyst. Said catalyst has high activity and stability.
Description
Technical field
The present invention relates to a kind of O composite metallic oxide catalyst that is used for biodiesel synthesis and preparation method thereof, relate in particular to the lanthanum metal oxide of ester-interchange method biodiesel synthesis or O composite metallic oxide catalyst of lanthanum and preparation method thereof.
Background technology
Biodiesel is a kind of form of biomass energy.The main component of biodiesel is a fatty acid methyl ester, be a kind of with vegetable oil and animal tallow be main material production, character and the closely similar fuel oil of ordinary diesel oil.Biodiesel has renewable, environmentally friendly and transportation, storage and advantage safe in utilization.
The preparation method of biodiesel has physics method and chemical method, but the physics method can cause carbon deposit and make problem such as lubricating oil viscosity increase.Chemical method comprises high temperature pyrolytic cracking and ester-interchange method, and the major product of high temperature pyrolytic cracking is a biogasoline, and biodiesel is its byproduct.By contrast, ester-interchange method is a kind of better preparation method.Ester-interchange method is to carry out ester exchange reaction with animal or plant grease and methyl alcohol under catalyst action, generates corresponding fatty acid methyl ester, is drying to obtain biodiesel through washing again.At present, the used catalyst system and catalyzing of ester-interchange method production biodiesel can be divided into homogeneous catalysis system and heterogeneous catalysis system, but homogeneous catalysis system exists and is difficult to separate, bring problems such as three-waste pollution and energy consumption height, and adopt the technology of heterogeneous catalyst systems simple, can not bring pollution problem because of producing corresponding salt, the recyclable utilization of heterogeneous catalysis yet.Therefore, efficient, the environment amenable heterogeneous catalysis of exploitation has great importance.
At present, being used for the catalyst that fatty glyceride and methyl alcohol ester exchange reaction biodiesel synthesis use is homogeneous catalyst mostly.Come biodiesel synthesis as in CN1560197A and CN1197937C, adopting toluenesulfonic acid to make catalyst, in US6712867B1, adopt NaOH or KOH to make catalyst and come biodiesel synthesis, and CN1743417A adopts KOH and sodium alkoxide to come biodiesel synthesis as catalyst respectively among CN1400281A and the US20050011112A1.
Adopt homogeneous catalyst,, have the cost height, separate, reclaim problems such as difficulty and contaminated environment, its commercial Application is restricted though the productive rate of fatty glyceride and methyl alcohol ester exchange reaction biodiesel synthesis, reaches the balance time weak point up to more than 93%.In order to overcome the shortcoming of homogeneous catalyst, adopt heterogeneous solid acid alkali catalytic agent to come catalytically synthesizing biological diesel oil among the CN1580190A, the yield of biodiesel can reach 90%.In WO2006050925A1, use MgO or MgO-Al
2O
3Make the catalyst of biodiesel synthesis, the yield of biodiesel can reach about 92%.But, use MgO or MgO-Al
2O
3During catalyst, the temperature of ester exchange reaction has limited it in industrial application up to 250 ℃.Hak-Joo Kim etc. (Hak-Joo Kim, Bo-Seung Kang, Min-JuKim, Young Moo Park, et al.Catalysis today, 93-95 (2004): 315-320) studied Na, NaOH loads on γ-Al
2O
3On the carrier to the catalytic activity of rapeseed oil and methyl alcohol ester exchange biodiesel synthesis.Find Na/NaOH/ γ-Al
2O
3Activity of such catalysts is the highest, and the productive rate of biodiesel is about 93%.But this loaded catalyst is difficult to return to the problem of initial activity after having loss of active component and regeneration after the repeated use.(Galen J.Suppes such as Galen J.Suppes, Mohanprasad A.Dasari, Eric J.Doskocil, et al.Appl Catal A, 2004,257:213-223) studied molecular sieve and oxide catalyst catalytic performance to soya-bean oil and methyl alcohol ester exchange biodiesel synthesis.Found that when adopting the ETS-10 molecular sieve to make catalyst, the yield of biodiesel can reach 95%.But this molecular sieve catalyst is subject in the grease influence of free aliphatic acid and inactivation.
Rare earth is widely used in aspects such as oil, chemical industry and environmental protection as catalysis material, though have the reported in literature rare earth oxide in the esterification of acid and alcohol, have preferably catalytic activity (Hao Qiang breathes out brave. chemistry of forest product and industry, 2000,20 (3): 17-21; Tang D Y, Huang J Y, Zhou Y H, et al.J Mol Cata A:Chemical, 1999,147:159-163.), but do not see the research report that has lanthanum metal oxide and composite oxides thereof to be used for the ester exchange reaction biodiesel synthesis both at home and abroad as yet.
Summary of the invention
The present invention is directed to problems of the prior art, a kind of lanthanum metal oxide of ester-interchange method biodiesel synthesis or composite oxide catalysts of lanthanum and preparation method thereof of being used for is provided.
Technical solution of the present invention is as follows:
The catalyst that is used for the ester-interchange method biodiesel synthesis of the present invention is by lanthana (La
2O
3) or the composite metal oxide (La of lanthanum
2O
3-MO
x) form, the composite metal oxide of lanthanum wherein, the percentage by weight of lanthana is 40%～99%, MO
xPercentage by weight be 1～60%.
Above-mentioned said M is meant one of following metal: Zn, Mg, Zr, Al, Ca.
Above-mentioned O composite metallic oxide catalyst, its preparation method concrete steps are as follows:
1. lanthanum salt or lanthanum salt and other slaine are dissolved in respectively in the distilled water, are made into mass percent respectively and are: 7%～20% solution;
2. being made into mass percent with distilled water and sodium carbonate or NaOH is 10%～25% sodium carbonate or sodium hydroxide solution;
3. sodium carbonate that 2. mixed solution that lanthanum salting liquid that 1. step is prepared or lanthanum solution and other slaine are formed and step prepare or sodium hydroxide solution and stream add, pH=7～8 of control solution, mix stirring, reacted 0.5～1.0 hour, and had precipitation after having reacted and generate;
4. with step 3. the sediment of gained be placed in the baking oven, with 100～120 ℃ of dryings of temperature 9～14 hours;
5. with the 4. dried sediment of step in Muffle furnace with 450～800 ℃ temperature roasting 3～10 hours, take out the composite oxide catalysts that promptly makes lanthanum oxide catalyst or lanthanum.
Above-mentioned steps 1. in said lanthanum salt be meant lanthanum nitrate, other slaine is meant one of following slaine: zinc nitrate, magnesium nitrate, aluminum nitrate, zirconyl nitrate, calcium nitrate.
Get the ZnO-La for preparing
2O
3Catalyst sample carries out XRD and characterizes, and finds that composite oxides do not have new crystalline phase to occur, and illustrate that this catalyst is by ZnO and La
2O
3Form.The XRD figure spectrum is seen accompanying drawing 1.
The present invention compared with prior art has following beneficial effect:
1, catalytic activity height, La of the present invention
2O
3Or La
2O
3-MOx catalyst has very high catalytic activity to the reaction of ester-interchange method biodiesel synthesis.The best homogeneous catalyst sodium alkoxide of its biodiesel production rate and present catalytic activity is suitable.
2, catalyst is easy to separate, reclaim.There are problems such as product separation, recycling difficulty in homogeneous catalyst, and product quality is caused certain influence, and catalyst of the present invention very easily separates with product.
3, do not pollute the environment and equipment.The homogeneous acid base catalyst is in catalytic reaction process, and a large amount of acid of meeting by-product, salt etc. pollute and severe corrosion equipment environment.And catalyst of the present invention in use both do not polluted the environment can etching apparatus yet.
4, regeneration easily, good stability.Catalyst of the present invention belongs to metal oxide or composite metal oxide, can reuse repeatedly, only needs simple roasting can recover active.And support type Na/NaOH/ γ-Al
2O
3Catalyst exists loss of active component, active structure to change, and is difficult to return to initial activity after the regeneration.
Description of drawings:
Fig. 1 .ZnO, ZnO-La
2O
3And La
2O
3The XRD diffraction pattern of catalyst.
Abscissa is 2 θ angles, and ordinate is a diffracted intensity.
Spectral line 1 is the XRD figure of ZnO, and spectral line 2 is n
ZnO/ n
La2O3=1 XRD figure, spectral line 3 are freshly prepd La
2O
3XRD figure, the La that spectral line 4 was to use
2O
3XRD figure.
The specific embodiment
Embodiment 1
The preparation of O composite metallic oxide catalyst:
1, gets 29.8g Zn (NO
3)
26H
2O adds 200g distilled water, is made into the solution of 8.2% (mass percent).Get 43.3g La (NO
3)
36H
2O adds 200g distilled water, is made into the solution of 13.3% (mass percent).
2, get 36g Na
2CO
3, add 200g distilled water, be made into the solution of 15% (mass percent).
3, with La (NO
3)
3, Zn (NO
3)
2And Na
2CO
3Three kinds of solution also flow in the adding beaker, the pH=7.5 mixing stirring of control solution, and afterreaction finished in 40 minutes;
4, filter the back gained and be deposited in 90 ℃ of baking ovens dry 12 hours;
5, with the 750 ℃ of roastings 5 hours in Muffle furnace of dried sediment, promptly make La
2O
3-ZnO catalyst, it is standby that drier is put in taking-up.
Embodiment 2
Catalyst with embodiment 1 preparation adopts rapeseed oil and methyl alcohol ester-interchange method biodiesel synthesis
1, in having the there-necked flask of condenser pipe, add the La that makes among the embodiment 1
2O
3Catalyst 3.9g, methyl alcohol 32.0g, rapeseed oil 100.0g;
2, be warmed up to 65 ℃, stirring and refluxing finishes reaction after 10 hours;
3, it is centrifugal under the 2000r/min rotating speed to take out reactant mixture, reclaims catalyst, and supernatant liquid is carried out air-distillation, reclaims excessive methyl alcohol, and again with the liquid standing demix, lower floor is a glycerine, and the upper strata is the product biodiesel;
4, use gas chromatographic analysis after getting a certain amount of supernatant liquid constant volume, the conversion ratio of determining the rapeseed oil of ester exchange reaction with internal standard method is 99.5%;
5, the catalyst of recovery is through after cleaning repeatedly, 90 ℃ dry 10 hours down, 750 ℃ of roastings 5 hours in Muffle furnace are again taken out and are put into drier in order to using next time.
Embodiment 3
The preparation process of O composite metallic oxide catalyst is identical with embodiment 1, but changes the kind of other slaine.Get 25.6g Mg (NO
3)
26H
2O adds the solution that distilled water 150g is made into 8.4% (mass percent); Get 37.5gAl (NO
3)
39H
2O adds the solution that distilled water 150g is made into 11.4% (mass percent); Get 26.7g ZrO (NO
3)
22H
2O adds the solution that distilled water 150g is made into 13.1% (mass percent); Get 23.6g Ca (NO
3)
24H
2O adds the solution that distilled water 150g is made into 9.8% (mass percent).The kind of base metal salt in the catalyst that makes is also changed, as shown in table 1.Adopt the ester-interchange method biodiesel synthesis with the catalyst that makes, reaction condition is identical with embodiment 2, and its catalytic performance the results are shown in Table 1
The different M of table 1 are to La
2O
3The influence of-MOx catalyst activity
| Parent M | La 2O 3/MgO | La 2O 3/Al 2O 3 | La 2O 3/ZrO 2 | La 2O 3/CaO |
| Biodiesel production rate/% | 98.6 | 98.1 | 97.9 | 98.4 |
Embodiment 4
The preparation process of O composite metallic oxide catalyst is identical with embodiment 1, but changes the consumption of other slaine, makes La in the catalyst that makes
2O
3, the mass ratio of ZnO also changes, and is as shown in table 2.Adopt the ester-interchange method biodiesel synthesis with the catalyst that makes, reaction condition is identical with embodiment 2, and its catalytic performance the results are shown in Table 2
The influence of the different lanthanum zinc comparison of table 2 catalyst activity
| La 2O 3: ZnO (mass ratio) | -/100 | 4/3 | 2/1 | 4/1 | 100/- |
| Conversion ratio/% | 34.8 | 81.4 | 89.9 | 97.5 | 99.5 |
Embodiment 5
The preparation process of O composite metallic oxide catalyst is identical with embodiment 1 with parent quality consumption, makes parent but change different zinc compounds, makes that the mass ratio of lanthana and zinc oxide is La in the catalyst that makes
2O
3: ZnO=4: 1.Adopt the ester-interchange method biodiesel synthesis with the catalyst that makes, reaction condition is identical with embodiment 2, and its catalytic performance the results are shown in Table 3
Embodiment 6
The preparation process of O composite metallic oxide catalyst is identical with embodiment 1 with parent quality consumption, but changes different precipitating reagents, makes that the mass ratio of lanthanum and zinc is La in the catalyst that makes
2O
3: ZnO=4: 1.Adopt the ester-interchange method biodiesel synthesis with the catalyst that makes, reaction condition is identical with embodiment 2, and its catalytic performance the results are shown in Table 3
The different parents of table 3 (precipitating reagent) are to the influence of catalyst activity
| Parent (precipitating reagent) | LaX 3/ZnX 2 | LaX 3/ZnY 2 | LaX 3/ZnX 2 a | LaX 3/ZnX 2 b |
| Biodiesel production rate/% | 97.5 | 98.1 | 98.5 | 97.4 |
X-NO
3 -，Y-Ac
-
A:NaOH makes the catalyst b:NH of precipitating reagent preparation
4OH makes the catalyst of precipitating reagent preparation
Embodiment 7
The preparation process of O composite metallic oxide catalyst is identical with embodiment 1 with parent quality consumption, makes that the mass ratio of lanthanum and zinc is La in the catalyst that makes
2O
3: ZnO=4: 1 but the sintering temperature difference.Adopt the ester-interchange method biodiesel synthesis with the catalyst that makes, reaction condition is identical with embodiment 2, and its catalytic performance the results are shown in Table 4
Table 4 sintering temperature is to the influence of catalyst activity
| Sintering temperature/℃ | 450 | 550 | 650 | 750 | 800 |
| Biodiesel production rate/% | 89.5 | 93.4 | 95.9 | 97.5 | 94.3 |
Claims (4)
1. a catalyst that is used for the ester-interchange method biodiesel synthesis is characterized in that, this catalyst is made up of the composite metal oxide of lanthana or lanthanum, the composite metal oxide of lanthanum wherein, and the percentage by weight of lanthana is 40%～99%, MO
xPercentage by weight be 1～60%.
2. according to the catalyst of claim 1, described M is meant one of following metal: Zn, Mg, Zr, Al, Ca.
3. according to the Preparation of catalysts method that is used for the ester-interchange method biodiesel synthesis of claim 1, its concrete steps are as follows:
1. lanthanum salt or lanthanum salt and other slaine are dissolved in respectively in the distilled water, are made into mass percent respectively and are: 7%～20% solution;
2. being made into mass percent with distilled water and sodium carbonate or NaOH is 10%～25% sodium carbonate or sodium hydroxide solution;
3. sodium carbonate that 2. mixed solution that lanthanum salting liquid that 1. step is prepared or lanthanum solution and other slaine are formed and step prepare or sodium hydroxide solution and stream add, pH=7～8 of control solution, mix stirring, reacted 0.5～1.0 hour, have precipitation to generate;
4. with step 3. the sediment of gained be placed in the baking oven, with 100～120 ℃ of dryings of temperature 9～14 hours;
5. with the 4. dried sediment of step in Muffle furnace with 450～800 ℃ temperature roasting 3～10 hours, promptly make the composite oxide catalysts of lanthanum oxide catalyst or lanthanum.
4. according to the preparation method of claim 3, wherein step 1. in said lanthanum salt be meant lanthanum nitrate, other slaine is meant one of following slaine: zinc nitrate, magnesium nitrate, aluminum nitrate, zirconyl nitrate, calcium nitrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101250777A CN100475333C (en) | 2006-11-20 | 2006-11-20 | Catalyst for synthesizing bio diesel oil and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101250777A CN100475333C (en) | 2006-11-20 | 2006-11-20 | Catalyst for synthesizing bio diesel oil and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1966142A true CN1966142A (en) | 2007-05-23 |
| CN100475333C CN100475333C (en) | 2009-04-08 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009143159A1 (en) * | 2008-05-19 | 2009-11-26 | Wayne State University | Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils |
| DE102008036295A1 (en) | 2008-08-04 | 2010-02-11 | Bayer Technology Services Gmbh | Catalyst composition for transesterification |
| WO2010148057A1 (en) * | 2009-06-16 | 2010-12-23 | Wayne State University | ZnO NANOPARTICLE CATALYSTS FOR USE IN TRANSESTERIFICATION AND ESTERIFICATION REACTIONS AND METHOD OF MAKING |
| US8975426B2 (en) | 2008-05-19 | 2015-03-10 | Wayne State University | ZnO nanoparticle catalysts for use in transesterification and esterification reactions and method of making |
| CN105642267A (en) * | 2016-02-24 | 2016-06-08 | 太原工业学院 | Biodiesel catalyst X-Ca-Zn-Al-O and preparation method |
| CN105642268A (en) * | 2016-02-24 | 2016-06-08 | 太原工业学院 | Biodiesel catalyst X-Ca-Mg-Al-O and preparation method |
| CN110665488A (en) * | 2019-09-30 | 2020-01-10 | 山东大学 | Acid-base double-nature solid catalyst, preparation and application thereof in producing biodiesel |
-
2006
- 2006-11-20 CN CNB2006101250777A patent/CN100475333C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009143159A1 (en) * | 2008-05-19 | 2009-11-26 | Wayne State University | Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils |
| US8163946B2 (en) | 2008-05-19 | 2012-04-24 | Wayne State University | Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils |
| US8895764B2 (en) | 2008-05-19 | 2014-11-25 | Wayne State University | ZnO nanoparticle catalysts for use in biodiesel production and method of making |
| US8975426B2 (en) | 2008-05-19 | 2015-03-10 | Wayne State University | ZnO nanoparticle catalysts for use in transesterification and esterification reactions and method of making |
| DE102008036295A1 (en) | 2008-08-04 | 2010-02-11 | Bayer Technology Services Gmbh | Catalyst composition for transesterification |
| WO2010015331A2 (en) * | 2008-08-04 | 2010-02-11 | Bayer Technology Services Gmbh | Catalyst composition for use in transesterification |
| WO2010015331A3 (en) * | 2008-08-04 | 2010-06-10 | Bayer Technology Services Gmbh | Catalyst composition for use in transesterification |
| WO2010148057A1 (en) * | 2009-06-16 | 2010-12-23 | Wayne State University | ZnO NANOPARTICLE CATALYSTS FOR USE IN TRANSESTERIFICATION AND ESTERIFICATION REACTIONS AND METHOD OF MAKING |
| CN105642267A (en) * | 2016-02-24 | 2016-06-08 | 太原工业学院 | Biodiesel catalyst X-Ca-Zn-Al-O and preparation method |
| CN105642268A (en) * | 2016-02-24 | 2016-06-08 | 太原工业学院 | Biodiesel catalyst X-Ca-Mg-Al-O and preparation method |
| CN105642267B (en) * | 2016-02-24 | 2018-06-05 | 太原工业学院 | Biodiesel catalyst X-Ca-Zn-Al-O and preparation method |
| CN110665488A (en) * | 2019-09-30 | 2020-01-10 | 山东大学 | Acid-base double-nature solid catalyst, preparation and application thereof in producing biodiesel |
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| Publication number | Publication date |
|---|---|
| CN100475333C (en) | 2009-04-08 |
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