CN102936045A - Preparation method of solid catalyst for biodiesel production - Google Patents
Preparation method of solid catalyst for biodiesel production Download PDFInfo
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- CN102936045A CN102936045A CN2012104219409A CN201210421940A CN102936045A CN 102936045 A CN102936045 A CN 102936045A CN 2012104219409 A CN2012104219409 A CN 2012104219409A CN 201210421940 A CN201210421940 A CN 201210421940A CN 102936045 A CN102936045 A CN 102936045A
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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
Abstract
The invention relates to a preparation method of a solid catalyst for biodiesel production, belonging to the field of oil product processing. The preparation method of a solid catalyst for biodiesel production is characterized by comprising the following steps: (1) preparing phosphotungstic acid: dissolving a certain amount of sodium tungstate hydrate and disodium hydrogen phosphate in boiling water while stirring, adding a certain amount of concentrated hydrochloric acid while continuously stirring, cooling, then adding ethyl ether, and drying to obtain the phosphotungstic acid for later use; and (2) preparing a solid cesium phosphotungstate catalyst: respectively preparing a certain amount of cesium carbonate and the prepared phosphotungstic acid into solutions, adding the cesium carbonate into the phosphotungstic acid solution while stirring, stirring for a certain time, then standing at room temperature for a certain time, and evaporating the water content at a certain temperature to obtain a white solid, namely the solid cesium phosphotungstate catalyst. The solid catalyst prepared by the invention has the following advantages: the solid catalyst has high specific surface area and super high acidity; under the low-temperature reaction conditions, the conversion rate of biodiesel through catalytic preparation can be up to 91% or above; the solid catalyst can be used repeatedly, etc.
Description
Technical field
The present invention relates to a kind of preparation method of the solid catalyst for production of biodiesel, belong to the oil product manufacture field.
Background technology
Biofuel is the renewable energy source of cleaning, the liquid fuel that it is made take the oil plant waterplant such as oil-yielding shrubs fruit, the engineering microalgaes such as the oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistache and animal grease, biodiesel etc. as raw material is the petroleum diesel surrogate of high-quality.Biofuel is typical case's " green energy resource ", greatly develops biofuel to sustainable economic development, advances energy substitution, alleviates environmental stress, and the control urban atmospheric pollution has important strategic importance.
The method of at present, production biofuel generally has homogeneous acid, base catalysis method.Homogeneous phase base catalysis method catalytic activity is high, and is still very responsive to free fatty acids a small amount of in the raw material and moisture, and saponification reaction occurs easily, causes biofuel product separation difficulty.The acid catalysis method of homogeneous phase is take sulfuric acid, phosphoric acid, hydrochloric acid and organic sulfonic acid etc. as catalyzer, and etching apparatus produces a large amount of acid-bearing wastewaters easily, and subsequent disposal is complicated, and the separation of product is difficulty relatively.In addition, also have some solid acid catalysis to prepare the method for biofuel, but all require the temperature of transesterification reaction higher (about 230 ℃), condition is harsh, unsuitable industrialization promotion.For this reason, a kind of solid acid catalyst that can carry out at a lower temperature transesterify of research has certain economic and social profit.
Summary of the invention
The present invention aims to provide a kind of preparation method of the solid catalyst for production of biodiesel, its solid catalyst that makes has high-specific surface area and superpower acidity, under the low-temp reaction condition, the transformation efficiency of catalysis for preparing biodiesel oil can reach more than 91%, and the advantage such as can be repeatedly used.
The preparation method of a kind of solid catalyst for production of biodiesel of the present invention comprises.
(1) preparation of phospho-wolframic acid: a certain amount of tungstic acid hydrate sodium and Sodium phosphate dibasic under agitation are dissolved in the boiling water, continue to stir lower a certain amount of concentrated hydrochloric acid that adds.Adding obtains phospho-wolframic acid with ether, drying after the cooling, and is for subsequent use.
(2) solid phospho-wolframic acid cesium salt is urged the preparation of body agent: a certain amount of cesium carbonate and above-mentioned prepared phospho-wolframic acid difference wiring solution-forming, cesium carbonate is stirred in the adding Salkowski's solution, room temperature leaves standstill certain hour after stirring certain hour, transpiring moisture at a certain temperature, obtaining white solid is that solid phospho-wolframic acid cesium salt is urged the body agent.
Preferably, the amount ratio of tungstic acid hydrate sodium, Sodium phosphate dibasic and the concentrated hydrochloric acid described in the step (1) is 100:10-15:80.
Preferred, the amount ratio of the cesium carbonate described in the step (2) and phospho-wolframic acid is 1:7-9.
Further preferably, the described churning time of step (2) is 0.5h, and time of repose is 20h, and vaporization temperature is 50 ℃.
Still more preferably, the amount ratio of tungstic acid hydrate sodium, Sodium phosphate dibasic and the concentrated hydrochloric acid described in the described step (1) is 100:12:80, and the amount ratio of the cesium carbonate described in the step (2) and phospho-wolframic acid is 1:8.
The solid catalyst that the present invention makes has high-specific surface area and superpower acidity, and under the low-temp reaction condition, the transformation efficiency of catalysis for preparing biodiesel oil can reach more than 91%, and the advantage such as can be repeatedly used.
Embodiment
Embodiment one.
(1) preparation of phospho-wolframic acid: get 100g tungstic acid hydrate sodium and 13g Sodium phosphate dibasic and under agitation be dissolved in the boiling water, continue to stir the lower 80mL of adding concentrated hydrochloric acid.Adding obtains the 83g phospho-wolframic acid with ether, drying after the cooling, and is for subsequent use.
(2) solid phospho-wolframic acid cesium salt is urged the preparation of body agent: get respectively 10g cesium carbonate and 80g phospho-wolframic acid, wiring solution-forming, again the cesium carbonate solution stirring is added in the Salkowski's solution, leave standstill 20h in room temperature after stirring 0.5h, transpiring moisture under 50 ℃ of temperature obtains the 78g white solid and is solid phospho-wolframic acid cesium salt and urges the body agent (main component is Cs
2.5H
0.5PW
12O
40).
Embodiment two.
(1) preparation of phospho-wolframic acid: get 100g tungstic acid hydrate sodium and 15g Sodium phosphate dibasic and under agitation be dissolved in the boiling water, continue to stir the lower 80mL of adding concentrated hydrochloric acid.Adding obtains the 84.7g phospho-wolframic acid with ether, drying after the cooling, and is for subsequent use.
(2) solid phospho-wolframic acid cesium salt is urged the preparation of body agent: get respectively 10g cesium carbonate and 90g phospho-wolframic acid, wiring solution-forming, again the cesium carbonate solution stirring is added in the Salkowski's solution, leave standstill 20h in room temperature after stirring 0.5h, transpiring moisture under 50 ℃ of temperature, obtaining the 69g white solid is that solid phospho-wolframic acid cesium salt is urged body agent (main component Cs
2H
0.5PW
12O
40).
Embodiment three.
(1) preparation of phospho-wolframic acid: get 100g tungstic acid hydrate sodium and 13g Sodium phosphate dibasic and under agitation be dissolved in the boiling water, continue to stir the lower 80mL of adding concentrated hydrochloric acid.Adding obtains the 82.1g phospho-wolframic acid with ether, drying after the cooling, and is for subsequent use.
(2) solid phospho-wolframic acid cesium salt is urged the preparation of body agent: get respectively 10g cesium carbonate and 70g phospho-wolframic acid, wiring solution-forming, again the cesium carbonate solution stirring is added in the Salkowski's solution, leave standstill 20h in room temperature after stirring 0.5h, transpiring moisture under 50 ℃ of temperature, obtaining the 74g white solid is that solid phospho-wolframic acid cesium salt is urged body agent (main component Cs
3H
0.5PW
12O
40).
Embodiment four.
Production biofuel catalytic activity relatively.
Under the starting material of identical catalyzed production biodiesel, the stagnant catalyst that the present invention is prepared and classical acid (H
2SO
4), solid acid (TiO
2-SO
4 2-) catalytic activity compare.Comparative result is as follows.
Can find out that by upper table the prepared catalyzer of the present invention has than classical acid (H
2SO
4) stronger catalytic activity, and catalytic activity is low in the classical acid catalyzed transesterification, needs two step acid catalysiss, and speed of response is slower, and yield is also lower, and product and catalyzer are not easily separated, and corrosive equipment does not have reusability.And with solid acid (TiO
2-SO
4 2-) catalyzer compares, the catalytic activity of the catalyzer that the present invention is prepared slightly reduces, but the needed temperature of transesterification reaction reduces greatly.
Claims (5)
1. preparation method who is used for the solid catalyst of production of biodiesel is characterized in that comprising:
(1) preparation of phospho-wolframic acid: a certain amount of tungstic acid hydrate sodium and Sodium phosphate dibasic under agitation are dissolved in the boiling water, continue to stir lower a certain amount of concentrated hydrochloric acid that adds; Adding obtains phospho-wolframic acid with ether, drying after the cooling, and is for subsequent use;
(2) solid phospho-wolframic acid cesium salt is urged the preparation of body agent: a certain amount of cesium carbonate and above-mentioned prepared phospho-wolframic acid difference wiring solution-forming, cesium carbonate is stirred in the adding Salkowski's solution, room temperature leaves standstill certain hour after stirring certain hour, transpiring moisture at a certain temperature, obtaining white solid is that solid phospho-wolframic acid cesium salt is urged the body agent.
2. the preparation method of solid catalyst as claimed in claim 1, the amount ratio that it is characterized in that tungstic acid hydrate sodium, Sodium phosphate dibasic and the concentrated hydrochloric acid described in the described step (1) is 100:10-15:80.
3. the preparation method of solid catalyst as claimed in claim 1, the amount ratio that it is characterized in that the cesium carbonate described in the described step (2) and phospho-wolframic acid is 1:7-9.
4. the preparation method of solid catalyst as claimed in claim 1 is characterized in that the described churning time of described step (2) is 0.5h, and time of repose is 20h, and vaporization temperature is 50 ℃.
5. such as the preparation method of claim 1 or 4 described solid catalysts, the amount ratio that it is characterized in that tungstic acid hydrate sodium, Sodium phosphate dibasic and the concentrated hydrochloric acid described in the described step (1) is 100:12:80, and the amount ratio of the cesium carbonate described in the step (2) and phospho-wolframic acid is 1:8.
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| CN2012104219409A CN102936045A (en) | 2012-10-30 | 2012-10-30 | Preparation method of solid catalyst for biodiesel production |
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| CN2012104219409A CN102936045A (en) | 2012-10-30 | 2012-10-30 | Preparation method of solid catalyst for biodiesel production |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101472498B1 (en) * | 2013-04-04 | 2014-12-15 | 고려대학교 산학협력단 | A method for preparing light oil from extra heavy oil using cesium substituted heteropolyacid catalyst and method for regenerating the catalyst |
| CN104607241A (en) * | 2013-11-04 | 2015-05-13 | 上海工程技术大学 | Composite acid catalyst used for preparing biodiesel, and preparation method and applications thereof |
| CN104646059A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Heteropolyacid cesium salt containing hydrocracking catalyst, preparation and application thereof |
| CN105854943A (en) * | 2016-03-31 | 2016-08-17 | 江西理工大学 | Preparation method of rare earth modified heteropoly acid catalyst and biodiesel |
-
2012
- 2012-10-30 CN CN2012104219409A patent/CN102936045A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101472498B1 (en) * | 2013-04-04 | 2014-12-15 | 고려대학교 산학협력단 | A method for preparing light oil from extra heavy oil using cesium substituted heteropolyacid catalyst and method for regenerating the catalyst |
| CN104607241A (en) * | 2013-11-04 | 2015-05-13 | 上海工程技术大学 | Composite acid catalyst used for preparing biodiesel, and preparation method and applications thereof |
| CN104646059A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Heteropolyacid cesium salt containing hydrocracking catalyst, preparation and application thereof |
| CN105854943A (en) * | 2016-03-31 | 2016-08-17 | 江西理工大学 | Preparation method of rare earth modified heteropoly acid catalyst and biodiesel |
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Application publication date: 20130220 |