CN101186834A

CN101186834A - Method for preparing biological diesel oil from rubber seed oil

Info

Publication number: CN101186834A
Application number: CNA2007101922497A
Authority: CN
Inventors: 吴应环; 钱刚; 钱雷; 钱生球
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-12-24
Filing date: 2007-12-24
Publication date: 2008-05-28
Anticipated expiration: 2027-12-24
Also published as: CN101186834B

Abstract

Provided is a process for producing biodiesel, belonging to the technical field of grease modification. The process is characterized in that inedible oils with high acid value, such as rubber seed oil is employed, raw bran oil, raw corn oil, and low carbon alcohol accomplish two reactions of esterificationand and alcoholysis in a single process, and the key technology for achieving biodiesel with high efficiency is esterification and alcoholysis of catalysts.

Description

Production method for preparing biodiesel from rubber seed oil

Technical Field

The invention belongs to the technical field of grease modification, and discloses a method for preparing methyl ester of fatty acid, namely biodiesel.

Background

With the demands of human production and life, the non-renewable oil and coal stocks are less and less, the oil price is continuously increased, the shortage of energy sources becomes the first major problem which needs to be solved urgently by human beings, and the development of renewable biological energy sources is a science and technology leading-edge project which is concerned all over the world.

Currently, research on bioenergy has focused on fuel ethanol and biodiesel, the chemical component of which is methyl ester of fatty acid. The canada and other countries have been successfully developed decades ago, and the methyl ester of rapeseed oil fatty acid is produced by using the abundant rapeseeds and methanol under the action of an alkaline catalyst, and the methyl ester is transported to a tractor, a diesel vehicle, power generation and the like in the canada, australia and other countries, so that the emission pollution of diesel oil tail gas extracted from petroleum can be greatly reduced, and the power is not reduced.

The research is also carried out in China. The edible oil is mainly used as a raw material, the source and the cost are limited, the waste oil is extracted from swill, the quantity is limited, and the large-scale production cannot be realized.

The non-edible oils, such as rubber seed oil, wild resin oil, crude bran oil and crude corn oil, have too high free acid value, so that the conventional method needs to lose effectiveness by using an alkaline catalyst, and the removal of the acid has low yield and poor economic benefit.

The Hainan island and Yunnan Xishuangbanna in China have 1500 ten thousand mu of rubber forest, except rubber tapping, a large number of acorns are not well utilized and are self-generated and self-extinguished, the acorns contain 30% of oil by analysis, 50kg of the oil seeds can be collected in each mu, the potential oil source is about 30 ten thousand tons, the acorns produce the oil, and the problems are also solved, firstly, ① seeds contain a large amount of lipase, 1% of the oil can be decomposed in hot days every hour, the acid value is large, the free acid must be refined by alkali by using a traditional ester exchange method, the loss is large, only 500-600 kg of the oil in each ton, ② raw rubber seeds cannot be stored, the seeds are rotten after several months, and the annual balanced production and development plan are influenced.

Disclosure of Invention

Aiming at the problems of low oil yield and difficult storage of raw materials, the invention adopts the following process:

the raw rubber seeds are inactivated instantly at high temperature for several seconds at 120 ℃, and the treated rubber seeds can be stored for a long time. In the processing steps, the crude oil can be completely utilized by esterification and ester exchange.

The invention has the beneficial effects that: the oil yield is increased to 98% from 50% to 60% in the prior art, the reaction condition is mild, the solid catalyst can be recycled, and the environment is not polluted.

Detailed Description

The specific implementation method of the invention is as follows:

the esterification catalyst is sulfonic acid resin, sulfonated coal, and dehydrating agent is added to complete the esterification of free acid into methyl ester quickly. Separating resin, adding alcoholysis catalyst comprising caustic soda and sodium methoxide to obtain yield over 98%.

The reaction temperature is 80 ℃ in the esterification stage, the alcoholysis temperature is 60 ℃, and the biodiesel can be obtained by stirring. Crude bran oil and crude corn oil can also be produced according to the method.

Example 1:

① removing impurities from the collected rubber seeds, boiling with 120 deg.C hot air for 15 s to kill lipase, cooling, and storing.

② squeezingthe oil with a squeezer, and filtering to obtain crude oil.

③ adding 1000kg crude oil into 200kg methanol, dehydrating, adding 20kg sulfonic acid resin with mass ratio of 2%, 5kg anhydrous sodium sulfate as water absorbent, adsorbing water generated by esterification reaction, stirring at 80 deg.C, refluxing for 2 hr, and checking acid value as end point.

④ separating solid catalyst and water absorbent, adding sodium methoxide 0.5% and sodium hydroxide 0.5% in crude oil, and reacting at 60 deg.C for one hour.

⑤ the catalyst is neutralized with glacial acetic acid and the lower layer of glycerol is released by standing.

⑥ adding active white diesel 10 kg. with the mass ratio of 1% of oil mass, stirring for 0.5h at 80 ℃, and filtering by a filter press to obtain light-colored transparent biodiesel.

Example 2:

using crude bran oil with acid value more than 30

① taking 2000kg of raw bran oil, adding 500kg of methanol, dehydrating under reduced pressure for 0.5 hour, adding 5kg of sulfonated coal and 5kg of concentrated sulfuric acid as dehydrating agents, absorbing water generated in the reaction, stirring and refluxing for 2 hours at 80 ℃, checking the acid value to determine the end point, discharging dilute sulfuric acid, and separating the catalyst.

② 10kg of a mixture of sodium hydroxide and sodium methoxide (1: 1 by mass) was added, and the reaction was stirred at 60 ℃ for 1 hour.

③ neutralizing the catalyst with glacial vinegar, standing, and discharging the lower layer glycerol.

④ and heating and distilling under the vacuum degree of more than 756mmHg, and cutting the methyl ester fraction to obtain pure biodiesel.

Claims

1. The production method of the biodiesel is characterized by comprising the following steps: the inedible high acid value rubber seed oil, crude bran oil and crude corn oil are used as raw materials, and are subjected to esterification and ester exchange reaction with low-carbon alcohol, and light-colored biodiesel, namely fatty acid methyl ester, is obtained through distillation or decoloration. The specific contents are as follows:

① selecting a non-edible oil, and mixing with lower alcohol at a certain ratio.

② adding esterification catalyst and water absorbent, reacting at 80 deg.C for 2 hr, and separating catalyst.

③ alcoholysis catalyst is added, the reaction is carried out at 60 ℃ for 1 hour, and the catalyst is neutralized.

④ vacuum distilling, and collecting low carbon alcohol ester to obtain the product.

2. The claim 1, wherein the inedible oil is rubber seed oil with high acid value, crude bran oil, crude corn oil, and crude cottonseed oil, and the mass ratio of the raw materials to the low carbon alcohol is 1: 0.2 to 1: 0.3.

3. The method according to claim 1, wherein the lower alcohol is methanol, ethanol, isopropanol, or butanol.

4. The process as claimed in claim 1, wherein the esterification catalyst is sulfonic acid resin, sulfonated coal, and the water absorbent is anhydrous sodium sulfate or concentrated sulfuric acid.

5. The process of claim 1, wherein thealcoholysis catalyst is a mixture of sodium hydroxide and sodium methoxide with a mass ratio of 1: 1, and the total amount of catalyst is 1: 0.05 by mass of the oil.