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

A high-acid value grease and biodiesel technology, which is applied in the preparation of biological raw materials, biofuels, and liquid hydrocarbon mixtures, can solve problems such as high corrosion, equipment investment, increased production energy consumption, and complex components of acidic active compositions. , to achieve the effect of reducing energy consumption and alkali consumption, expanding the range of raw material selection, and good reusability

Inactive Publication Date: 2009-08-19
NANJING UNIV OF FINANCE & ECONOMICS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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 oil phase needs to be neutralized by adding an excessive amount of alkali before the basic catalytic system can carry out the transesterification reaction. The process is complicated, the processing process is long, and the equipment investment and production energy consumption are greatly increased rise
[0005] CN1887417A discloses a method of esterifying acidified oil by using an acidic catalytic active composition containing complex rare earth solid acid, cobalt and titanium solid acid, but the acidic active composition has complex components and high price
CN1904013A also mentions a method for reducing the acid value of oil, that is, in a fixed bed reactor, high acid value oil and monohydric alcohol are mixed for esterification, but this method requires high temperature and high pressure conditions

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] In reactor, add 50ml soybean oil (density is 0.92g / m 3 ), 4 grams of oleic acid, 20ml methanol (density of 0.79g / cm 3 ), 1.0 g SO 4 2- / Al 2 o 3 / ZrO 2 Solid acid catalyst (wherein Al 2 o 3 Content is ZrO 2 4% of molar weight), under the condition of normal pressure and 55 ℃, esterification reaction was carried out for 3 hours, and the acid value of the reaction solution was 1.7. After the reaction was finished, the reaction solution was filtered, and the solid acid catalyst was collected for regeneration and reuse. The filtrate and 0.7 g of NaOH were added to the reactor, heated to 65° C., and transesterified at normal pressure for 1 hour. After the reaction was finished, the layers were left to stand, the upper layer was fatty acid methyl ester and a small amount of methanol, and the lower layer was glycerol, methanol and alkali. After methanol was distilled off from the upper layer, 46.2 grams of biodiesel was obtained. The total reaction yield was 92.4%. ...

Embodiment 2

[0025] After removing impurities and dehydrating the waste oil collected from the restaurant, take 40 grams (acid value 20.1) and 20 ml of methanol, 1.2 grams of SO 4 2- / Al 2 o 3 / ZrO 2 Solid acid catalyst (Al 2 o 3 Content is ZrO 2 5% of the molar amount) were mixed and added into the reactor, and under the conditions of normal pressure and 65° C., the esterification reaction was carried out for 3.5 hours, and the acid value of the reaction solution was reduced to 2.4. After the reaction was finished, the reaction solution was filtered, and the solid acid catalyst was filtered out. 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 was finished, the layers were left to stand, the upper layer was fatty acid methyl ester and a small amount of methanol, and the lower layer was glycerol, methanol and alkali. After methanol was distilled off from the upper layer, 33.6 grams o...

Embodiment 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 (wherein Al 2 o 3 Content is ZrO 2 2% of the molar weight), under the conditions of normal pressure and 60 DEG C, the esterification reaction was carried out for 2 hours, and the acid value of the reaction solution was 1.5. After the reaction was finished, the reaction solution was filtered, and the solid acid catalyst was collected to be reused in the province. The filtrate and 1.8 grams of NaOH were added to the reactor, heated to 68 ° C, and transesterified at normal pressure for 1.5 hours. After the reaction was finished, the layers were left to stand, the upper layer was fatty acid methyl ester and a small amount of methanol, and the lower layer was glycerol, methanol and alkali. After methanol was distilled off from the upper layer, 91.2 grams of biodiesel was obtained. The total reaction yield 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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Patent Type & Authority Patents(China)
IPC IPC(8): C10G3/00
CPCY02E50/13Y02E50/10Y02P30/20
Inventor 曹崇江
Owner NANJING UNIV OF FINANCE & ECONOMICS
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