CN1818027A

CN1818027A - Production of biological diesel oil by catalyst consisting of phase-transferring agent mixture

Info

Publication number: CN1818027A
Application number: CNA2006100339938A
Authority: CN
Inventors: 张展洪; 张杰才
Original assignee: Individual
Current assignee: Individual
Priority date: 2006-03-03
Filing date: 2006-03-03
Publication date: 2006-08-16
Anticipated expiration: 2026-03-03
Also published as: CN100494317C

Abstract

Production of biological diesel oil with phase transfer agent mixture as catalyst is carried out maripa oil and methanol ester exchange reacting under the existence of phase transfer agent mixture to obtain biological diesel oil and glycerine, molecular rearranging, separating out catalyst by filter, laying aside, laminating, distilling the upper layer coarse ester at 65 degrees C to obtain the final product. The upper layer is coarse product and the lower layer is mixture of glycerine and excess methanol. It is simple, has no waste- water, environmental pollution and can be re utilization.

Description

Prepare method of bio-diesel oil with the consisting of phase-transferring agent mixture controlling catalyst

(1) technical field:

The present invention relates to eco-friendly green, field of renewable energy technology.Specifically be meant with the consisting of phase-transferring agent mixture controlling catalyst and prepare method of bio-diesel oil.

(2) background technology:

Diesel oil is a kind of important petroleum products, and the diesel oil usage quantity is occupied bigger component in the oil fuel structure in each country of the world, has become important dynamic fuel oil.In the world, the development of vehicle dieselization trend, the use of following diesel oil can be increasing in all trades and professions demand, and the exploitation of petroleum resources has been arrived exhausted day by day even has been begun to the greatest extent.The raising of people's environmental consciousness begins oil-fired substitute research and development simultaneously.Biofuel is to be the renewable energy source of raw material production with the animal-plant oil, is the high-quality surrogate that substitutes petrifaction diesel.China is vast in territory, also is large agricultural country, and agricultural resource is anxious to be waited to develop, and utilizes Vegetable oil lipoprotein production biofuel, is to adjust the farm crop economic structure for rural economy, rural development and rural demography search out, and improves farmers' income, has also opened up vast market for agricultural simultaneously.The research and development biofuel is not only benefited the nation and the people, and is had realistic meaning.

With animals and plants is that raw materials such as grease or waste edible oil carry out transesterification reaction with (methyl alcohol, ethanol) in the presence of acid, alkaline catalysts, and product is biofuel (fatty acid methyl ester, ethyl ester), and byproduct is a glycerine.Traditional esterification technique is to use homogeneous catalyst, as NaOH, the KOH aqueous solution, sodium methylate and sulfuric acid etc., consumption is generally about 1% of grease weight, and temperature of reaction is about 65%, reaction is fast, productive rate also high (can reach 95%), but maximum shortcoming is the aftertreatment problem.After product must neutralize, be with massive laundering to pH value neutrality, and brought a large amount of trade effluents, and cause environmental pollution, increase wastewater treatment cost is increased.With overcritical on-catalytic method and fatty enzyme process owing to complex manufacturing, equipment requirements height, long reaction time cause the production cost height.

(3) summary of the invention:

The objective of the invention is to overcome above-mentioned preparation method's deficiency, propose a kind of employing consisting of phase-transferring agent mixture controlling catalyst and prepare method of bio-diesel oil, solved in the aftertreatment that traditional employing liquid acid or alkali as a catalyst bring and washing and produce problems such as a large amount of trade effluents, contaminate environment.It is simple that the consisting of phase-transferring agent mixture controlling catalyst is used for greasy trans-esterification processes, and transesterify speed and transformation efficiency all are significantly improved, and reacted 30 minutes, and its transformation efficiency is up to 99%.May be because consisting of phase-transferring agent has changed the physico-chemical property of reaction mixture, emulsification the mixed system of grease and methyl alcohol, increased the contact area of reactant, quickened speed of reaction, reduced temperature of reaction, increased product yield.Excessive methanol is reusable.It is neutral that product and byproduct all are, so the washing that need not neutralize.Aftertreatment is very convenient, and no waste water produces, and free from environmental pollution, the renewable repeated use of catalyzer has reduced production cost.

(4) realize above-mentioned technical scheme:

1, consisting of phase-transferring agent mixture controlling catalyst mixes with 1 part of triethyl benzyl ammonia chloride and sodium stannate 1 part (by weight) and to be the consisting of phase-transferring agent mixture catalyzer.

2, prepare method of bio-diesel oil with the consisting of phase-transferring agent mixture controlling catalyst.1: 6 (mol) ratio of grease and methyl alcohol, esterification under the condition of brute force stirring and heating, under normal pressure～3Mpa pressure, 50 ℃～100 ℃ of temperature, reaction times 1～2h, consisting of phase-transferring agent mixture controlling catalyst add-on is 1%～5% to carry out the transesterify molecular rearrangement reaction.Its recovery rate can reach more than 99%.Reacting liquor while hot is filtered, and isolates catalyzer, the filtrate standing demix.The upper strata is biofuel and excessive methanol mixture, is the product biofuel behind 65 ℃ of distillation for removing methanol of low temperature.Lower floor is glycerine and carbinol mixture, is pure glycerine after methyl alcohol is extracted in distillation.Product biofuel and glycerine pH value are neutral, need not neutralize and wash.Avoid the trouble of aftertreatment, prevented the industrial wastewater pollution environment effectively.

Following reaction transesterify molecular transposition takes place at catalyzer and methyl alcohol heating back in grease:

Grease carries out the transesterify molecular transposition at catalyzer and methyl alcohol, and 1mol grease and the reaction of 3mol methyl alcohol have generated 3mol fatty acid methyl ester and 1mol glycerine.

Embodiment:

Embodiment 1

Raw material: drying is handled plam oil, methyl alcohol, consisting of phase-transferring agent mixture controlling catalyst.With plam oil 343 grams (0.4mol) and methyl alcohol 76.8 grams (2.4mol), 1: 6 (mol) ratio of grease and methyl alcohol adds in three mouthfuls of 500ml round-bottomed flasks and stirs, and adds grease weight 1.5%5.148 gram consisting of phase-transferring agent mixture controlling catalyst, be heated to 65 ℃ of back flow reaction after 2 hours, stop heating.Reacting liquor while hot is filtered catalyst separating is gone out, and standing demix is divided into two layers up and down behind the 2h then.

With supernatant liquid 65 ℃ distill out excessive methanol after, promptly get biofuel.After lower floor's liquid excessive methanol steamed, promptly get glycerine.Upper strata biofuel and lower floor's glycerine pH value are neutrality.Product has been avoided the homogeneous catalysis method without aftertreatment, need neutralize, process such as washing.Prevented the industrial wastewater pollution environment effectively.The fatty acid methyl ester of chromatogram detection of biological diesel oil is 95.8%, and the biofuel recovery rate is up to 99.5%.Biofuel product and China 0# diesel oil main performance index are close.

Embodiment 2

Raw material: drying is handled soybean oil, methyl alcohol, consisting of phase-transferring agent mixture controlling catalyst.

With soybean oil 372 grams (0.4mol) and methyl alcohol 76.8 gram (2.4mol) greases and 1: 6 (mol) ratio of methyl alcohol, add in three mouthfuls of 500ml round-bottomed flasks and stir, add grease weight 1.5%5.58 gram consisting of phase-transferring agent mixture controlling catalyst, be heated to 65 ℃ of back flow reaction after 2 hours, stop heating, reacting liquor while hot is filtered catalyst separating is gone out, and standing demix divides two layers up and down behind the 2h then.

With supernatant liquid 65 ℃ distill out excessive methanol after, promptly get biofuel.After lower floor's liquid excessive methanol steamed, promptly get glycerine.Upper strata biofuel and lower floor's glycerine pH value are neutrality.Product has been avoided the homogeneous catalysis method without aftertreatment, need neutralize, process such as washing.Prevented the industrial wastewater pollution environment effectively.The fatty acid methyl ester of chromatogram detection of biological diesel oil is 95.6%, and the biofuel recovery rate is up to 99.3%.Biofuel product and China 0# diesel oil main performance index are close.

Embodiment 3

Raw material: drying is handled Tallow Inedible Grade, methyl alcohol, consisting of phase-transferring agent mixture controlling catalyst.With Tallow Inedible Grade 372 grams (0.4mol) and methyl alcohol 76.8 grams (2.4mol), 1: 6 (mol) ratio of grease and methyl alcohol, add in three mouthfuls of 500ml round-bottomed flasks and stir, add grease weight and add grease weight 1.5%5.58 gram consisting of phase-transferring agent mixture controlling catalyst, be heated to ℃ back flow reaction after 2 hours, stop heating.Reacting liquor while hot is filtered catalyst separating is gone out, and standing demix is divided into two layers up and down behind the 2h then.

With supernatant liquid 65 ℃ distill out excessive methanol after, promptly get biofuel.After lower floor's liquid excessive methanol steamed, promptly get glycerine.Upper strata biofuel and lower floor's glycerine pH value are neutrality.Product has been avoided the homogeneous catalysis method without aftertreatment, need neutralize, process such as washing.Prevented the industrial wastewater pollution environment effectively.The fatty acid methyl ester of chromatogram detection of biological diesel oil is 95.3%, and the biofuel recovery rate is up to 99.1%.Biofuel product and China 0# diesel oil main performance index are close.

Embodiment 4

Raw material: drying is handled soybean oil, ethanol, consisting of phase-transferring agent mixture controlling catalyst.

With soybean oil 325.5 grams (0.35mol) and ethanol 96.6 gram (2.1mol) greases and 1: 6 (mol) ratio of ethanol, add in three mouthfuls of 500ml round-bottomed flasks and stir, add grease weight 1.5%4.88 gram consisting of phase-transferring agent mixture controlling catalyst, be heated to 79 ℃ of back flow reaction after 2 hours, stop heating, reacting liquor while hot is filtered catalyst separating is gone out, and standing demix divides two layers up and down behind the 2h then.

With supernatant liquid 79 ℃ distill out excess ethyl alcohol after, promptly get biofuel.After lower floor's liquid excess ethyl alcohol steamed, promptly get glycerine.Upper strata biofuel and lower floor's glycerine pH value are neutrality.Product has been avoided the homogeneous catalysis method without aftertreatment, need neutralize, process such as washing.Prevented the industrial wastewater pollution environment effectively.The fatty-acid ethyl ester content of chromatogram detection of biological diesel oil is 95.7%, and the biofuel recovery rate is up to 99.5%.Biofuel product and China 0# diesel oil main performance index are close.

Claims

1, prepares method of bio-diesel oil with the consisting of phase-transferring agent mixture controlling catalyst.It is characterized in that: under the condition that the consisting of phase-transferring agent mixture controlling catalyst exists with grease and methyl alcohol with 1: 4～1: 6 (mol) ratio, at normal pressure～3Mpa, temperature under 50 ℃～100 ℃, reaction times 1～2h.Consisting of phase-transferring agent mixture controlling catalyst consumption is a grease weight 1%～5%.Carry out the transesterification reaction molecular transposition, after reaction finished, filtered while hot was isolated catalyzer, left standstill layering behind the 2h.The upper strata is biofuel after steaming methyl alcohol, and lower floor is glycerine after steaming excessive methanol, and levels product P H value is neutrality.

2, according to claim 1ly prepare method of bio-diesel oil with the consisting of phase-transferring agent mixture controlling catalyst.It is characterized in that: consisting of phase-transferring agent is that 1 part of triethyl benzyl ammonia chloride and 1 part of mixed of sodium stannate even (by weight) are the consisting of phase-transferring agent mixture controlling catalyst.

3, according to claim 1ly prepare method of bio-diesel oil with the consisting of phase-transferring agent mixture controlling catalyst.It is characterized in that: consisting of phase-transferring agent mixture controlling catalyst, consumption are grease weight 1%～5%.

4, according to claim 1ly prepare method of bio-diesel oil with the consisting of phase-transferring agent mixture controlling catalyst.It is characterized in that: used grease is animal grease such as available pig, ox, sheep, fish, also available soybean oil, rapeseed oil, Oleum Gossypii semen, Oleum Cocois, plam oil, genetically engineered soybean oil and useless food and drink oil and oil plant tankage.Described low-carbon alcohol is methyl alcohol, ethanol or the mixture of the two.