CN105396573A - Preparation method of catalyst for producing biodiesel - Google Patents

Abstract

The invention provides a preparation method of a catalyst, and particularly relates to a catalyst applied to production of biodiesel, belonging to the technical field of catalyst preparation. The preparation method comprises the following steps: taking and uniformly mixing zirconium n-butoxide, penta-n-butoxy niobium, n-zirconium ethoxide and isobutanol to obtain a mixed solution; then taking a saltpeter solution and drilling into the mixed solution, stirring uniformly to react, and cooling to room temperature; taking the lower-layer milky white liquid in the reactant obtained in step 1, adjusting pH with ammonia water, then adding CeO2 powder and Y2O3 powder, stirring uniformly, then rising temperature for reaction, cooling and then aging; and filtering the aging solution obtained in step 2, and roasting the powder, thus obtaining the catalyst. The compound catalyst prepared according to the invention is reasonable in active ingredient ratio, large in specific surface area, good in effect and high in conversion rate which can be up to more than or equal to 96%, and the content of prepared fatty acid methyl ester can be up to more than or equal to 97%.

Description

A kind of preparation method producing the catalyst of biodiesel

Technical field

The invention provides a kind of preparation method of catalyst, particularly relate to a kind of catalyst being applied to production of biodiesel, belong to catalyst preparation technical field.

Background technology

Biodiesel (Biodiesel) refers to the water plant greases such as oil crops, Wild oil plant and engineering and animal fat, food garbage wet goods to be the reproducibility diesel fuel of the replaced petrifaction diesel that feedstock oil is made by ester exchange process.Biodiesel is the one of biomass energy, and it is the mono alkyl ester of a kind of LCFA that the technology such as biomass economy thermal cracking obtain.Typical " green energy resource ".It is the substitute of the petroleum diesel of high-quality.

The advantage of biodiesel includes: 1. have excellent environmental protection characteristic.Sulfur content is low.2. there is good cryogenic engine startability.Additive-free cold filter plugging point reaches-20 DEG C.3. there is good greasy property.Make the wear rate of engine cylinder-body and connecting rod low, long service life.5. there is good fuel performance.6. there is renewable performance.7. biodiesel is in harmonious proportion with certain proportion and petrifaction diesel and uses, and can reduce oil consumption, improve dynamic property, and reduce tail gas pollution.

The production method of biodiesel mainly includes (1) chemical production method, its primary raw material is the plant such as rapeseed oil and soya-bean oil or animal fat, biodiesel etc., raw material and methyl alcohol or ethanol generate fatty acid ester under the effect of catalyst, and then obtained biodiesel and glycerine after hydrolysis.Chemical synthesis shortcoming: it is excessive that complex process, alcohol need, and it is high that following process need reclaim alcohol plant energy consumption; Color and luster is dark (perishable under unrighted acid high temperature; Esterification products difficulty reclaims, and cost is high; Production process has spent lye to discharge generation secondary pollution.(2) biological enzyme, it is that animal fat and low-carbon alcohols are carried out transesterification under the effect of lipase, generates fatty acid methyl ester and second fat; Advantage: mild condition, alcohol consumption are few, non-pollution discharge.Problems existing: to the low conversion rate of methanol/ethanol, be generally only 40% ~ 60%, by-product glycerin and shipwreck, in recovery, are not only formed product and suppress, and glycerine are toxic to immobilised enzymes, make immobilised enzymes shortening in service life.

For chemical synthesis, adopt the homogeneous catalyst catalysis grease such as NaOH to carry out ester exchange reaction to prepare biodiesel to have reaction speed fast, biodiesel yield advantages of higher, this type of catalyst is difficult with product separation, need washing be neutralized, and neutralize washing and can bring a large amount of industrial wastewaters.

Summary of the invention

The object of the invention is: provide a kind of and be applied to production of biodiesel catalyst used, it is high that it needs to have conversion ratio, the advantage easily reclaimed, concrete technical scheme is:

Produce a preparation method for the catalyst of biodiesel, comprise the steps:

1st step, by weight, gets tetrabutyl zirconate 20 ~ 30 parts, five n-butoxy niobium 5 ~ 10 parts, positive ethanol zirconium 40 ~ 50 parts, isobutanol 200 ~ 300 parts, mixes, obtain mixed solution; Then get salpeter solution 70 ~ 80 parts, drip in mixed solution, stir, make reaction 2 ~ 4 hours, let cool to room temperature;

2nd step, in the reactant of the 1st step gained, take off the milky white liquid of layer, regulate pH to 8 ~ 10 with ammoniacal liquor, then add CeO ₂powder 5 ~ 8 weight portion, Y ₂o ₃powder 5 ~ 8 weight portion, stirs, then is warming up to 70 ~ 90 DEG C of reactions 6 ~ 8 hours, after letting cool, and ageing 12 ~ 24 days at 20 ~ 30 DEG C;

3rd step, the ageing liquid of the 2nd step gained to be filtered, after powder is carried out roasting, obtained catalyst.

Preferred, the mass concentration of the salpeter solution in the 1st step is 10% ~ 20%.

Preferred, CeO in the 2nd step ₂the order number of powder is between 400 ~ 800 orders.

Preferred, Y in the 2nd step ₂o ₃the order powder of powder is between 400 ~ 800 orders.

Preferred, the sintering temperature of the 3rd step is 400 ~ 600 DEG C.

Preferred, the roasting time of the 3rd step is 3 ~ 6 hours.

Preferred, the intensification of roasting in the 3rd step and rate of temperature fall are 1 ~ 5 DEG C/min.

Beneficial effect: the composite catalyst that the present invention prepares, its active component reasonable mixture ratio, specific surface area of catalyst is large, and catalyst effect is good, and conversion ratio is high.Conversion ratio is high can reach more than 96%, and the content obtaining fatty acid methyl ester is high can reach more than 97%.

Detailed description of the invention

Embodiment 1

1st step, get tetrabutyl zirconate 20g, five n-butoxy niobium 5g, positive ethanol zirconium 40g, isobutanol 200g, mix, obtain mixed solution; Then get salpeter solution 70g, drip in mixed solution, stir, make reaction 2 hours, let cool to room temperature;

2nd step, in the reactant of the 1st step gained, take off the milky white liquid of layer, regulate pH to 8 ~ 10 with ammoniacal liquor, then add CeO ₂powder 5g, Y ₂o ₃powder 5g, stirs, then is warming up to 70 DEG C of reactions 6 hours, after letting cool, and ageing 12 days at 20 DEG C;

3rd step, the ageing liquid of the 2nd step gained to be filtered, after powder is carried out roasting, obtained catalyst.

The mass concentration of the salpeter solution in the 1st step is 10%, CeO in the 2nd step ₂the order number of powder is between 400 ~ 800 orders, Y ₂o ₃the order powder of powder is between 400 ~ 800 orders, and sintering temperature is 400 DEG C, and roasting time is 3 hours, and intensification and rate of temperature fall are 1 DEG C/min.

Embodiment 2

1st step, get tetrabutyl zirconate 30g, five n-butoxy niobium 10g, positive ethanol zirconium 50g, isobutanol 300g, mix, obtain mixed solution; Then get salpeter solution 80g, drip in mixed solution, stir, make reaction 4 hours, let cool to room temperature;

2nd step, in the reactant of the 1st step gained, take off the milky white liquid of layer, regulate pH to 10 with ammoniacal liquor, then add CeO ₂powder 8g, Y ₂o ₃powder 8g, stirs, then is warming up to 90 DEG C of reactions 8 hours, after letting cool, and ageing 24 days at 30 DEG C;

3rd step, the ageing liquid of the 2nd step gained to be filtered, after powder is carried out roasting, obtained catalyst.

The mass concentration of the salpeter solution in the 1st step is 20%, CeO in the 2nd step ₂the order number of powder is between 400 ~ 800 orders, Y ₂o ₃the order powder of powder is between 400 ~ 800 orders, and sintering temperature is 600 DEG C, and roasting time is 6 hours, and intensification and cooling rate rate are 5 DEG C/min.

Embodiment 3

1st step, get tetrabutyl zirconate 25g, five n-butoxy niobium 7g, positive ethanol zirconium 45g, isobutanol 250g, mix, obtain mixed solution; Then get salpeter solution 75g, drip in mixed solution, stir, make reaction 3 hours, let cool to room temperature;

2nd step, in the reactant of the 1st step gained, take off the milky white liquid of layer, regulate pH to 9 with ammoniacal liquor, then add CeO ₂powder 6g, Y ₂o ₃powder 6g, stirs, then is warming up to 80 DEG C of reactions 7 hours, after letting cool, and ageing 20 days at 25 DEG C;

3rd step, the ageing liquid of the 2nd step gained to be filtered, after powder is carried out roasting, obtained catalyst.

The mass concentration of the salpeter solution in the 1st step is 15%, CeO in the 2nd step ₂the order number of powder is between 400 ~ 800 orders, Y ₂o ₃the order powder of powder is between 400 ~ 800 orders, and sintering temperature is 500 DEG C, and roasting time is 4 hours, and intensification and rate of temperature fall are 3 DEG C/min.

Performance test

Get rapeseed oil 20Kg, methyl alcohol 18Kg, the catalyst 1Kg of above each embodiment gained, more solito ester exchange reaction carries out biodiesel preparation, and the content of conversion ratio and obtained fatty acid methyl ester is as shown in the table, with the NaOH homogeneous catalysis method of routine in contrast.

	Embodiment 1	Embodiment 2	Embodiment 3	Reference examples
					Conversion ratio %	96.1	96.9	97.8	90.1
Content w/w	97.1％	97.2％	98.7％	94.5％

As can be seen from the table, the catalyst that the present invention prepares has the high advantage of conversion ratio, can reach more than 96%, and the content obtaining fatty acid methyl ester is high can reach more than 97%.

Claims (1)

1. produce a preparation method for the catalyst of biodiesel, it is characterized in that, comprise the steps:

1st step, by weight, gets tetrabutyl zirconate 20 ~ 30 parts, five n-butoxy niobium 5 ~ 10 parts, positive ethanol zirconium 40 ~ 50 parts, isobutanol 200 ~ 300 parts, mixes, obtain mixed solution; Then get salpeter solution 70 ~ 80 parts, drip in mixed solution, stir, make reaction 2 ~ 4 hours, let cool to room temperature;

2nd step, in the reactant of the 1st step gained, take off the milky white liquid of layer, regulate pH to 8 ~ 10 with ammoniacal liquor, then add CeO ₂powder 5 ~ 8 weight portion, Y ₂o ₃powder 5 ~ 8 weight portion, stirs, then is warming up to 70 ~ 90 DEG C of reactions 6 ~ 8 hours, after letting cool, and ageing 12 ~ 24 days at 20 ~ 30 DEG C;

3rd step, the ageing liquid of the 2nd step gained to be filtered, after powder is carried out roasting, obtained catalyst.