CN101186834B

CN101186834B - Method for preparing biological diesel oil from rubber seed oil

Info

Publication number: CN101186834B
Application number: CN2007101922497A
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: 2012-05-23
Anticipated expiration: 2027-12-24
Also published as: CN101186834A

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

Rubber seed oil prepares the working method of biofuel

Technical field

The invention belongs to the oil modification technical field, the methyl esters for preparing a kind of lipid acid is a method of bio-diesel oil.

Background technology

Along with the needs of human being's production and life, non-renewable oil, coal storage are fewer and feweri, and oil price rises steadily, and the energy in short supply becomes the human cardinal task that solves be badly in need of, and developing reproducible bioenergy is the common scientific and technological forward position project of paying close attention in the whole world.

At present, the research of bioenergy concentrates on alcohol fuel and biofuel, and its Chemical Composition of so-called biofuel is the methyl esters of lipid acid.States such as Canada are in just successfully exploitation decades ago; Semen Brassicae campestris that use is abounded with and methyl alcohol are under the basic catalyst effect; The methyl esters that generates Uni Ace R lipid acid is transported in tractor, diesel vehicle, generating etc. extremely successful on Canada and Australia and other places; Not only can replace the diesel exhaust exhaust emission that from oil, extracts and reduce a lot, and power does not reduce.

Domestic also someone studies.Mainly use edible oil to be raw material, source and cost all are restricted, and also have and from swill, extract waste oil, and limited amount can not mass production.

And inedible oil, like rubber seed oil, wild sylvic oil, and hair oil extracted from rice husks, hair Semen Maydis oil because free acid value is too high, by traditional method, will loses efficacy with basic catalyst, and remove these acid, produced very lowly, and economic benefit is not good.

There are 1,500 ten thousand mu of rubber woods in China Hainan Island and Xishuangbanna, Yunnan, and except that rubber tapping, a large amount of rubber seeds do not have fine utilization; Run its course, through analyzing, rubber seed oil-containing 30% can be collected the 50kg oilseeds for every mu; Potential oil sources is about 300,000 tons, and the rubber seed produces oil, and a lot of difficult problems is also arranged, at first; 1. give birth to seed and contain a large amount of lipase, per hour can decompose 1% grease in hot day, acid value is very big, with traditional ester exchange method; Must remove these free acids with alkali refining, lose very greatly, oil recovery rate per ton is 500～600kg only.2. the untreated rubber seed can not be deposited, and some months is just mashed to break down, influence year balanced production and evolutionary operation(EVOP).

Summary of the invention

, raw material low to above-mentioned oil yield is difficult for the difficult problem of preservation, and patent of the present invention adopts following technology:

The untreated rubber seed, with high temperature moment the enzyme that goes out just can achieve the goal 120 ℃ of several seconds, but the rubber seed long-term storage of handling.On procedure of processing, first esterification transesterify more just can utilize crude oil fully.

The invention has the beneficial effects as follows: oil yield rises to 98% by 50% to 60% of prior art, and reaction conditions is gentle, and solid catalyst can recycle, and is free from environmental pollution.

Embodiment

Practical implementation method of the present invention is following:

Esterifying catalyst is a sulfonate resin, and sulphonated coal adds dewatering agent, can accomplish fast the free acid esterification is become methyl esters.Separation resin adds the alcoholysis catalysts that caustic soda and sodium methylate are formed again, and yield can reach more than 98%.

Temperature of reaction, Esterification Stage are 80 ℃, 60 ℃ of alcoholysis, and stirring can get biofuel.The hair oil extracted from rice husks, the hair Semen Maydis oil also can be with reference to this method production.

Embodiment 1:

1. with the rubber seed of collecting, removal of impurities is killed lypase in 120 ℃ of hot gas flow boiling heating 15 seconds, and cooling is deposited, and is subsequent use.

2. use squeezing machine, by prior art, pressed oil is crude oil after filtering.

3. crude oil 1000kg is added methyl alcohol 200kg, dehydration, adding mass ratio and be 2% is the 20kg sulfonate resin, and the 5kg SODIUM SULPHATE ANHYDROUS 99PCT is a water-retaining agent, and the water that the absorption esterification generates in 80 ℃, stirs, and refluxes 2 hours, and the inspection acid value is a terminal point.

4. solid catalyst and water-retaining agent, adding mass ratio was 0.5% sodium methylate and 0.5% sodium hydroxide in the crude oil, in 60 ℃ of reactions one hour.

5. use the Glacial acetic acid min. 99.5 catalyst neutralisation, leave standstill and emit lower floor's glycerine.

6. adding oil mass mass ratio 1% active white scholar is 10kg.Stir 0.5h in 80 ℃.Filter with pressure filter, get the light-coloured transparent biofuel.

Embodiment 2:

With acid value greater than more than 30 the hair oil extracted from rice husks

1. get a mao oil extracted from rice husks 2000kg, added methyl alcohol 500kg decompression dehydration 0.5 hour, add sulphonated coal 5kg, vitriol oil 5kg is as dewatering agent, the water that absorption reaction generates, and in 80 ℃ of stirring and refluxing 2 hours, the inspection acid value was confirmed terminal point, and emits dilute sulphuric acid, separating catalyst.

2. add sodium hydroxide and sodium methylate mixture (its mass ratio is 1: 1) 10kg, in 60 ℃ of stirring reactions 1 hour.

3. extremely neutral with ice vinegar catalyst neutralisation, leave standstill, emit lower floor's glycerine.

4. in vacuum tightness greater than 756mmHg, add thermal distillation, cut the methyl esters fraction, pure biofuel.

Claims

1. the working method of biofuel is characterized in that: with the rubber seed removal of impurities, kill lypase 15 seconds in 120 ℃ of hot gas flows boiling heating; Cooling is used the squeezing machine filtration to obtain non-edible high acid value rubber seed oil and is raw material, and first esterification is carried out transesterification reaction with low-carbon alcohol again; Obtain light biofuel through distillation or decolouring; Esterifying catalyst is sulfonate resin or sulphonated coal, and water-retaining agent is a SODIUM SULPHATE ANHYDROUS 99PCT, and concrete steps are following:

1. feed intake mass ratio 1: 0.2 to 1: 0.3 of non-edible high acid value rubber seed oil and low-carbon alcohol,

2. add esterifying catalyst and water-retaining agent, with 80 ℃ of reactions 2 hours, separating catalyst,

3. add alcoholysis catalysts,, use the Glacial acetic acid min. 99.5 catalyst neutralisation in 60 ℃ of reactions 1 hour.

4. ester of low-carbon alcohol is collected in vacuum distilling, cuts the methyl esters cut, gets pure biofuel product.

2. said according to claim 1, low-carbon alcohol is any one in (1) methyl alcohol, (2) ethanol, (3) Virahol, (4) butanols.