Method of preparing biological diesel oil from high acid value grease by solid acid pretreatment

A high acid value oil and biodiesel technology, applied in the preparation of biological raw materials, biofuels, liquid hydrocarbon mixtures, etc., can solve the problems of high corrosion, equipment investment, increased production energy consumption, complex composition of acid active compositions, etc. , to reduce energy consumption and alkali consumption, expand the range of raw material selection, and achieve good reusability.

Inactive Publication Date: 2007-08-15
NANJING UNIV OF FINANCE & ECONOMICS
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  • Summary
  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

[0004] Therefore, the subject of utilizing waste oil with high acid value to prepare biodiesel has received extensive attention. For example, in patent documents such as CN1382762A and CN1412278A, it has been reported that waste oil with high acid value is used as a raw material, and a liquid acid catalyst is used to prepare biodiesel. However, the catalytic efficiency is not high, the reaction time is long, and the corrosion is large
US4652406, CN1556174 etc. adopt a pretreatment step to reduce the content of free fatty acid, promptly carry out esterification reaction with monohydric alcohol (such as methyl alcohol) in the presence of liquid acid catalyst, the acid value in the oil phase is reduced, but after pretreatment, The liquid acid in the oil phase must be removed, and the acid left in the

Method used

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Examples

Experimental program
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Example Embodiment

[0020] Example 1:

[0021] Add 50ml soybean oil (density 0.92g / cm 3 ), 4g oleic acid, 20ml methanol (density 0.79g / cm 3 ), 1.0 g SO 4 2- / Al 2 O 3 / ZrO 2 Solid acid catalyst (in which Al 2 O 3 The content is ZrO 2 4% of the molar amount), under normal pressure and 55° C., the esterification reaction was carried out for 3 hours, and the acid value of the reaction solution was 1.7. After the reaction, the reaction solution was filtered to filter out the solid acid catalyst and collected for regeneration and reuse. The filtrate and 0.7 g of NaOH were added to the reactor, heated to 65° C., and transesterified under normal pressure for 1 hour. After the reaction is completed, the layers are allowed to stand for separation, the upper layer is fatty acid methyl ester and a small amount of methanol, and the lower layer is glycerin, methanol and alkali. After the upper layer was distilled to remove methanol, 46.2 g of biodiesel was obtained. The total yield of the reaction was 92.4%. The...

Example Embodiment

[0024] Example 2:

[0025] After the waste oil collected from the restaurant is dehydrated by removing impurities, take 40 grams (acid value 20.1) and 20ml methanol, 1.2g SO 4 2- / Al 2 O 3 / ZrO 2 Solid acid catalyst (Al 2 O 3 The content is ZrO 2 5% of the molar amount) was mixed and added to the reactor, and the acid value of the reaction liquid was reduced to 2.4 under the conditions of normal pressure and 65° C. for 3.5 hours of esterification reaction. After the reaction, the reaction liquid was filtered to filter out the solid acid catalyst, the filtrate and 0.8 g of NaOH were added to the reactor, heated to 60° C., and transesterified under normal pressure for 2 hours. After the reaction is completed, the layers are allowed to stand for separation, the upper layer is fatty acid methyl ester and a small amount of methanol, and the lower layer is glycerin, methanol and alkali. After the upper layer was distilled to remove methanol, 33.6 g of biodiesel was obtained. The total ...

Example Embodiment

[0026] Example 3:

[0027] Add 100ml soybean oil, 5g oleic acid, 25ml methanol, 1.5g Al to the reactor 2 O 3 / WO 3 / ZrO 2 Solid acid catalyst (in which Al 2 O 3 The content is ZrO 2 2% of the molar amount), under normal pressure and 60°C, the esterification reaction is carried out for 2 hours, and the acid value of the reaction solution is 1.5. After the reaction, the reaction solution was filtered to filter out the solid acid catalyst and collected for reuse in the province. The filtrate and 1.8 g of NaOH were added to the reactor, heated to 68°C, and transesterified under normal pressure for 1.5 hours. After the reaction is completed, the layers are allowed to stand for separation, the upper layer is fatty acid methyl ester and a small amount of methanol, and the lower layer is glycerin, methanol and alkali. After the upper layer was distilled to remove methanol, 91.2 g of biodiesel was obtained. The total yield of the reaction was 94.0%.

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Abstract

The invention discloses a preparing method of biological diesel through pre-disposing high acid grease with solid acid, which comprises the following steps: proceeding esterified pre-disposing reaction with high acid value and monohydric alcohol under the condition of existing solid acid activator at normal pressure and 50-90 deg.c; filtering out of solid acid activator; regenerating; using repeatedly; adding alkali NaOH or KOH activator into filtering liquid; proceeding ester exchange reaction; producing biological diesel; choosing solid acid activator from H-ZSM-5 type molecular sieve or composite oxides SO42-/ZrO2 blended with assisted composition Ga2O3 or Al2O3 or WO3/ZrO2; setting the blending quantity of Ga2O3 or Al2O3 make up 1-9% of ZrO2 mole weight. This invention does not possess corrosion and pollution, which can make base catalysis ester exchange reaction to be easy.

Description

technical field [0001] The invention relates to a method for preparing biodiesel from oil with high acid value, in particular to a method for preparing biodiesel by using a solid acid catalyst to pretreat the oil with high acid value. Background technique [0002] As we all know, oil is a non-renewable energy source, but it has been proven that more than half of the global oil reserves have been exploited, and people are eager to open up new energy sources. In addition, a large amount of exhaust gas emitted by automobiles powered by petroleum has seriously polluted the living environment of human beings, and improving automobile exhaust pollution has become an urgent problem to be solved. As countries around the world pay more and more attention to energy issues and environmental protection issues, it is urgent to find a renewable and environmentally friendly new energy source to replace the increasingly depleted oil resources and protect the earth's environment on which peo...

Claims

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Application Information

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IPC IPC(8): C10G3/00
CPCY02E50/13Y02E50/10Y02P30/20
Inventor 曹崇江
Owner NANJING UNIV OF FINANCE & ECONOMICS
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