CN101451071A - Biodiesel preparation method and removable production apparatus thereof - Google Patents
Biodiesel preparation method and removable production apparatus thereof Download PDFInfo
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- CN101451071A CN101451071A CNA2007101787813A CN200710178781A CN101451071A CN 101451071 A CN101451071 A CN 101451071A CN A2007101787813 A CNA2007101787813 A CN A2007101787813A CN 200710178781 A CN200710178781 A CN 200710178781A CN 101451071 A CN101451071 A CN 101451071A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention relates to a method for preparing biodiesel and a movable production device. The method adopts brand-new esterification-transesterification two-step technology of combining a catalyst-free high-temperature glycerin esterification process and a high-efficient base catalysis transesterification process. Specifically, glycerin is used to pre-esterify free fatty acid in a lipin material under the condition of catalyst-free, high-temperature and low-pressure reaction in order that the lipin material reaches the requirement of base catalysis transesterification reaction and further produces the biodiesel. Simultaneously, material pretreatment equipment, pre-esterification equipment, transesterification equipment, product separation, reclaiming and refining equipment and a control station are integrated into a movable platform so as to develop the movable production device for continuously and automatically producing the biodiesel. The invention is in particular suitable for acidified acid, trench oil and other waste lipin with dispersive source and great fluctuation of acid price and is also suitable for a wood oil material in unevenly distributed regions and seasons; and certainly, the invention is also suitable for plant hair oil, greatly simplifies the process and has higher production efficiency.
Description
Technical field
The invention belongs to production of biodiesel Technology and biofuel through engineering approaches technical field, relate in particular to and a kind ofly be applicable to that different quality raw oil materials prepare method of bio-diesel oil.
The invention still further relates to a kind of packaged type production of biodiesel device that is used to realize above-mentioned preparation method.
Background technology
The production of biodiesel technology research and utilization for many years, major technique research generally comprises three aspects: chemical catalysis grease transformation technology, enzyme catalysis grease transformation technology and do not have the overcritical transformation technology of catalysis, and the industrial production of biofuel all adopts chemical catalysis at present, thereby the chemical method catalyzed production biodiesel is the maximum and the hottest technical field of research in the production of biodiesel technology.Chemical catalysis generally is divided into again according to the difference of reaction type and utilizes an acidic catalyst catalysis fatty acid esterification to prepare biodiesel technology and utilize basic catalyst catalyzing glycerol ester transesterificationization to prepare biodiesel technology.In chemical method production biofuel, the cost of raw material accounts for 70%-80% of biofuel cost, adopt catering trade waste oil, sewer oil, acidifying oil, the discarded fat of various animal and each kind of plant and the woody oleiferous plants crop of low value not only can turn waste into wealth, and can reduce the production of biodiesel cost effectively without the purified crude oil.But these low value grease common characteristic are exactly all to contain a certain amount of free fatty acids in the grease, and special, catering trade waste oil, sewer oil and acidifying oleic acid lose seriously, and acid number is generally at 70-185mgKOH/g.And chemical bases catalysis method production biofuel requires harshness to glyceride stock, and acid value of lipids must be reduced to below the 2mgKOH/g.Therefore, utilize the Technology of the higher glyceride stock production biofuel of free fatty acid contents such as waste animal and vegetable oil to be the two-step approach production process route at present, promptly at first utilize short carbon chain alcohol esterification generation fatty acid methyl ester such as free lipid acid and methyl alcohol in an acidic catalyst fcc raw material grease, reduce to reach of the requirement of base catalysis transesterification raw material with acid value with raw oil material; Isolate sulfuric acid or solid acid catalyst and fatty acid methyl ester, glyceryl ester and little fat acid mixture behind the acid-catalyzed esterification reaction,, then generally adopt the immobilization bed bioreactor if adopt the solid acid catalysis esterification; Transesterification takes place in the fatty acid methyl ester that then will wash or need not wash, glyceryl ester and little fat acid mixture and a certain amount of methanol mixed under the catalysis of alkali catalyst, generate fatty acid methyl ester (biofuel) and byproduct glycerine; Reaction back separate methyl esters mutually and glycerine mutually, and in and residual basic catalyst in the two-phase, then respectively through the distillation purification to obtain biofuel product and by-product glycerin respectively.
It is all to adopt free lipid acid and methyl alcohol generation esterification in an acidic catalyst fcc raw material grease that above traditional two-step approach is produced the most outstanding characteristics of biodiesel processes, to reduce the acid value of raw oil material.Numerous technical patents all concentrate in the improvement research of acid catalyzed esterification process, the aspects such as improvement that contained novel acid screening of catalyst, Catalytic processes, but still be difficult to overcome classical acid catalysis pre-esterifying process inherent defective, also classical acid catalysis pre-esterifying process do not had breakthrough.Traditional acid catalyzed esterification technology greatest problem is that the acid-catalyzed esterification reaction specificity is poor, at acid catalysis free fatty acids and methyl alcohol generation esterification reaction process, also be accompanied by the generation of the esterolytic side reaction of catalyzing glycerol, esterification reaction process control difficulty, directly cause esterification mix products complicated component and quality fluctuation big, in actual production, be difficult to know fatty acid methyl ester and glyceryl ester content separately in the esterification mix products, the difficulty of determining that causes second step base catalysis transesterification metallization processes parameter, the lighter causes reaction not exclusively, the diesel product quality is produced in influence, weight person causes the material saponification, cause producing failure, be difficult to realize automatization and serialization production.In addition, classical acid catalytic esterification technology itself exists still that poor, the pure consumption of adaptability to raw material is excessive, catalytic efficiency is low, the reaction times is long, low, the effective energy utilization rate of effective efficiency of pcr product is low and problem such as the energy consumption waste is serious and acid water pollution is serious in actual production.
Remove outside the technical factor, the raw material problem is the bottleneck that restricts China's biofuel industry development at present, though China has abundant oil crops resource and huge acidifying oil and the sewer oil of output, exist raw material sources dispersion, oil crops plantation shortage scale and sewer oil collection difficulty and quality and be difficult to problems such as assurance.Utilizing the woody oleiferous plants plant simultaneously is the characteristic and the advantage of China's development biofuel, China is vast in territory, the region span is big, hydrothermal resources distributes different, woody oleiferous plants plant resources kind is rich and varied, according to preliminary investigation, national wild woody oleiferous plants oil content in plants is at about 1000 kinds more than 15%, and wherein oleaginousness is at about 300 kinds more than 20%.But mainly being grown in mountain region and knob, production, to be subject to seasonal restrictions, to collect and transport difficulty and energy resource density low be woody oleiferous plants plant distinguishing feature.And the development abroad road is still mainly followed in China's biofuel industry development at present, ignores China's present stage national conditions, thereby and attempts to realize in a short time that in China the centralized cooked mode of biofuel greatly develops the maximization biodiesel production facility.This has just produced China's conspicuous contradiction that resource is disperseed and processing is concentrated of stage biofuel development now, is reflected in glyceride stock in collection, transportation and storage process.Raw materials cost accounts for about 70%～80% of biofuel product cost, and the collection of raw material and transportation difficulty will cause China's biofuel finished product to lose price competitiveness, also will be difficult to guarantee simultaneously biofuel processing enterprise raw material supplying demand.
In sum, the pre-esterification two-step approach of existing classical acid catalysis is produced the biodiesel processes technology and is existed technical many deficiencies and defective, and the biodiesel production facility immobilized development mode that maximizes also is difficult to adapt to China present stage biofuel glyceride stock and supplies with characteristics, can't solve the raw material bottleneck problem of restriction China biofuel development.And the present invention is directed to that the pre-esterification two-step approach of classical acid catalysis produces that the biodiesel processes technology exists defective and deficiency and the Technology and the production unit of the pre-esterification two-step approach of cover catalyst-free raw material production biofuel are developed in the design of novelty, and first development and design packaged type production of biodiesel device, propose production of biodiesel device packaged type notion, solved the problem of the raw material bottleneck of China's biofuel industry development from the angle of industrialization technology.Method for producing biodiesel that the present invention relates to and removable production apparatus thereof not only can well adapt to characteristics such as the fluctuation of China present stage material quality is big, source dispersion, and can realize the production of the low cost of biofuel, efficient, energy-conservation, high-quality and environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and removable production apparatus thereof of novel biofuel, to overcome defective and the deficiency that the pre-esterification two-step approach of classical acid catalysis production production of biodiesel technology exists, and adapt to China's present stage oil resource dispersion, region and season distribution inequality and quality is difficult to raw material supplying characteristics such as assurance, solve the biodiesel raw material problem from the industrialization technology angle, avoided the overlapping investment construction of biofuel processing enterprise.Thereby realize the production of the low cost of biofuel, efficient, energy-conservation, high-quality and environmental protection, for a new road is explored in China's biofuel industrialized development.
For achieving the above object, the invention provides a kind of brand-new " esterification-transesterificationization " two-step approach that adopts catalyst-free high temperature glycerine esterification process to combine and prepare method of bio-diesel oil, the steps include: with efficient base catalysis transesterification process
(a) glyceride stock heating fusion after-filtration is removed wherein insoluble impurities, adds glycerine, under the situation of not adding any catalyzer, and in 150-350 ℃, preferred 280-320 ℃; Vacuum tightness 350-600mmHg, preferred 400-500mmHg; Carry out pre-esterification reactor under the inert gas protection; Wherein the mol ratio of free lipid acid is 0.3-1.5 in glycerine and the grease raw material;
(b) glyceride mixture of step a and methanol mixed, and the methanol solution that adds sodium hydroxide or potassium hydroxide in 50-80 ℃, carries out transesterification under the inert gas protection as catalyzer; Wherein, the mol ratio of methyl alcohol and glyceryl ester is 4:1-9:1, preferred 5:1-6:1; The consumption of sodium hydroxide or potassium hydroxide accounts for 0.8-2wt% of glyceryl ester quality, preferred 1%-1.5wt%;
(c) product of step b is the mutually light and raw glycerine heavy phase of thick methyl esters through centrifugation; Wherein: thick methyl esters gently in inert gas protection underpressure distillation down, obtains methyl alcohol, biofuel product and pitch respectively; The raw glycerine heavy phase is carried out underpressure distillation through washing neutralization basic catalyst wherein, obtains methyl alcohol and glycerine respectively;
(d) methyl alcohol that obtains among the step c reenters step b and participates in reaction; The glycerine that obtains reenters step a and participates in reaction.
Described preparation method, wherein, the grease raw material among the step a is catering trade waste oil, sewer oil, acidifying oil, the discarded fat of various animal, each kind of plant and woody oleiferous plants crop crude oil, wherein free fatty acid content is at 5-80wt%.Especially, this process is particularly useful for waste oils such as the great acidifying oil of acid value fluctuation range, sewer oil, the discarded fat of various animals and plants, and when adopting each kind of plant and woody oleiferous plants crop crude oil, process can be simplified greatly, and production efficiency can be higher.
Described preparation method, wherein, the concentration of methanol solution of sodium hydroxide or potassium hydroxide is 10% among the step b.
Described preparation method wherein, has all adopted protection of inert gas in esterification reaction process and the fatty acid methyl ester still-process, and inert gas is helium, argon gas, nitrogen and carbonic acid gas.
The packaged type device that is used to realize above-mentioned preparation method provided by the invention, its prominent feature is with reaction unit and the automatization supervisory control desk is integrated is arranged on the packaged type platform, form a self-contained complete opposition packaged type production of biodiesel system, include:
One metab and skeleton structure, the support platform of formation removable production apparatus.
One plate-and-frame filter press is used for glyceride stock is filtered;
At least one pre-esterification reactor still, and can connect by a plurality of pre-esterification reactor stills, be provided with agitator in the pre-esterification reactor still, be used for the glyceride stock after filtering is carried out pre-esterification reactor; This pre-esterification reactor still connects a vacuum pump, to keep the vacuum tightness of pre-esterification reactor still;
At least one transesterification still, and can connect by a plurality of transesterification stills, be used for the pre-esterification reactor product is carried out transesterification;
One whizzer is used for the transesterification product is separated;
One fatty acid methyl ester distillation tower is used for the isolated thick methyl esters of whizzer is gently carried out underpressure distillation mutually, obtains methyl alcohol, biofuel and pitch respectively;
One inert gas gas-holder and gas path pipe is used for pre-esterification reactor still, transesterification still and fatty acid methyl ester distillation tower are carried inert gas;
In one and cleaning of evaporator, be used for the basic catalyst of the isolating raw glycerine heavy phase of whizzer is neutralized;
One glycerine one-level distillation tower, glycerine secondary distillation tower and purification of glycerin tower and glycerine circulation line, be used for the raw glycerine heavy phase of the basic catalyst that neutralized is carried out underpressure distillation and refining, obtain methyl alcohol and glycerine respectively, and will be delivered to the glycerine raw material storage tank through a part of glycerine behind the glycerine one-level distillation tower distillatory and carry out recycle;
One refining methanol tower is used for circulating to do to be delivered to the transesterification still after the processed from the methyl alcohol of fatty acid methyl ester distillation tower and glycerol distillation tower.
One oil burning package boiler or motor device are used to provide the power of packaged type production of biodiesel device, wherein the oil burning package boiler pitch that can also burn and produce in the production process.
One automatization supervisory control desk with the automatization control of whole biofuel serialization production process, is realized the automatization control of whole process of production.
Described packaged type device wherein, is equipped with raw material storage tank and product storage tank on moveable platform; Wherein the glyceride stock storage tank is connected with plate-and-frame filter press.
Described packaged type device, wherein, the pre-esterification reactor still is provided with stirrer.
Described packaged type device, wherein, a plurality of pre-esterification reactor stills, the series connection of a plurality of transesterification still are used.
By enforcement of the present invention, it has following advantage:
1, production of biodiesel device packaged type notion and develop a cover packaged type continuously producing biodiesel device is proposed, the characteristics that are difficult to guarantee at China's oil resource dispersion, region and season distribution inequality and quality, solve the biodiesel raw material bottleneck problem from the industrial technology angle, improved the utilization ratio of production of biodiesel device.Packaged type biofuel device can or be produced needs and transfer to another production site by traffic system from a production site according to the raw material supplying variation, it is a mobile production of biodiesel factory, avoided domestic one side production of biodiesel factory to be subjected to raw material restriction under-capacity operation, the difficult situation of the continuous duplicate construction of production of biodiesel factory has realized that really according to specific time and site rationally utilizes the production biofuel of various resource intensive formulas on the other hand.Can be seen by above-mentioned analysis, be subjected to today of the serious restriction of raw material bottleneck in China's biofuel industry development at present, development packaged type production of biodiesel device has high feasibility and good and economic.
2, adopt the free pre-esterification techniques of fatty acid glycerine in the novel catalyst-free grease oil plant, under the reaction conditions of catalytic high temperature decompression, directly the free fatty acids in the glyceride stock is changed into and be glyceryl ester without any need for chemical catalyst, reaction conditions by high temperature decompression goes out reaction system to the moisture evaporation that produces in the moisture that contains in the glyceride stock itself and the esterification reaction process simultaneously, thereby guarantee the specificity of reaction, shortened the reaction times and guaranteed high esterification yield, and aqueous hardly pre-esterification mix products helps the carrying out of transesterification more.This technological invention is the breakthrough to traditional acid catalysis pre-esterifying process, overcome that the acid water pollution that classical acid catalysis pre-esterifying process self is difficult to overcome is serious, equipment and pipeline corrosion, long reaction time, reaction specificity be poor, multiple reaction takes place simultaneously, and esterification process is difficult to control, the product component complexity, effectively efficiency of pcr product carboniogenesis low, the vitriol oil causes the product color variation and is unfavorable for realizing defective such as automatization serialization production.By above-mentioned analysis as can be seen, the free pre-esterification techniques Technology of fatty acid glycerine is extremely strong to the adaptability of glyceride stock in this catalyst-free grease oil plant, and help realizing the serialization and the automatization of producing, more enterprise has saved the huge investment that acid water pollution is handled that is used for simultaneously, has the high economic feasibility and the production feature of environmental protection.
3, the acyl acceptor that adopts of the present invention be the glycerol (glycerine) that is different from low carbon chain alcohol such as traditional methyl alcohol with glyceride stock in free lipid acid generation esterification.And classical acid catalysis methanol pre-esterification reactor product component complexity, every batch of fluctuation of the concrete content of fatty acid methyl ester and glyceryl ester is big, directly causing transesterification metallization processes difficult parameters to determine, is the major cause that causes the incomplete or excessive saponification reaction failure of transesterification.And glycerine and free fatty acids esterification product are glyceryl ester, thereby guaranteed the unicity of the composition of esterification mix products, only contain glyceryl ester, thereby make ensuing transesterification conditional parameter stable, help the control of production process, more help realizing the serialization automatic production and improve biofuel product yield and quality.And can realize the circulation and the recovery of glycerine in the preparation of biofuel, the cost that economizes in raw materials has more important economic implications in today that the glycerine price continues to drop.
4, the present invention goes for the raw oil material production biofuel of different qualities, the permission free fatty acid content haves a wide reach, raw material sources are extensive, and the raw materials pretreatment process is simple, only need get final product through simple filtration, can be production of biodiesel factory and save the facility investment that is used for raw materials pretreatment in a large number, improve raw material availability.
5, the present invention has adopted feeding inert gas sfgd. in the whole process of production of biodiesel; avoided biofuel product deterioration by oxidation in process of production; thereby improve the quality and the yield of biofuel product, and make the biofuel product have preferable color and luster.
6, the present invention has realized part material and power self-sufficiency in the production process, and whole process of production middle part any waste residue of generation and pollutent, is the production process of a clean environment firendly.
7, the present invention has realized that the biofuel serialization produces, and is convenient to the enforcement of automatization control, makes that the production technique operating process is simple, safety, environmental protection, efficient, helps enhancing productivity, and saves the labor management cost.
Description of drawings
Fig. 1 is a production of biodiesel process flow sheet of the present invention.
Fig. 2 is a packaged type production of biodiesel device plot plan of the present invention.
1: the glyceride stock storage tank
2: the glycerine raw material storage tank
3: plate-and-frame filter press
4: the rare gas element gas-holder
5: the pre-esterification reactor still
6: the methyl alcohol storage tank
7: potassium hydroxide/sodium storing ball
8: screw feeder
9: potassium methylate/sodium solution storage tank
10: the transesterification still
11: the phosphoric acid storage tank
12: the refining methanol tower
13: the fatty acid methyl ester distillation tower
14: whizzer
15: glycerine one-level distillation tower
16: glycerine secondary distillation tower
17: in and cleaning of evaporator
18: the purification of glycerin tower
19: biofuel product storage tank
20: asphalt storage
21: the glycerol product storage tank
22: the phosphate fertilizer storage tank
23: the automatization supervisory control desk
24: oil burning package boiler/motor device
25: metab and skeleton structure
Embodiment
The method that can utilize different quality glyceride stock continuously producing biodiesels and packaged type production of biodiesel device that the present invention proposes, it comprises glyceride stock storage tank (1), glycerine raw material storage tank (2), methyl alcohol storage tank (6), potassium hydroxide/sodium storing ball (7), plate-and-frame filter press (3), pre-esterification reactor still (5), transesterification still (10), whizzer (14), fatty acid methyl ester distillation tower (13), in and cleaning of evaporator (17), glycerine one-level distillation tower (15), glycerine secondary distillation tower (16), purification of glycerin tower (18), refining methanol tower (12), biofuel product storage tank (19), asphalt storage (20), glycerol product storage tank (21), phosphate fertilizer storage tank (22), oil burning package boiler (24) and inertial gas tank (4) and the air-channel system that leads to each reactor distillation tower, these equipment are by various stainless steel pipes, valve is connected with various types of pumps, be integrated on the metab and outsidely fixed by the metallic framework structure of certain specification size, while packaged type production of biodiesel device also is furnished with the automatization supervisory control desk, to realize the automatic production of biofuel.
The object of the invention to solve the technical problems can also be applied to the following technical measures to achieve further.
In the device of the present invention, its raw materials pretreatment system is made up of interchanger, plate-and-frame filter press and glyceride stock storage tank, and do not need any raw material dehydration equipment, wherein interchanger heated oil fat raw material is beneficial to filtration treatment so that be sewer oil, the fusing of frying wet goods waste oil of curdled appearance under normal temperature condition, in filter process and add diatomite, remove the insoluble solid impurities in the glyceride stock as flocculating aids.
The required strong alkali catalyst of transesterification is liquid sodium methylate/potassium solution, solid alkali sodium hydroxide or potassium hydroxide mix dissolving and make sodium methylate/potassium solution by being transported in potassium methylate/sodium solution storage tank methyl alcohol with the certain mass ratio through screw feeder in potassium hydroxide/sodium storing ball, and wherein the methyl alcohol transport pipe is furnished with online well heater.
The supporting vacuum pump that is provided with of pre-esterifying kettle of free lipid acid and glycerine generation esterification in the glyceride stock, and can one or several linear being cascaded according to needs of production pre-esterification reactor still.
Be provided with the glycerol subsidence device between pre-esterification reactor still and the transesterification still, behind the pre-esterification reactor still, be provided with heat-energy recovering apparatus simultaneously.
Be provided with the heat exchanger that is used for pre-esterification products energy recovery between pre-esterification reactor still and the glycerol subsidence equipment, can adopt fixedly plate-type heat exchanger or U-shaped tubular heat exchanger.
The transesterification still is according to one or several linear being cascaded of needs of production.
The fatty acid methyl ester still-process is the mode that adopts underpressure distillation, can adopt molecular distillation tower, scraper plate distillation tower and falling-film distillation tower, and discharge port is furnished with the bitumen recovery device at the bottom of vacuum still.
In be with water washing process that to adopt concentration be in 30%-85% the phosphoric acid solution and wash sodium methylate/potassium that raw glycerine contains in mutually that and discharge port is furnished with the phosphoric acid salt solid recovery unit at the bottom of neutralization tank.
The glycerol distillation process is to adopt the mode of underpressure distillation, can adopt scraper plate distillation tower and falling-film distillation tower.
Be provided with glycerine recycle pipeline in the device, the low-quality glycerine part that the heavy phase raw glycerine obtains behind the underpressure distillation column distillation is directly prepared against the pre-esterification reactor recycle in the blowback glycerine raw material storage tank, and redundance glycerine enters the further refining food grade glycerine that obtains of purification of glycerin tower.
The purification of glycerin process is made up of the strainer of filling adsorption tower and based thin film technology, can adopt activated carbon, molecular sieve, atlapulgite adsorption stuffing and micrometre grade thin film filter.
The refining methanol process is the mode of filling adsorption, can adopt the molecular sieve filling adsorption tower to remove and reclaim the moisture that contains in the methyl alcohol, utilizes once more after methyl alcohol closed circulation pipeline pumps into the methyl alcohol storage tank.
The gas path pipe, the pressure loading valve that are provided with the rare gas element gas-holder in the device and are connected with pre-esterification reactor still, transesterification still and fatty acid methyl ester distillation tower.Rare gas element can adopt helium, argon gas, nitrogen and carbonic acid gas etc. not with the gas of grease generation oxidizing reaction.
Integrated automatization supervisory control desk on the device the biofuel whole process of production is carried out automatization control, has been realized the automatic production of packaged type production of biodiesel device.
Device production power resources of the present invention can be divided into two kinds, and the one, adopt electrically heated, the 2nd, adopt steam heating.When adopting electrically heated, be integrated with motor device on the packaged type device, each well heater, reactor and distillation tower are all corresponding accordingly is designed to electrically heated; When adopting steam heating, be integrated with oil burning package boiler on the packaged type device, and supportingly corresponding steam-heated pipe line arranged or directly utilize on-the-spot existing Boiler Steam power system.Adopt electrically heated or on-the-spot Boiler Steam power system to build investment with device, can design and build the higher removable production apparatus of unit volume production capacity for the advantage of producing power is to save the huge space of packaged type device.
The present invention can be integrated into raw material storage tank and product storage tank on the packaged type production of biodiesel device according to needs of production, also can adopt external raw material storage tank of pipe connection and product storage tank, only integrated pretreatment equipment, pre-esterification equipment, transesterification equipment, product Separation and Recovery and major equipments such as purification apparatus and automatization supervisory control desk are to save packaged type production of biodiesel device space.
The present invention can be according to the variation and the needs of production of raw material supplying, with one or some in parallel uses of packaged type production of biodiesel device, to obtain bigger throughput.
Outstanding feature of the present invention is with reaction unit and the automatization supervisory control desk is integrated is arranged on the packaged type platform, form a self-contained complete opposition packaged type production of biodiesel system, its outside dimension and quality meet National Traffic System transportation standard, can or produce needs and transfer to another production site by traffic system from a production site according to the raw material supplying variation, be a mobile production of biodiesel factory.
Technical process of the present invention is particularly suitable for waste oils such as the great acidifying oil of acid value fluctuation range, sewer oil, the discarded fat of various animals and plants, and when adopting each kind of plant and woody oleiferous plants crop crude oil, process can be simplified greatly, and production efficiency can be higher.Various glyceride stocks such as catering trade waste oil, sewer oil, acidifying oil, the discarded fat of various animal and various woody oleiferous plants crop greases, generate biofuel product and by-product glycerin through raw materials pretreatment, catalyst-free glycerine high temperature pre-esterification reactor, highly basic alcoholic solution catalysis transesterification and product separation purification Production Flow Chart, wherein methyl alcohol and partial glycerol are the circulation of a sealing in whole flow process.Specifically may further comprise the steps:
A) the online heating of the glyceride stock of the different free fatty acid contents in glyceride stock storage tank fusion removes by filter wherein through plate-and-frame filter press (3) that insoluble impurities enters in the pre-esterification reactor still (5);
B) in pre-esterification reactor still (5), under the reaction conditions of high temperature decompression catalyst-free, free lipid acid and glycerine generation esterification in the raw oil material, the water that moisture that itself contains in the raw material and esterification are produced is isolated reaction system by reduction vaporization;
C) glyceride mixture pumps in the transesterification still (10) and methanol mixed after the esterification, simultaneously sodium hydroxide/potassium the solid catalyst in potassium hydroxide/sodium storing ball (7) by screw feeder (8) be conveyed in potassium methylate/sodium solution storage tank (9) with methyl alcohol storage tank (6) in the methanol mixed dissolving that pumps into, make potassium methylate/sodium solution and pump in the transesterification still (10), catalyzing glycerol ester mixture and methyl alcohol carry out transesterification in the transesterification still;
D) the transesterification mix products is divided into the mutually light and raw glycerine heavy phase of thick methyl esters after whizzer (14) separates;
E) thick methyl esters gently pumps into mutually in the fatty acid methyl ester distillation tower (13) and carries out underpressure distillation, obtains methyl alcohol, biofuel product and pitch respectively, and the methyl alcohol of recovery enters in the refining methanol tower (12) and handles;
F) utilize the phosphoric acid solution washing with cleaning of evaporator in pumping into after raw glycerine is separated, neutralization basic catalyst wherein, enter in the glycerine one-level distillation tower (15) behind the separation phosphoric acid salt solid and carry out underpressure distillation, obtain methyl alcohol and glycerine respectively, the methyl alcohol that reclaims enters in the refining methanol tower (12) and handles, circulation is used for and the free lipid acid generation esterification of glyceride stock in a part of blowback glycerine raw material storage tank in the glycerine herein, redundance enters in glycerine secondary distillation tower (16) and the purification of glycerin tower (18) and carries out underpressure distillation and refining, to obtain food grade glycerine;
G) methyl alcohol that reclaims in the reaction process concentrates in the refining methanol tower (12), removes the moisture that wherein contains, and pumps into methyl alcohol storage tank (6) then in order to the recycle of glyceryl ester transesterification.The above step is the process that the serialization of continuously feeding and discharging is continuously produced, do not have any residue contamination in process of production and produces, and be the production process of a clean environment firendly.(consulting Fig. 1)
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid method for producing biodiesel and packaged type production of biodiesel device, wherein said glyceride stock comprises catering trade waste oil, sewer oil, acidifying oil, the discarded fat of various animal, each kind of plant and the woody oleiferous plants crop crude oil without refining, it is characterized in that all having in the raw oil material certain content even the very high free fatty acids of content, free fatty acid content all has splendid adaptability 5%-80%.Be fit to especially, more the source disperse, be subjected to region and season distribution restriction obviously, collect characteristics such as transportation difficulty and quality fluctuation are bigger outstanding more catering trade waste oil, sewer oil and woody oleiferous plants crop glyceride stocks such as crude oil without refining.If adopting raw plant oil certainly is raw material, process can be simplified greatly, and production efficiency can be higher.
Described glyceride stock pretreatment stage includes only the filtration treatment of glyceride stock, glyceride stock generally is heated to 40-60 ℃, be the grease of curdled appearance such as catering trade waste oil, sewer oil, the discarded fat of various animal and some woody oleiferous plants crop crude oil under the normal temperature with fusing, add super-cell and remove by filter solid impurity in the glyceride stock through plate-and-frame filter press without refining.
In the described glyceride stock pre-esterification reactor process with raw material in the short chain alcohol of free lipid acid generation esterification be glycerine, glycerine is the technical grade glycerine of purity 95% or the raw glycerine that reclaims through the simple distillation reaction; Short chain alcohol with glyceryl ester generation transesterification in the transesterification is methyl alcohol, ethanol or many alcohol mixtures.
The esterification of described glyceride stock free fatty acids and glycerine is without any need for chemistry and biological catalyst, and pre-esterification reactor still temperature is controlled at 150-350 ℃, and the preferred temperature scope is 280-320 ℃; The vacuum degree control of pre-esterification reactor still is between 350-600mmHg, and preferable vacuum ranges is 400-500mmHg.
The glycerine inventory that adds changes according to free fatty acid content difference in the raw oil material, and the molar ratio range of free lipid acid is 0.3-1.5 in the add-on of glycerine and the raw oil material, and preferable range is 1.1-1.4.
The catalyzer that described catalyzing glycerol ester and methyl alcohol generation transesterification prepare the employing of fatty acid methyl ester is sodium hydroxide/potassium, sodium hydroxide/potassium solid at first in having the potassium methylate of condensation reflux unit/sodium solution storage tank according to mass ratio 1:9 and methanol mixed, stir and also to be heated to 50-60 ℃ to promote the dissolving of sodium hydroxide/potassium in methyl alcohol, to be mixed with concentration being that sodium methylate/potassium solution of 10% is standby.
Described glyceride mixture and methyl alcohol generation transesterification prepare in the process of fatty acid methyl ester, what adopt is at first with after glyceride mixture and the pure methanol mixed, the back adds potassium methylate/sodium methanol solution catalyzer, the molar ratio range of total add-on of methyl alcohol and glyceryl ester is controlled at 4:1-9:1, and preferable range is 5:1-6:1; Sodium hydroxide/potassium catalyst levels accounts for 0.8-2wt% of glyceryl ester quality, and preferable range is 1%-1.5wt%; Transesterification still temperature is controlled at 50-80 ℃, and preferred temperature is 60-70 ℃; Stir speed (S.S.) is controlled at 200-600r/min, and preferable stir speed (S.S.) is 300-400r/min.
In the process of described fatty acid methyl ester underpressure distillation, the isolated glycerine that comprises fatty acid methyl ester, methyl alcohol, a small amount of unreacted glyceryl ester and about 0.5% mass ratio in the light thick mutually methyl esters of behind the transesterification.In the fatty acid methyl ester vacuum still, at first under 120 ℃, distill out unnecessary unreacted methanol, and send into refining recycle in the refining methanol tower.The cut that cuts 120-250 ℃ is as the biofuel product; Boiling range is greater than 250 ℃ last running such as high boiling point macromole, some high molecular polymers and unreacted glyceryl ester in the distillation tower, distillates from the bottom of tower, becomes residual oil or pitch, can be used for boiler combustion fuel.
Reclaim the method that adopts molecular sieve adsorption to dewater in the refining methanol process, molecular sieve is molecular sieve that can the person's of choosing property adsorbed water molecule, as potassium A type (3A) molecular sieve.
Described raw glycerine reduces pressure in the distillatory process mutually, includes the fatty acid methyl ester of glycerine, methyl alcohol, saponified, an alkali metal salt and about mass ratio 1.5% behind the transesterification in the isolated heavy phase raw glycerine.Behind the sodium methylate/potassium that in 30%-85% phosphoric acid solution, contains in mutually with the washing raw glycerine, send in the glycerine one-level distillation tower and carry out underpressure distillation, 150 ℃ of distillation tower temperature, obtain a low-quality glycerine part and pump into the head tank recycle through the glycerine recycle system, unnecessary glycerine continues to enter in the glycerine secondary distillation tower and carries out underpressure distillation, after this 220 ℃ of distillation tower temperature entering the processing of decolouring in the purification of glycerin tower and obtaining the food grade glycerol product.
The active effect of technical scheme of the present invention, technical manual and technique means and this invention that more than developed and the beneficial effect that can reach, those skilled in the art can be implemented according to the content of present technique specification sheets, but utilize the method for above-mentioned announcement and technology contents to make a little modification, variation or modification, all still belong in the technical scheme scope of the present invention.Below be preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Embodiment
With free fatty acid content is that 40% catering trade waste oil raw material is an example, and concrete composition analysis of waste oil and lipid acid are formed and seen Table 1 and table 2 respectively.
Composition analysis in the table 1 catering trade waste oil
The composition of lipid acid in the table 2 catering trade waste oil
With 200Kg be solid state catering trade waste oil by heat exchanger heats to 40-60 ℃ so that it is fused into liquid state, through plate-and-frame filter press (3), and to adopt diatomite be flocculating aids, and filtration pressure difference is 0.3-0.4Mpa, insoluble solid impurities in the filtering catering trade waste oil.
Filtered waste oil mixes with 60Kg industry glycerol (98%) to be sent in the pre-esterification reactor still (5); under logical protection of inert gas, be heated to 300 ℃; and maintenance reactor pressure is 500mmHg; stir speed (S.S.) is controlled at 400r/min, carries out glycerol subsidence and carries out energy recovery by heat exchanger behind the reactor that pumps behind the reaction 3h.
When the temperature of pre-esterification products glyceride mixture is reduced to 60-70 ℃, send in the transesterification still (10) with 11Kg methyl alcohol mixed evenly after, the mass ratio that pumps into 56Kg again is 10% methanol solution of sodium methylate, the carrying out of catalysis transesterification, stir speed (S.S.) is controlled at 400r/min, react and pump the transesterification still after 3 hours and carry out whizzer (14) and separate, the light fatty acid methyl ester that contains 196Kg in mutually approximately of crude fatty acid methyl ester, 10Kg glycerine and 6-7Kg methyl alcohol, the raw glycerine heavy phase contains 38Kg glycerine approximately, 14-15Kg methyl alcohol, 3-4Kg fatty acid methyl ester, the an alkali metal salt that 1Kg is saponified and a large amount of.
Crude fatty acid methyl ester is gently sent into mutually in the fatty acid methyl ester distillation tower (13) and is carried out underpressure distillation, working pressure is 5mmHg, at first residuing in the methyl alcohol of fatty acid methyl ester in mutually at 120 ℃ distillates from top of tower, import in the refining methanol tower (12) and utilize molecular sieve-4 A 3 to remove the water that wherein contains, blowback methyl alcohol storage tank (6) is standby; 120-250 ℃ middle runnings is derived and is condensed to biofuel product storage tank (19) as the biofuel product in the collection vacuum still, and quality is about 190Kg, and the last running more than 250 ℃ distillates at the bottom of tower, pumps into asphalt storage (20).
During the raw glycerine heavy phase is sent into and cleaning of evaporator (17), the concentration that adds 5.8Kg is the washing that neutralizes of 85% phosphoric acid solution, settlement separate phosphoric acid salt and saponified being transported in the phosphate fertilizer storage tank (22) that goes out; The about 56Kg of raw glycerine sends in the glycerine one-level vacuum still (15), and working pressure 400mmHg under 150 ℃ of the temperature, distills out out the about 14Kg of wherein residual aqueous methanol, imports in the refining methanol tower (12); The glycerine that obtains is about a 40Kg part through in the glycerine recycle pipeline blowback glycerine raw material storage tank (2), recycling, remainder glycerine pumps into and carries out second distillation (220 ℃) and activated carbon decolorizing refining in glycerine secondary distillation tower (16) and the purification of glycerin tower (18), pumps in the glycerol product storage tank (21) after reaching food grade glycerine.
Wherein partial glycerol is the circulation of a sealing in whole process of production, altogether four kinds of products: biofuel, pitch, food grade glycerine and phosphate fertilizer, the about 190Kg of main products biofuel wherein, the raw oil material utilization ratio is about 95%.
Claims (8)
1, a kind of biodiesel oil preparing process the steps include:
(a) glyceride stock heating fusion after-filtration is removed wherein insoluble impurities, adds glycerine, and in 150-350 ℃, vacuum tightness 350-600mmHg carries out pre-esterification reactor under the inert gas protection; Wherein the mol ratio of free lipid acid is 0.3-1.5 in glycerine and the grease raw material;
(b) glyceride mixture of step a and methanol mixed, and the methanol solution that adds sodium hydroxide or potassium hydroxide in 50-80 ℃, carries out transesterification under the inert gas protection as catalyzer; Wherein, the mol ratio of methyl alcohol and glyceryl ester is 4:1-9:1; The consumption of sodium hydroxide or potassium hydroxide accounts for 0.8-2wt% of glyceryl ester quality;
(c) product of step b is the mutually light and raw glycerine heavy phase of thick methyl esters through centrifugation; Wherein: thick methyl esters gently in inert gas protection underpressure distillation down, obtains methyl alcohol, biofuel product and pitch respectively; The raw glycerine heavy phase is carried out underpressure distillation through washing neutralization basic catalyst wherein, obtains methyl alcohol and glycerine respectively;
(d) methyl alcohol that obtains among the step c reenters step b and participates in reaction; The glycerine that obtains reenters step a and participates in reaction.
2, preparation method as claimed in claim 1, wherein, glyceride stock among the step a is catering trade waste oil, sewer oil, acidifying oil, the discarded fat of various animal, each kind of plant and the woody oleiferous plants crop crude oil without refining, and wherein free fatty acid content is at 5-80wt%.
3, preparation method as claimed in claim 1, wherein, among the step a, temperature of reaction is 280-320 ℃, vacuum tightness is 400-500mmHg.
4, preparation method as claimed in claim 1, wherein, the concentration of methanol solution of sodium hydroxide or potassium hydroxide is 10% among the step b.
5, preparation method as claimed in claim 1, wherein, the mol ratio of methyl alcohol and glyceryl ester is 5:1-6:1 among the step b.
6, preparation method as claimed in claim 1, wherein, inert gas is helium, argon gas, nitrogen and carbonic acid gas.
7, a kind of packaged type production of biodiesel device that is used to realize the described preparation method of claim 1 comprises:
One metab and skeleton structure, the support platform of formation removable production apparatus;
One plate-and-frame filter press is used for glyceride stock is filtered;
At least one pre-esterification reactor still, or the series connection of a plurality of pre-esterification reactor still are provided with agitator in the pre-esterification reactor still, are used for the free lipid acid of the glyceride stock after filtering is carried out esterification; This pre-esterification reactor still connects a vacuum pump, with the vacuum tightness of maintenance pre-esterification reactor still, and is connected with the protection of inert gas device;
At least one transesterification still, or the parallel connection of a plurality of transesterification still are used for the pre-esterification reactor product is carried out transesterification;
One whizzer is used for the transesterification product is separated;
One fatty acid methyl ester distillation tower is used for the isolated thick methyl esters of whizzer is gently carried out underpressure distillation mutually, obtains methyl alcohol, biofuel and pitch respectively;
One inert gas gas-holder and gas path pipe is used for pre-esterification reactor still, transesterification still and fatty acid methyl ester distillation tower are carried inert gas;
In one and cleaning of evaporator, be used for the basic catalyst of the isolating raw glycerine heavy phase of whizzer is neutralized;
One glycerine one-level distillation tower, glycerine secondary distillation tower and purification of glycerin tower and glycerine circulation line, be used for the raw glycerine heavy phase of the basic catalyst that neutralized is carried out underpressure distillation and refining, obtain methyl alcohol and glycerine respectively, and will be delivered to the glycerine raw material storage tank through a part of glycerine behind the glycerine one-level distillation tower distillatory and carry out recycle;
One reclaims the refining methanol tower, is used for carrying out recycle to do to be delivered to the methyl alcohol storage tank after the processed from the methyl alcohol of fatty acid methyl ester distillation tower and glycerol distillation tower;
One oil burning package boiler or motor device are used to provide the power of packaged type production of biodiesel device, wherein the oil burning package boiler pitch that can burn and produce in the production process;
One automatization supervisory control desk is used for the automatization control of whole biofuel serialization production process, realizes the automatization control of packaged type production of biodiesel device.
8, removable production apparatus as claimed in claim 7 wherein, is equipped with raw material storage tank and product storage tank on moveable platform; Wherein the glyceride stock storage tank is connected with plate-and-frame filter press.
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| CN101818101A (en) * | 2010-03-10 | 2010-09-01 | 王志学 | Biodiesel esterification device and process method |
| CN101831358A (en) * | 2010-05-27 | 2010-09-15 | 江春德 | Method for producing biodiesel by using waste oil and fat |
| CN103013681A (en) * | 2012-12-28 | 2013-04-03 | 北京石油化工学院 | Method for preparing fatty acid methyl ester by using waste edible oil |
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| CN101818101A (en) * | 2010-03-10 | 2010-09-01 | 王志学 | Biodiesel esterification device and process method |
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| CN103502410A (en) * | 2011-04-14 | 2014-01-08 | 阿尔法拉瓦尔股份有限公司 | A process for autocatalytic esterification of fatty acids |
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| CN103013681A (en) * | 2012-12-28 | 2013-04-03 | 北京石油化工学院 | Method for preparing fatty acid methyl ester by using waste edible oil |
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| CN105038995A (en) * | 2015-08-21 | 2015-11-11 | 中国林业科学研究院林产化学工业研究所 | Non-catalytic esterification deacidification method for high-acid-value grease |
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| CN106929163A (en) * | 2017-03-30 | 2017-07-07 | 迈安德集团有限公司 | A kind of deacidification system of waste grease |
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| CN106929163B (en) * | 2017-03-30 | 2023-03-28 | 迈安德集团有限公司 | Acid reducing system for waste oil |
| CN108277090A (en) * | 2018-01-30 | 2018-07-13 | 浙江工业大学 | A kind of preparation method of low-sulphur biodiesel |
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