CN1955254A

CN1955254A - Integral production method of bio-diesel oil and high protein feed

Info

Publication number: CN1955254A
Application number: CNA2005101146711A
Authority: CN
Inventors: 原玉明
Original assignee: Individual
Current assignee: Individual
Priority date: 2005-10-28
Filing date: 2005-10-28
Publication date: 2007-05-02
Anticipated expiration: 2025-10-28
Also published as: CN100584925C

Abstract

This invention discloses a comprehensive production method of biological diesel oil and high protein forage. The biological diesel oil is produced by lipid, and high protein forage is produced by meals. The preparation of biological diesel oil is that the lipid is thrown into reactor, and the weight ratio of lipid and methanol is 1:0.12-1.0, and the accelerant whose weight amount is 1-12% that of lipid mixes methanol. The reaction is conducted under 50-90DEG C for 2-20 hour, and the mixture enters into rectifying tower for distillation at 30-40DEG C. Methanol and glycerine is separated and fatty acid methyl ester is obtained, which is just biological diesel oil. The preparation of protein forage is that meals are putted into steam-washing container, and superheated vapor is sent after agitation. When the temperature is 100-130DEG C, glucosinolate toxin in rapeseed is washed with steam condensed water. The mixture of water and dregs of meals are putted into reduced pressure distillating still after deastringent. The washing toxin water is vaporize after reducing pressure and pulled out with steam-water jet pump. High protein forage is obtained from dried and shattered dregs of meals.

Description

The integrated process for production of a kind of biofuel and high-protein feed

Technical field

Technical solutions according to the invention belong to the liquid hydrocarbon mixture of being made by the non-hydrocarbons material, concretely, are to belong to from oxygen containing organism to prepare liquid hydrocarbon mixture, as fatty oil, lipid acid, according to International Patent Classification, belong to C10G 3/00 field.

Background technology

Natural oil is a kind of non-renewable energy, and its resource is day by day exhausted, and the various countries' common concern and the research renewable energy resources substitute oil.Biofuel is to be the renewable energy source of raw material production with Vegetable oil lipoprotein or animal grease.

The production of domestic biofuel, as China's patent No. 200410038292.4 " a kind of solid acid, base catalysis prepare method of bio-diesel oil ", it is under the condition of solid acid or solid base catalyst existence, utilizes the transesterification reaction of soybean oil and methyl alcohol to obtain biofuel.Reaction finishes the back separates catalyzer with whizzer earlier from reaction soln, standing demix then, and the upper strata is a coarse products, lower floor is glycerine and methanol mixture.To get biofuel behind the thick ester water-bath distillation in upper strata, get purified glycerine behind lower floor's water-bath distillation, but the methyl alcohol recirculation that distills out be used.

China's patent No. 02133591.5 " a kind of production method of bio-diesel oil " and for example, it is to utilize the tankage and the edible refiltered oil that are produced in the vegetable oil refining process to be raw material, through acidifying removal of impurities, continuously dehydrating, esterification, recovery methyl alcohol, leave standstill, tell lower floor, reclaim glycerine, continuous still battery obtains explained hereafter biofuel such as finished product.

The weak point of above-mentioned patent is with the single preparation biofuel of grease.

Summary of the invention

The objective of the invention is to propose the integrated process for production of a kind of biofuel and high protein feed.It adopts biofuel coproduction high protein feed, can also fully utilize simultaneously to extract other byproduct.

The object of the present invention is achieved like this: it by obtaining proteinaceous grouts after the oil expression, produces high-protein feed again by the grease production biofuel.Comprise following two parts:

(1) production method of biofuel

The present invention is raw material with the grease, as rapeseed oil (or other Vegetable oil lipoprotein, as soya-bean oil, peanut oil, plam oil, sunflower seed oil, the grease that Viscotrol C and wild plant fruit extract, reclaim waste oil or animal grease), drop in the reactor, grease and methyl alcohol weight ratio are 1: 0.12～1.0, catalyzer with grease weight 1～12%, as tosic acid (or the vitriol oil, the sulfonic acid type macroporous resin, sulfonic compound, alkaline matter such as sodium hydroxide, sodium methylate etc. or inorganic salts such as manasseite etc.) mix the back with methanol solution and under 50～90 ℃ of reflux temperatures, carry out 2～20 hours reaction, grease and methyl alcohol carry out transesterification reaction, after finishing, reaction keep 30～40 ℃ temperature to enter in the rectifying tower, respectively at normal pressure, decompression continuous rectification down, isolate methyl alcohol and glycerine, and yield can reach 92～95% fatty acid methyl ester, i.e. biofuel after obtaining rectifying.

(2) production method of high-protein feed

With the proteinaceous grouts that obtain after the Semen Brassicae campestris oil expression is raw material, contains 30～40% protein in its grouts, because its puckery and contain toxic substance such as sulphur glucoside as the feed of high protein, must carry out the processing that detoxification is taken away the puckery taste.Will make not subject to severe risks of damage of nutritive ingredient and loss in treating processes, this production method adopts that superheated vapour is instantaneous removes astringent taste and toxin by rapeseed cake dregs.Protein content can bring up to 40～50%, and virus elimination rate can reach 90%.

The present invention is a raw material with the grouts that obtain after extracting oil, being placed on vapour as rapeseed meal washes in the still, through stirring the superheated vapour that feeds 1～2Mpa, make temperature reach 100～130 ℃, and the pressure that makes vapour wash still remains under 1～2Mpa, part vapor condenses Cheng Shui, under 100～130 ℃ temperature, use inherent glucosinolate toxin in the agglomerative steam condensate washing oil vegetable seed, continue to keep 100～130 ℃ of temperature, took away the puckery taste through 10～20 minutes, after handling, water, dregs of rice slag mixture is put into the underpressure distillation still fast, dregs of rice slag is by expanded in decompression process, make 100～130 ℃ washing toxin water vapor after the instantaneous decompression, be drawn out of after the decompression of carbonated drink squirt pump, dregs of rice slag also is dried, cooling then can obtain protein content and can reach 40～45% virus elimination rates and can reach 90% high-protein feed after pulverizer is pulverized.

The main performance index of biofuel reaches the index of No. 0 diesel oil.The Semen Brassicae campestris dregs of rice are carried out detoxification and remove the processing of astringent taste, superheated vapour with 1～2MPa is washed away the detoxification element at 100～130 ℃ of short period of time wash-ins, continue to add the heat extraction astringent taste, and instant decompression has expansion when emitting material, make the feed of removing toxin slightly savory, reduce pressure simultaneously the toxin and the water of gasification are extracted out.Remaining material becomes high protein feed through drying and crushing, is used to raise pig, fish, chicken etc.The simple cost of the treatment process of the Semen Brassicae campestris dregs of rice is low, and the sale of high protein feed (protein content can reach 40～45%) reduces the cost of biofuel significantly.

Advantage of the present invention and extremely long-pending effect

1. this integrated process for production production biofuel simultaneously and high-protein feed help large-scale production.

2. employed catalyzer can reclaim as sulfonic acid type macroporous resin and manasseite etc., can repeatedly use after washing drying.

3. grease is in the presence of catalyzer, carries out mixture after the transesterification reaction with methyl alcohol, and it is refining to carry out the serialization flash liberation in rectifying tower; guarantee to reclaim the quality of methyl alcohol, glycerine; guarantee the quality of biofuel, reduced processing links, reduced waste liquid and waste residue.

Embodiment

Embodiment 1: rapeseed oil and methanol solution (content 〉=98%), with weight ratio is that 1: 0.12 amount drops in the reactor, the tosic acid that adds grease weight 5% again, reaction is about 6 hours under reflux state, behind the stopped reaction, material changed over to maintain the temperature at 30～35 ℃ in the storage tank, enter continuously in the rectifying tower is that mixture one-time continuous in rectifying tower disposes, it is stand-by that methyl alcohol is separated inflow methyl alcohol storage tank by cat head, from side mouth branch line, separate water outlet simultaneously, after water and methyl alcohol dispose, with the glycerine of tower still bottom and fatty acid methyl ester rectifying separation under reduced pressure, yield be can obtain and 92% fatty acid methyl ester, i.e. biofuel reached.

Embodiment 2. rapeseed oils and methanol solution (content 〉=98%) are that 1: 0.4 amount drops in the reactor with weight ratio, the tosic acid that adds grease weight 5% again, reaction is about 4 hours under reflux state, behind the stopped reaction, material changed over to maintain the temperature at 30～35 ℃ in the storage tank, enter in the rectifying tower continuously, it is stand-by that methyl alcohol is separated inflow methyl alcohol storage tank by cat head, from side mouth branch line, separate water outlet simultaneously, after water and methyl alcohol dispose, with the glycerine of tower still bottom and fatty acid methyl ester rectifying separation under reduced pressure, can obtain yield and be 95% fatty acid methyl ester, reclaim glycerine simultaneously.

Embodiment 3. rapeseed oils and methanol solution (content 〉=98%) are that 1: 0.3 amount drops in the reactor with weight ratio, and other steps are with embodiment 2.

Embodiment 4. rapeseed oils and methanol solution (content 〉=98%) are that 1: 0.4 amount drops in the reactor with weight ratio, the vitriol oil that adds grease weight 5% is a catalyzer, reaction is about 6 hours under reflux state, behind the stopped reaction, material changed over to maintain the temperature at 30～35 ℃ in the storage tank, enter in the rectifying tower continuously, it is stand-by that methyl alcohol is separated inflow methyl alcohol storage tank by cat head, from side mouth branch line, separate water outlet simultaneously, after water and methyl alcohol dispose, with the glycerine of tower still bottom and fatty acid methyl ester rectifying separation under reduced pressure, can obtain yield and be 95% fatty acid methyl ester, reclaim glycerine simultaneously.

Embodiment 5. is a catalyzer with the vitriol oil of grease weight 8%, and other steps are with embodiment 4.

Embodiment 6. is a catalyzer with the vitriol oil of grease weight 10%, and other are with step embodiment 4.

Embodiment 7. rapeseed oils and methanol solution (content 〉=98%) are that 1: 0.4 amount drops in the reactor with weight ratio, the sulfonic acid type macroporous resin that adds grease weight 8% is an esterifying catalyst, reaction is about 4 hours under reflux state, stopped reaction, the cooling after-filtration is isolated resin, after washing drying, recycle, the reaction mixture that filters out enters in the rectifying tower continuously, it is stand-by that methyl alcohol is separated inflow methyl alcohol storage tank by cat head, from side mouth branch line, separate water outlet simultaneously, after water and methyl alcohol dispose,, can obtain yield and be 95% fatty acid methyl ester with the glycerine of tower still bottom and fatty acid methyl ester rectifying separation under reduced pressure.

The sulfonic acid type macroporous resin that embodiment 8. adds grease weight 5% is an esterifying catalyst, and other steps are with embodiment 7.

The sulfonic acid type macroporous resin that embodiment 9. adds grease weight 10% is an esterifying catalyst, and other steps are with embodiment 7.

Embodiment 10. rapeseed oils and methanol solution (content 〉=98%) are that 1: 0.4 amount drops in the reactor with weight ratio, the manasseite (self-control) that adds grease weight 5% is a catalyzer, reaction is about 6 hours under reflux state, stopped reaction, the cooling after-filtration is isolated catalyzer, can recycle after the washing drying, the filtrate that filters out is that reaction mixture enters in the rectifying tower continuously, it is stand-by that methyl alcohol is separated inflow methyl alcohol storage tank by cat head, from side mouth branch line, separate water outlet simultaneously, after water and methyl alcohol dispose,, can obtain yield and be 92% fatty acid methyl ester with the glycerine of tower still bottom and fatty acid methyl ester rectifying separation under reduced pressure.

The manasseite (self-control) that embodiment 11. adds grease weight 8% is a catalyzer, and its other steps are with embodiment 10.

The manasseite (self-control) that embodiment 12. adds grease weight 10% is a catalyzer, and its other steps are with embodiment 10.

Claims

1. the integrated process for production of biofuel and high-protein feed, it by obtaining proteinaceous grouts after the oil expression, produces high-protein feed again by the grease production biofuel, it is characterized in that:

(A) production method of biofuel:

With the grease is raw material, as rapeseed oil, drop in the reactor, grease and methyl alcohol weight ratio are 1: 0.12～1.0,1～12% catalyzer with grease weight, mix the back with methanol solution as tosic acid and under 50～90 ℃ of reflux temperatures, carry out 2～20 hours reaction, grease and methyl alcohol carry out transesterification reaction, after finishing, reaction keep 30～40 ℃ temperature to enter in the rectifying tower, continuous rectification under normal pressure, decompression respectively, isolate methyl alcohol and glycerine, and yield can reach 92～95% fatty acid methyl ester, i.e. biofuel after obtaining rectifying;

(B) production method of high-protein feed:

With the grouts that obtain after the oil expression is raw material, being placed on vapour as rapeseed meal washes in the still, through stirring the superheated vapour that feeds 1～2Mpa, make temperature reach 100～130 ℃, and the pressure that makes vapour wash still remains under 1～2Mpa, part vapor condenses Cheng Shui, under 100～130 ℃ temperature, use inherent glucosinolate toxin in the agglomerative steam condensate washing oil vegetable seed, continue to keep 100～130 ℃ of temperature, took away the puckery taste through 10～20 minutes, after handling, water, dregs of rice slag mixture is put into the underpressure distillation still fast, dregs of rice slag is by expanded in decompression process, make 100～130 ℃ washing toxin water vapor after the instantaneous decompression, be drawn out of after the decompression of carbonated drink squirt pump, dregs of rice slag also is dried, cooling then can obtain protein content and can reach 40～45% after pulverizer is pulverized, virus elimination rate can reach 90% high-protein feed.

2. the integrated process for production of a kind of biofuel according to claim 1 and high-protein feed is characterized in that grease that above-mentioned grease also can select other Vegetable oil lipoprotein such as soya-bean oil, peanut oil, plam oil, sunflower seed oil, Viscotrol C and wild plant fruit for use and extract, reclaims waste oil or animal grease.

3. the integrated process for production of a kind of biofuel according to claim 1 and high-protein feed, it is characterized in that above-mentioned catalyzer, also can select the vitriol oil, sulfonic acid type macroporous resin, sulfonic compound, alkaline matter such as sodium hydroxide, sodium methylate or inorganic salts such as manasseite for use.