CN102078825B - Solid catalyst for preparing biodiesel by utilizing normal-pressure ester exchange method and preparation method thereof - Google Patents
Solid catalyst for preparing biodiesel by utilizing normal-pressure ester exchange method and preparation method thereof Download PDFInfo
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- CN102078825B CN102078825B CN200910225897.7A CN200910225897A CN102078825B CN 102078825 B CN102078825 B CN 102078825B CN 200910225897 A CN200910225897 A CN 200910225897A CN 102078825 B CN102078825 B CN 102078825B
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- diphosphonic acid
- sodium
- biodiesel
- solid catalyst
- hydroxy ethylene
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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
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- 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 discloses a solid catalyst for preparing biodiesel by utilizing a normal-pressure ester exchange method and a preparation method thereof. The preparation method disclosed by the invention is characterized by comprising the following steps: by taking cobalt salt, hydroxyethylidene diphosphonic acid, sodium hydroxide and an organic template agent as raw materials, synthesizing basic hydroxyethylidene diphosphonic acid sodium cobaltate by utilizing a hydrothermal method; filtering, drying, grinding, sieving, and then, soaking in a sodium hydroxide solution; and subsequently, baking for 3-6 hours at 250-300 DEG C to finally prepare a basic hydroxyethylidene diphosphonic acid sodium cobaltate-sodium hydroxide solid catalyst. The solid catalyst prepared by the method disclosed by the invention has higher catalytic activity in the process of preparing the biodiesel by utilizing the normal-pressure ester exchange method and can obtain higher yield of the biodiesel, wherein the yield can reach about 92%. In the invention, the biodiesel prepared from soybean oil has the advantages of mild reaction conditions, simple operation, low energy consumption and small pollution and has higher popularization and application values.
Description
Technical field
The present invention relates to a kind of alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid Catalysts and its preparation method of biodiesel of being prepared by soya-bean oil for normal pressure ester-interchange method, belong to biodiesel fabricating technology field.
Background technology
Along with the exhaustion increasingly of fossil energy, the regenerative resource of finding environmental protection becomes the grand strategy direction that realizes social sustainable development.The biodiesel that the living resources of take are prepared as the natural animal-plant grease in source is typical regenerative resource.Biodiesel is that a kind of mono alkyl ester is containing oxygen clean fuel, the advantages such as lubricity that have recyclability, environment friendly, have good burning performance, security performance are good, good.Biodiesel is as a kind of form of biomass energy, its preparation method mainly adopts ester-interchange method at present, by transesterification, high viscosity animal and plant fat is converted into low viscosity low-carbon ester of fatty acid, No. 98811443.7 patents of Chinese patent for example, No. 20040074760 patents of United States Patent (USP).
Due to the expensive and easy inactivation of enzyme catalyst, therefore its prospects for commercial application is little.Traditional method for producing biodiesel is the method for liquid acid, base catalysis substantially, and the problem of existence is that catalyst liquid acid or quantity of alkali consumption are large, and post processing is very complicated, and production cost is high, and particularly product must be through washing.Conventionally the volume that consumes water will, at the more than 20 times of biodiesel, cause severe contamination to environment after discharge.This has offset the environment friendly of biodiesel as green energy resource to a great extent, and has weakened current biodiesel with respect to fossil diesel fuel slight advantages economically.And the solid base catalysts such as traditional CaO, MgO, although easily separated, stability is not high, can not be acidproof water-fast, in last handling process, also may bring a large amount of industrial wastewaters, and cause environmental pollution.
Therefore, in view of above shortcoming, improve the deficiency of existing catalyst, develop the solid catalyst of high efficiency high stable, and be applied to become one of crucial research contents in biodiesel fabricating technology field in the preparation process of biodiesel.And metal phosphinate/phosphoric acid Coordination Polymer with open-framework structure is the very important functional material of a class, diversity, the dissolubility of its structure are low, stability is high and the physicochemical properties of various novelties have been opened up new way for manufacturing and developing special new catalytic material.According to the literature, up to the present, use metal phosphinate/phosphoric acid Coordination Polymer catalysis biological diesel oil preparation feedback aspect, bibliographical information comprises catalysis grease ester exchange reactions such as using solid phosphoric acid trisodium salt, vanadium phosphate acyl salt.
Summary of the invention
The object of this invention is to provide a kind of high efficiency high stable solid catalyst for normal pressure preparing biodiesel by ester interchange and preparation method thereof.
The invention provides a kind of alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst for normal pressure preparing biodiesel by ester interchange, it is characterized in that thering is following composition and percentage by weight:
Alkali formula hydroxy ethylene diphosphonic acid cobalt sodium (Na
6co
7(OH)
2(hedpH)
6(H
2o)
10) 94～99%
NaOH (NaOH) 6～1%
A preparation method for alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst of normal pressure preparing biodiesel by ester interchange, is characterized in that having following process and step:
Cobalt chloride or cobalt nitrate are dissolved with 5～20 times of water gagings, add 0.5～2 times of amount hydroxy ethylene diphosphonic acid and 0.5～2 times amount organic formwork agent pyrazine or 4,4'-Bipyridine, after stirring, add again the NaOH of 8～12 times of amounts.Mixture is enclosed in reactor, in 120～160 ℃ of reactions filtration after 24～72 hours, the dry alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid that obtains.Above-mentioned gained alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid is flooded to sodium hydroxide solution after grinding, sieving, flood 24 hours, the concentration of sodium hydroxide solution is 0.05～0.5mol/L.Then in deionized water for stirring, soak 8 hours, at 250～300 ℃, cure 3～6 hours subsequently, finally make alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst.
For normal pressure ester-interchange method, by soya-bean oil, prepared purposes and the using method thereof of hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst of biodiesel, it is characterized in that thering is following using method:
In reactor, add a certain amount of soya-bean oil and methyl alcohol, molar ratio of methanol to oil is 3: 1～10: 1; Add a certain amount of above-mentioned alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst making, the consumption of catalyst is 1%～5% of soya-bean oil quality again; Under magnetic stirrer is mixed, under 50～70 ℃ of condition of normal pressure, carry out ester exchange reaction 3～7 hours, after reaction, isolate solid catalyst, the upper strata product taking out after layering is biodiesel.
The solid catalyst that the present invention makes is prepared the reaction of biodiesel by soya-bean oil for normal pressure ester-interchange method, have higher catalytic activity and stability; Reaction condition is gentle, easy to operate, catalyst separation is simple, energy consumption is low, it is little to pollute, and has higher application value.
The specific embodiment
Now see specific embodiments of the invention narrations with in rear.
Embodiment 1
Technical process and step in the present embodiment are as follows:
(1) design determines that composition and the percentage by weight of solid catalyst are:
Alkali formula hydroxy ethylene diphosphonic acid cobalt sodium (Na
6co
7(OH)
2(hedpH)
6(H
2o)
10) 96%
NaOH (NaOH) 4%
(2) cobalt chloride is dissolved with 10 times of water gagings, add 2 times of amount hydroxy ethylene diphosphonic acids and 1 times of amount organic formwork agent pyrazine, after stirring, add again the 1M NaOH of 10 times of amounts.Mixture is enclosed in reactor, in 140 ℃ of reactions filtration after 48 hours, the dry alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid that obtains.Above-mentioned gained alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid is flooded to sodium hydroxide solution after grinding, sieving, flood 24 hours, the concentration of sodium hydroxide solution is 0.4mol/L.Then in deionized water for stirring, soak 8 hours, at 260 ℃, cure 4 hours subsequently, finally make alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst.
(3) in reactor, add a certain amount of soya-bean oil and methyl alcohol, molar ratio of methanol to oil is 6: 1; Add a certain amount of above-mentioned alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst making, the consumption of catalyst is 3% of soya-bean oil quality again; Under magnetic stirrer is mixed, under 60 ℃ of condition of normal pressure, carry out ester exchange reaction 5 hours, after reaction, isolate solid catalyst, the upper strata product taking out after layering is biodiesel.
Get the above-mentioned biodiesel making 4 μ L and be dissolved in 300 μ L n-hexanes, then get this mixed liquor 2 μ L, and take ethyl magarate as interior mark, utilize the productive rate of gas chromatographic detection fatty acid methyl ester.In the present embodiment, measured biodiesel production rate is 92.3%.
Embodiment 2
The present embodiment is identical with step with the process in above-described embodiment 1.Different: in (2) step, cobalt nitrate to be dissolved with 10 times of water gagings, add 1.5 times of amount hydroxy ethylene diphosphonic acids and 2 times of amount organic formwork agent 4,4'-Bipyridines, after stirring, add again the 1M NaOH of 10 times of amounts.Mixture is enclosed in reactor, in 150 ℃ of reactions filtration after 36 hours, the dry alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid that obtains.
After ester exchange reaction, materials and carry out gas chromatographic detection, the biodiesel production rate recording is 90.2%.
Embodiment 3
The present embodiment is identical with step with the process in above-described embodiment 2.Different: in (2) step, at stoving temperature, be 300 ℃, the time of curing is 6 hours.When (3) step is prepared biodiesel, the temperature of ester exchange reaction is 70 ℃, and the reaction time is 4 hours.
After ester exchange reaction, materials and carry out gas chromatographic detection, the biodiesel production rate recording is 91.6%.
Embodiment 4
The present embodiment is identical with step with the process in above-described embodiment 1.Different: in (3) step, molar ratio of methanol to oil is 5: 1, the consumption of catalyst is 2% of soya-bean oil quality; Under magnetic stirrer is mixed, under 60 ℃ of condition of normal pressure, carry out ester exchange reaction 4 hours.
After ester exchange reaction, materials and carry out gas chromatographic detection, the biodiesel production rate recording is 87.5%.
Embodiment 5
The present embodiment is identical with step with the process in above-described embodiment 1.Different: in (3) step, molar ratio of methanol to oil is 6: 1, the consumption of catalyst is 2% of soya-bean oil quality; Under magnetic stirrer is mixed, under 60 ℃ of condition of normal pressure, carry out ester exchange reaction 5 hours.
After ester exchange reaction, materials and carry out gas chromatographic detection, the biodiesel production rate recording is 88.2%.
Embodiment 6
The present embodiment is identical with step with the process in above-described embodiment 1.Different: in (3) step, molar ratio of methanol to oil is 5: 1, the consumption of catalyst is 3% of soya-bean oil quality; Under magnetic stirrer is mixed, under 70 ℃ of condition of normal pressure, carry out ester exchange reaction 4 hours.
After ester exchange reaction, materials and carry out gas chromatographic detection, the biodiesel production rate recording is 89.7%.
Claims (2)
1. for alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst of normal pressure preparing biodiesel by ester interchange, it is characterized in that thering is following composition and percentage by weight:
Alkali formula hydroxy ethylene diphosphonic acid cobalt sodium (Na
6co
7(OH)
2(hedpH)
6(H
2o)
10) 94～99%
NaOH (NaOH) 6～1%
, its preparation method has following process and step:
Cobalt chloride or cobalt nitrate are dissolved with 5～20 times of water gagings, add 0.5～2 times of amount hydroxy ethylene diphosphonic acid and 0.5～2 times of amount organic formwork agent pyrazine or 4, 4 '-bipyridyl, after stirring, add again the NaOH of 8～12 times of amounts, mixture is enclosed in reactor, in 120～160 ℃ of reactions, after 24～72 hours, filter, the dry alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid that obtains, by above-mentioned gained alkali formula hydroxy ethylene diphosphonic acid cobalt sodium solid through grinding, after sieving, flood sodium hydroxide solution, flood 24 hours, the concentration of sodium hydroxide solution is 0.05～0.5mol/L, then in deionized water for stirring, soak 8 hours, at 250～300 ℃, cure 3～6 hours subsequently, finally make alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst.
2. for normal pressure ester-interchange method, by soya-bean oil, prepared a using method for hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst of biodiesel, it is characterized in that thering is following using method:
In reactor, add a certain amount of soya-bean oil and methyl alcohol, molar ratio of methanol to oil is 3:1～10:1; Add a certain amount of alkali formula hydroxy ethylene diphosphonic acid cobalt sodium-sodium hydrate solid catalyst claimed in claim 1, the consumption of catalyst is 1%～5% of soya-bean oil quality again; Under magnetic stirrer is mixed, under 50～70 ℃ of condition of normal pressure, carry out ester exchange reaction 3～7 hours, after reaction, isolate solid catalyst, the upper strata product taking out after layering is biodiesel.
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| CN101559359A (en) * | 2009-04-30 | 2009-10-21 | 上海大学 | Solid base catalyst used for preparing biodiesel by ester interchange and preparation method thereof |
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Patent Citations (2)
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|---|---|---|---|---|
| JP3736021B2 (en) * | 1997-04-17 | 2006-01-18 | Ｊｆｅスチール株式会社 | Method for separating and analyzing silicon and phosphorus |
| CN101559359A (en) * | 2009-04-30 | 2009-10-21 | 上海大学 | Solid base catalyst used for preparing biodiesel by ester interchange and preparation method thereof |
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