CN100480362C - Process for preparing biological diesel oil by using grease as raw material - Google Patents

Process for preparing biological diesel oil by using grease as raw material Download PDF

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CN100480362C
CN100480362C CNB2006100126772A CN200610012677A CN100480362C CN 100480362 C CN100480362 C CN 100480362C CN B2006100126772 A CNB2006100126772 A CN B2006100126772A CN 200610012677 A CN200610012677 A CN 200610012677A CN 100480362 C CN100480362 C CN 100480362C
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grease
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low
oil
biofuel
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CN1844331A (en
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刘德江
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Abstract

The invention relates to bioengineering and energy sphere, specifically to a method for preparation of biogenic diesel using grease stores, in which the steps are as follows: a. evenly mixing low-carbon ester and fall according to a mole ratio of 3:1-1 2:1, and driving them with pump into reactor which can autocontrol the temperature; b. adding culture solution of vital cells which are extensively cultured and 10-30 % of grease quality, keeping the culture temperature of the vital cells and the catalyzed reaction temperature between 20 DEG C and 60 DEG C, after 5-60 hours, producing biogenic diesel and glyceryl triformate (glyceryl triacetate) by-product; c. separating cell, biogenic diesel and glyceryl triformate (glyceryl triacetate) by-product with centrifugal process and filtration method; d. making glyceryl triformate (glyceryl triacetate) by-product react with carbinol to produce low-carbon ester for recycle; e. preparing biogenic diesel which can meet a criterion by short-range distillation and rectification of the crude product of biogenic diesel obtained by filtration. The method can make production costs of industry of the biogenic diesel less than production costs of chemical method.

Description

Utilize glyceride stock production method of bio-diesel oil
Technical field:
The present invention relates to biotechnology and energy field, specifically a kind of utilization cultivation living organisms cell catalysis contains glyceride stock and low-carbon ester carries out transesterification reaction production method of bio-diesel oil.
Background technology:
What the production method of biofuel employing at present was maximum is chemical method and biological process.The core of production of biodiesel is that grease and some low-carbon alcohol (methyl alcohol or ethanol) are carried out transesterification reaction under catalyst action, generates corresponding fatty acid methyl ester or ethyl ester.Chemical method be with acid, alkali is catalyzer.Biological process is to be catalyzer with the biological enzyme.Chemical method prepares the excessive alcohol of biofuel employing and reacts with grease under certain temperature, pressure and acid (or alkali) catalysis, needs to wash with water, neutralize, distill the excessive pure and mild by-product glycerin of recovery after reaction finishes.Chemical method is produced the specification of quality harshness to glyceride stock, and it is bigger to consume energy, and discharging of waste liquid is arranged, and invests shortcomings such as big.
Because free fatty acids and the less water of utilizing biological process production biofuel to have in reaction conditions gentleness, non-pollutant discharge, the glyceride stock do not influence advantages such as lipase-catalyzed reaction, the developing direction that meets Green Chemistry, thereby be subject to people's attention day by day.Preparing in the production technique of biofuel at the present biological process of reporting that utilizes, mainly is to utilize the acyl acceptor as reaction such as some low-carbon alcohol such as methyl alcohol, ethanol.Low-carbon alcohol has a strong impact on activity of enzyme reaction, reduce the work-ing life of enzyme, and byproduct of reaction glycerine influences mass transfer very easily attached to the enzyme molecular surface; The use of a large amount of organic solvents has not only increased the cost of whole production technology, and also the operation control for scale operation brings certain difficulty.
Summary of the invention:
Purpose of the present invention aims to provide a kind of glyceride stock production method of bio-diesel oil of utilizing, to solve the low-carbon alcohol that exists in the traditional biological method production method of bio-diesel oil problem, make the industrial production cost of biofuel be lower than the chemical method production cost to the inactivation influence of active somatic cell enzymic activity.
The technical scheme that realizes the foregoing invention purpose is: utilize its step of glyceride stock production method of bio-diesel oil as follows:
A, low-carbon ester and grease are mixed for 3:1~12:1 in molar ratio, with pump squeeze into can be temperature automatically controlled reactor;
B, add active somatic cell nutrient solution through enlarged culturing, add-on is an oil quality 10~30%, keeping the culture temperature and the catalyzed reaction temperature of active somatic cell is 20 ℃~60 ℃, and afterreaction generated biofuel and by product galloformin or vanay in 5~60 hours;
C, usefulness centrifuging, filtration method isolated cell, biofuel and by product galloformin or vanay;
D, by product galloformin or vanay and methyl alcohol reaction generate glycerine and low-carbon ester, and low-carbon ester recycles;
The biofuel that e, filtration obtain obtains standard compliant biofuel through short-range molecular distillation rectifying.
Low-carbon ester of the present invention is selected the low carbon chain ester of the wherein any one or two kinds of above combinations of methyl acetate, ethyl acetate, ethyl formate.
Active somatic cell of the present invention is chosen in cultivates animal and plant cells, microorganism cells, alga cells and all combinations more than the cell of genetic modification is wherein any one or two kinds of that can produce lipase in the breeding.
Grease of the present invention is selected the acidifying oil and the wherein any one or two kinds of above combinations of tankage of animal-plant oil, algae grease, grease-contained waste oil, vegetable and animals oils factory.
According to the glyceride stock production method of bio-diesel oil of utilizing of the present invention, its beneficial effect is the reaction conditions gentleness, with environmental friendliness, the reaction process simple controllable, the active somatic cell self-reproduction produces lipase and is that carbon source consumes glycerine and improved transformation efficiency with glycerine; By product front three (or second) acid glyceride after the separation further can obtain glycerine and low-carbon ester again with the methyl alcohol reaction, and the low-carbon ester of generation can be recycled; The raw material of whole technology is grease and low-carbon alcohol, and product is that fatty acid methyl (or second) ester is biofuel and glycerine.Compared with prior art, present method has solved the low-carbon alcohol that exists in the traditional biological method production method of bio-diesel oil problem to the inactivation influence of active somatic cell enzymic activity, makes the industrial production cost of biofuel be lower than the chemical method production cost.
Embodiment:
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1:
With ethyl acetate and soybean oil in molar ratio 3:1 mix, place can be temperature automatically controlled reactor, add cell culture fluid based on oil quality 30%, keep 38 ℃ of temperature, react that the transformation efficiency of grease conversion biodiesel is 91% after 40 hours.
Embodiment 2:
With methyl acetate and swill oil in molar ratio 12:1 mix, place can be temperature automatically controlled reactor, add cell culture fluid based on oil quality 20%, keep 40 ℃ of temperature, react that the transformation efficiency of grease conversion biodiesel is 92% after 22 hours.
Embodiment 3:
With ethyl formate and useless lard in molar ratio 8:1 mix, place can be temperature automatically controlled reactor, add cell culture fluid based on oil quality 10%, keep 40 ℃ of temperature, react that the transformation efficiency of grease conversion biodiesel is 94% after 60 hours.
Embodiment 4:
By product vanay 5.0Kg, methyl alcohol 0.53Kg, place can be temperature automatically controlled reactor, add 30g sodium hydroxide, keep 60 ℃ of reactions of temperature after 2.5 hours, 99% methanol conversion becomes methyl acetate, and the methyl acetate of generation can directly circulate after simple distillation and be used for the synthetic of biofuel.

Claims (4)

1, a kind of glyceride stock production method of bio-diesel oil of utilizing, its step is as follows:
A, low-carbon ester and grease are mixed for 3:1~12:1 in molar ratio, with pump squeeze into can be temperature automatically controlled reactor;
B, add active somatic cell nutrient solution through enlarged culturing, add-on is an oil quality 10~30%, keeping the culture temperature and the catalyzed reaction temperature of active somatic cell is 20 ℃~60 ℃, and afterreaction generated biofuel and by product galloformin or vanay in 5~60 hours;
C, usefulness centrifuging, filtration method isolated cell, biofuel and by product galloformin or vanay;
D, by product galloformin or vanay and methyl alcohol reaction generate glycerine and low-carbon ester, and low-carbon ester recycles;
The biofuel that e, filtration obtain obtains standard compliant biofuel through short-range molecular distillation rectifying.
2, the glyceride stock production method of bio-diesel oil of utilizing according to claim 1 is characterized in that described active somatic cell is chosen in animal and plant cells, microorganism cells, alga cells and all combinations more than the cell of genetic modification is wherein any one or two kinds of that can produce lipase in the cultivation breeding.
3, the glyceride stock production method of bio-diesel oil of utilizing according to claim 1 is characterized in that described low-carbon ester selects the low carbon chain ester of the wherein any one or two kinds of above combinations of methyl acetate, ethyl acetate, ethyl formate.
4, the glyceride stock production method of bio-diesel oil of utilizing according to claim 1 is characterized in that the acidifying oil and the wherein any one or two kinds of above combinations of tankage of described grease selection animal-plant oil, algae grease, grease-contained waste oil, vegetable and animals oils factory.
CNB2006100126772A 2006-04-30 2006-04-30 Process for preparing biological diesel oil by using grease as raw material Active CN100480362C (en)

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Application Number Priority Date Filing Date Title
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Publication number Priority date Publication date Assignee Title
CN101215233B (en) * 2008-01-09 2012-05-23 江门市江海区嘉诺化工发展有限公司 Technique for producing fatty acid methyl ester
MY180599A (en) * 2008-02-23 2020-12-03 Weifu Lee James Designer organisms for photobiological butanol production from carbon dioxide and water
CN103074389A (en) * 2013-02-04 2013-05-01 东莞市合能微生物能源有限公司 Method for preparing biodiesel by using biological enzyme

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Application publication date: 20061011

Assignee: TANGSHAN JINLIHAI BIODIESEL Corp.,Ltd.

Assignor: Liu Dejiang

Contract record no.: 2012990000645

Denomination of invention: Process for preparing biological diesel oil by using grease as raw material

Granted publication date: 20090422

License type: Exclusive License

Record date: 20120904

EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20061011

Assignee: TANGSHAN JINLIHAI BIODIESEL Corp.,Ltd.

Assignor: Liu Dejiang

Contract record no.: X2023990000629

Denomination of invention: Method for producing biodiesel using oil raw materials

Granted publication date: 20090422

License type: Common License

Record date: 20230620

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