CN113499749A - Method and device for continuously preparing biodiesel by multiple towers in series connection - Google Patents

Method and device for continuously preparing biodiesel by multiple towers in series connection Download PDF

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CN113499749A
CN113499749A CN202110820399.8A CN202110820399A CN113499749A CN 113499749 A CN113499749 A CN 113499749A CN 202110820399 A CN202110820399 A CN 202110820399A CN 113499749 A CN113499749 A CN 113499749A
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reaction
tank
tower
stirring reaction
biodiesel
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刘学军
李钦
计建炳
马葛菲
吕振霄
杜昊展
竺少铭
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/30—Accessories for evaporators ; Constructional details thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0208—Separation of non-miscible liquids by sedimentation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Abstract

The invention discloses a method and a device for continuously preparing biodiesel by connecting multiple towers in series, wherein the method comprises the following steps: feeding an alkaline alcohol solution and raw oil from the bottom of a primary stirring reaction tower, after stirring, mixing and reacting, discharging crude biodiesel and crude glycerin which is a byproduct thereof from the top of the tower, entering a static separation tank, quickly layering, collecting the crude glycerin at the lower layer, refluxing the crude glycerin part to the bottom of the primary stirring reaction tower, and recycling the catalyst and methanol dissolved in the crude glycerin; and (3) introducing the crude biodiesel at the upper layer in the static separation tank into the bottom of the second-stage stirring reaction tower, fully stirring and mixing the crude biodiesel with the alkali alcohol solution again for reaction, and discharging from the top of the tower. The method has the advantages of simple process, strengthened reaction process by combined use of the multi-stage stirring reaction tower, shortened reaction time, twice feeding of the catalyst and the methanol, improved utilization rate of raw materials, avoidance of excessive saponification of the oil by the catalyst, improvement of conversion rate by separation of glycerol, recycling of the methanol and the catalyst, saving production cost and suitability for industrial production.

Description

Method and device for continuously preparing biodiesel by multiple towers in series connection
Technical Field
The invention belongs to the technical field of biodiesel preparation, and particularly relates to a method and a device for continuously preparing biodiesel by connecting multiple towers in series.
Background
At present, two methods of acid catalysis and alkali catalysis are mainly used for industrially preparing the biodiesel. The industrialized alkaline catalyst is mainly used for liquid phase reaction catalyzed by KOH, NaOH and the like which are easily dissolved in methanol, and heterogeneous reaction catalyzed by solid base. Sodium hydroxide (or potassium hydroxide) is used as a catalyst, the acid value of the grease raw material is not more than 2 mg KOH/g, and the dosage of the catalyst is 0.5-2.0% of the weight of the grease. Compared with alkali catalysis, the acid catalyst can process high-acid-value raw materials, but the reaction speed of acid-catalyzed transesterification is very slow, and relatively high reaction temperature and alcohol-oil ratio are needed, so that an acid-catalyzed transesterification process is rarely used in biodiesel generation devices at home and abroad.
With the intensive research on biodiesel, the method for preparing biodiesel by ester exchange is gradually concerned. Compared with the traditional deacidification-acid catalysis esterification, the deacidification method for the glycerol esterification has no sulfuric acid waste water, the deacidification is more thorough, and the saponification is less during the ester exchange, for example, in the invention patent CN201410557750.9, little soap is generated during the alkali catalysis neutralization, which is beneficial to the glycerol recovery.
So far, many studies have been made on the preparation of biodiesel by transesterification, but few studies have been reported on the separation of glycerol, which is a product of the continuous preparation of biodiesel, to increase the conversion rate and recycle the catalyst and methanol in glycerol.
The prior art mostly improves the basic catalyst for ester exchange, for example, patent CN104289213A, provides a solid basic catalyst for preparing biodiesel, which is a supported catalyst obtained by supporting a certain mass of zinc oxide on a silica-alumina composite carrier. And the solid base catalyst belongs to a mesoporous structure, and is beneficial to improving the conversion rate of the ester exchange reaction. The invention patent CN103566916A discloses a preparation method of a novel catalyst for catalyzing biodiesel transesterification, and the magnalium composite oxide is prepared by a low supersaturation coprecipitation method, has high conversion efficiency, is nontoxic and harmless, does not contain heavy metal, and is environment-friendly. The invention patent CN101302433 proposes a method for preparing biodiesel by an exchange reaction of super-strong base catalyzed grease and low carbon alcohol ester, which simplifies the process, reduces the environmental pollution and further reduces the production cost.
The invention patent CN102212426A discloses a method for preparing biodiesel by grease continuous ester exchange and a used mixed cosolvent. The mixed cosolvent contains butanone or acetone, and also contains furfuryl alcohol or one or both of C4-C7 hydrocarbons. In the method for preparing the biodiesel by grease continuous ester exchange, the dosage of the mixed cosolvent is 5-30% of the volume of the lower alcohol. The cosolvent is mainly used for enhancing the intersolubility of triglyceride and lower alcohol, forming a homogeneous reaction system, increasing a reaction interface, accelerating the reaction speed and realizing the continuity of the production process of the biodiesel.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a method and a device for continuously preparing biodiesel by multiple towers in series connection, and the method and the device are particularly suitable for preparing biodiesel by an alkali-catalyzed transesterification method.
The method for continuously preparing the biodiesel by the multi-tower series connection is characterized by comprising the following steps of:
1) preparing an alkaline alcohol solution, and dividing the alkaline alcohol solution into two parts for feeding: preheating a first part of alkaline alcohol solution and raw oil to 55-65 ℃, then respectively introducing the preheated alkaline alcohol solution and the raw oil into the bottom of a first-stage stirring reaction tower through a delivery pump, carrying out stirring reaction, allowing a first-stage reaction product flowing out of the upper part of the first-stage stirring reaction tower to enter a static separation tank for standing and layering, collecting crude glycerin precipitated at the bottom of the static separation tank in a glycerin storage tank, discharging the crude glycerin in two parts, delivering one part of the crude glycerin to a post-treatment process, and delivering the other part of the crude glycerin to the bottom of the first-stage stirring reaction tower for reuse in reaction;
2) preheating the oil phase product on the upper layer of the static separation tank and the second part of alkaline alcohol solution to 55-65 ℃, then respectively introducing the preheated oil phase product and the second part of alkaline alcohol solution into the bottom of the second-stage stirring reaction tower through a delivery pump, carrying out stirring reaction, allowing the final reacted feed liquid to flow out of the top of the second-stage stirring reaction tower and enter a product collection tank for standing and layering, delivering the crude biodiesel on the upper layer into the biodiesel collection tank, and carrying out rotary evaporation and purification on the crude biodiesel to obtain the product.
The method for continuously preparing the biodiesel by the multi-tower series connection is characterized in that the reaction temperature in the step 1) is the same as that in the step 2), and is 55-65 ℃, preferably 60 ℃; the raw oil is vegetable oil, the alkaline alcohol solution is methanol solution dissolved with an alkaline catalyst, the alkaline catalyst is at least one of NaOH, KOH, sodium methoxide and potassium methoxide, and NaOH or KOH is preferred; the mass concentration of the alkali catalyst in the alkali alcohol solution is 3.5-5%.
The method for continuously preparing the biodiesel by multiple serially connected towers is characterized in that in the step 1), the mass flow rate ratio of raw oil introduced into the bottom of the primary stirring reaction tower to alkaline alcohol solution is 100: 10-20, preferably 100: 12-20; the mass flow rate ratio of the raw oil introduced into the bottom of the primary stirring reaction tower to the crude glycerol recycled for reaction is 100: 12-19; the residence time of the reaction liquid in the first-stage stirring reaction tower is 8-12 min, preferably 8.5-10 min.
The method for continuously preparing the biodiesel by multiple serially connected towers is characterized in that in the step 2), the mass flow rate ratio of an oil phase product introduced into the bottom of the second-stage stirring reaction tower to an alkaline alcohol solution is 100: 15-18, preferably 100: 17-18; the residence time of the reaction liquid in the secondary stirring reaction tower is 10-25 min, preferably 15-20 min.
The device for continuously preparing the biodiesel by adopting the multi-tower series connection is characterized by comprising two stages of stirring reaction towers, a glycerin storage tank, a static separation tank, a product collecting tank and a biodiesel collecting tank, wherein each stage of stirring reaction tower is formed by connecting a plurality of small reaction tanks in series from bottom to top, a bottom plate is arranged between every two adjacent small reaction tanks, a circular hole is formed in the center of the bottom plate, a stirring shaft vertically penetrates through each stage of stirring reaction tower, the stirring shaft penetrates through the circular hole in the center of the bottom plate, and the upper end of the stirring shaft penetrates out of the top of the stirring reaction tower and is connected with a motor; in the stirring reaction tower, at least one layer of stirring blade is fixedly arranged on a stirring shaft in each small reaction tank;
preheating raw oil, a first part of alkaline alcohol solution and crude glycerol, and introducing the preheated raw oil, the first part of alkaline alcohol solution and the crude glycerol into the bottom of the lowermost small reaction tank of the first-stage stirring reaction tower for reaction, wherein a liquid outlet of the uppermost small reaction tank of the first-stage stirring reaction tower is connected with a feed inlet of a static separation tank through a pipeline; the static separation tank plays a layering role, the bottom outlet of the static separation tank is connected with the glycerin storage tank through a crude glycerin recovery pump through a pipeline, the bottom outlet of the glycerin storage tank is divided into two paths, one path is discharged to a post-treatment process through a pipeline, and the other path is connected with the bottom inlet of the lowest small reaction tank of the first-stage stirring reaction tower through a crude glycerin feeding pump through a pipeline. And an upper oil phase product flowing out of the upper part of the static separation tank and a second part of alkaline alcohol solution are introduced into the bottom of the lowest small reaction tank of the second-stage stirring reaction tower to react, and a liquid outlet of the uppermost small reaction tank of the second-stage stirring reaction tower is connected with a feed inlet of a crude product collecting tank through a pipeline.
The device for continuously preparing the biodiesel by the multi-tower series connection is characterized in that the diameter of the circular hole is larger than that of the stirring shaft, and a clearance space between the circular hole and the stirring shaft forms a liquid flow channel between two adjacent small reaction tanks.
The device for continuously preparing the biodiesel by the multi-tower series connection is characterized in that each small reaction tank is of a hollow cylinder structure, one end of each small reaction tank is provided with an opening, the other end of each small reaction tank is closed by a bottom plate, and the centers of the bottom plates of the rest small reaction tanks except the lowest small reaction tank are provided with the circular holes;
wherein, the both ends outside of small-size reaction tank all is provided with circular clamp, and circular clamp between two adjacent small-size reaction tank tip passes through bolt fixed connection and is in the same place, compresses tightly two small-size reaction tanks fixedly together.
The device for continuously preparing the biodiesel by the multi-tower series connection is characterized in that the end parts of two ends of a small reaction tank are provided with circular grooves; when the two small reaction tanks are pressed and fixed together, the circular grooves at the ends of the two small reaction tanks are matched and embedded with polytetrafluoroethylene gaskets so as to seal and prevent leakage.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1. the invention aims at the technology of continuously preparing the biodiesel by catalyzing the vegetable oil and the methanol in an alkaline catalyst KOH and connecting a plurality of towers in series, the combined use of the multi-stage stirring reaction towers strengthens the reaction process, shortens the reaction time, feeds the catalyst and the methanol twice, namely improves the utilization rate of raw materials, also avoids the saponification of grease caused by excessive catalyst, the reaction of the crude biodiesel after the separation of the glycerin with new methanol and the catalyst, improves the conversion rate of the biodiesel, simultaneously reflows the crude glycerin, recycles the methanol and the alkaline catalyst dissolved in the crude glycerin, saves the production cost and is suitable for industrial production. By the method, the yield of the biodiesel can reach 97.5 percent.
2. In the stirring reaction tower structure, the tower reactor is formed by sequentially splicing a plurality of small reaction tanks, and has the advantages of flexible structure, simple assembly and convenient cleaning.
Drawings
FIG. 1 is a schematic structural diagram of a multi-tower series-connection continuous biodiesel preparation device.
FIG. 2 is a plan view of a small reaction vessel.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example (b): compare fig. 1-2.
The invention relates to a device for continuously preparing biodiesel by multiple serially connected towers, which comprises two stages of stirring reaction towers, a glycerol storage tank 12, a static separation tank 13, a product collection tank 14 and a biodiesel collection tank 15, wherein each stage of stirring reaction tower is formed by serially connecting a plurality of small reaction tanks 4 from bottom to top, a bottom plate 18 is arranged between every two adjacent small reaction tanks 4, a circular hole 19 is formed in the center of the bottom plate 18, a stirring shaft 2 vertically penetrates through each stage of stirring reaction tower, the stirring shaft 2 penetrates through the circular hole 19 in the center of the bottom plate 18, and the upper end of the stirring shaft 2 penetrates out of the top of the stirring reaction tower and is connected with a motor; in the stirring reaction tower, at least one layer of stirring paddle 3 is fixedly arranged on the stirring shaft 2 in each small reaction tank 4.
Referring to fig. 1, the raw oil, the first portion of the alkaline alcohol solution, and the crude glycerin are introduced into the bottom of the lowest small reaction tank 4 of the first-stage stirring reaction tower 16 through the raw oil feed pump 1, the first-stage alkaline alcohol feed pump 6, and the crude glycerin feed pump 7, respectively, to react, and the liquid outlet of the uppermost small reaction tank 4 of the first-stage stirring reaction tower 16 is connected to the feed inlet of the static separation tank 13 through a pipeline; the static separation tank 13 plays a role in layering, the bottom outlet of the static separation tank 13 is connected with the glycerin storage tank 12 through a crude glycerin recovery pump 8 by a pipeline, the bottom outlet of the glycerin storage tank 12 is divided into two paths, one path is discharged to a post-treatment process through a pipeline, and the other path is connected with the bottom inlet of the lowest small reaction tank 4 of the first-stage stirring reaction tower 16 through a crude glycerin feeding pump 7 by a pipeline.
The upper oil phase product and the second alkaline alcohol solution flowing out from the upper part of the static separation tank 13 are introduced into the bottom of the lowest small reaction tank 4 of the second-stage stirring reaction tower 17 for reaction (in comparison with fig. 1, the liquid outlet at the upper part of the static separation tank 13 is connected with the bottom inlet of the lowest small reaction tank 4 of the second-stage stirring reaction tower 17 through the biodiesel feed pump 9, and the second alkaline alcohol solution is introduced into the bottom of the lowest small reaction tank 4 of the second-stage stirring reaction tower 17 through the second-stage alkaline alcohol feed pump 10), and the liquid outlet of the uppermost small reaction tank 4 of the second-stage stirring reaction tower 17 is connected with the feed inlet of the crude product collection tank 14 through a pipeline. And (3) allowing the secondary reaction product to enter a crude product collecting tank 14 for layering, conveying the layered crude biodiesel on the upper layer to a biodiesel collecting tank 15 by using a biodiesel extracting pump 11, and separating and performing rotary evaporation to obtain a biodiesel product.
The diameter of the circular hole 19 is larger than that of the stirring shaft 2, and the clearance space between the circular hole 19 and the stirring shaft 2 forms a liquid flow channel between two adjacent small reaction tanks 4. Each small reaction tank 4 is a hollow cylinder structure, one end of the small reaction tank is provided with an opening, and the other end of the small reaction tank is closed by a bottom plate 18; the centers of the bottom plates 18 of the other small reaction tanks 4 except the lowest small reaction tank 4 are provided with the circular holes 19; wherein the both ends outside of small-size reaction tank 4 all is provided with circular clamp 5, and circular clamp 5 between 4 tip of two adjacent small-size reaction tanks passes through bolt fixed connection and is in the same place, compresses tightly two small-size reaction tanks 4 fixedly together.
The end parts of the two ends of the small reaction tank 4 are provided with circular grooves 20; when the two small reaction tanks 4 are pressed and fixed together, the circular grooves 20 at the ends of the two small reaction tanks 4 are embedded with polytetrafluoroethylene gaskets in a matching way so as to seal and prevent leakage.
A method for continuously preparing biodiesel by multiple towers in series connection comprises the following steps:
1) preparing an alkaline alcohol solution, and dividing the alkaline alcohol solution into two parts for feeding; preheating a first part of alkaline alcohol solution and raw oil to 55-65 ℃, then respectively introducing the solution and the raw oil into the bottom of a first-stage stirring reaction tower 16 through a delivery pump, carrying out stirring reaction, allowing a first-stage reaction product flowing out of the upper part of the first-stage stirring reaction tower 16 to enter a static separation tank 13 for standing and layering, collecting crude glycerin precipitated at the bottom of the static separation tank 13 in a glycerin storage tank 12, discharging the crude glycerin in two parts, delivering one part to a post-treatment process, and delivering the other part to the bottom of the first-stage stirring reaction tower 16 for reuse in reaction.
2) Preheating the oil phase product on the upper layer of the static separation tank 13 and the second part of alkaline alcohol solution to 55-65 ℃, then respectively introducing the preheated oil phase product and the second part of alkaline alcohol solution into the bottom of the second-stage stirring reaction tower 17 through a delivery pump, carrying out stirring reaction, finally allowing the reacted feed liquid to flow out of the top of the second-stage stirring reaction tower 17 and enter the product collection tank 14 for standing and layering, delivering the crude biodiesel on the upper layer into the biodiesel collection tank 15, and carrying out rotary evaporation and purification on the crude biodiesel to obtain the product.
The reaction temperature in the step 1) is the same as that in the step 2), and is 55-65 ℃, preferably 60 ℃; the raw oil is vegetable oil, the alkaline alcohol solution is methanol solution dissolved with an alkaline catalyst, the alkaline catalyst is at least one of NaOH, KOH, sodium methoxide and potassium methoxide, and NaOH or KOH is preferred; the mass concentration of the alkali catalyst in the alkali alcohol solution is 3.5-5%.
In the step 1), the mass flow rate ratio of the raw oil introduced into the bottom of the primary stirring reaction tower 16 to the alkaline alcohol solution is 100: 10-18, preferably 100: 10-16; the mass flow rate ratio of the raw oil introduced into the bottom of the primary stirring reaction tower 16 to the crude glycerol recycled for reaction is 100: 15-23; the residence time of the reaction liquid in the first-stage stirring reaction tower 16 is 8-12 min, preferably 8.5-10 min.
In the step 2), the mass flow rate ratio of the oil phase product introduced into the bottom of the secondary stirring reaction tower 17 to the alkaline alcohol solution is 100: 10-18, preferably 100: 10-16; the residence time of the reaction liquid in the secondary stirring reaction tower 17 is 10-25 min, preferably 10-20 min.
The production devices in the following examples 1 to 3 all adopt the structure shown in fig. 1, and 9 small reaction tanks 4 are connected in series in each stage of stirring reaction tower. Each small reaction tank 4 is of a cylindrical structure, the bottom of the small reaction tank 4 is 5cm in diameter and 4cm in height, the small reaction tank is hollow, one end of the small reaction tank is open, the other end of the small reaction tank is closed by a bottom plate 18, a circular hole 19 with the diameter of 1cm is formed in the center of the bottom plate, and a stirring shaft 2 with the diameter of 0.8cm penetrates through the circular hole 19 of each small reaction tank 4.
The first-stage stirring reaction tower 16 is provided with three feed inlets and a tower top discharge outlet, wherein the three feed inlets are an oil phase feed inlet, a methanol phase feed inlet and a refluxed crude glycerol feed inlet respectively, and the three feed inlets are fed by a raw oil feed pump 1, a first-stage alkaline alcohol feed pump 6 and a crude glycerol feed pump 7 respectively. The first-stage reaction product enters a static separation tank 13 to be kept stand and layered, the crude glycerin precipitated at the bottom of the static separation tank 13 is collected in a glycerin storage tank 12, then part of the crude glycerin flows back to the bottom of a first-stage stirring reaction tower 16, and the catalyst KOH and the methanol dissolved in the crude glycerin are recycled. The layered crude fatty acid methyl ester, the new methanol and the catalyst in the static separation tank 13 are introduced into the bottom of the second-stage stirring reaction tower 17 together to enhance the reaction and improve the conversion rate of the biodiesel. The first-stage stirring reaction tower 16 and the second-stage stirring reaction tower 17 are both placed in a super constant-temperature water bath at 60 ℃ for constant-temperature water bath heating.
In the following examples 1 to 3, the liquid holding capacity of each stirring reaction tower was about 650ml, and the total feed rate of the raw material oil phase and the methanol phase in the first stirring reaction tower 16 was controlled to 65 ml/min. Since the density of glycerol is higher than that of fatty acid methyl ester, crude glycerol is in the lower layer when the first-order reaction product enters the static separation tank 13 for stratification. And collecting the crude glycerol precipitated at the bottom of the static separation tank 13 in a glycerol storage tank 12, returning the crude glycerol to the first-stage stirring reaction tower 16 again at the rate of 6-12ml/min for reaction, and recycling the catalyst and the methanol dissolved in the crude glycerol.
And (3) inputting the fatty acid methyl ester layer on the upper layer of the static separation tank 13 into another secondary stirring reaction tower 17 with a similar structure, preheating the new methanol-catalyst mixture to 60 ℃, then introducing the mixture into the secondary stirring reaction tower 17 for reaction, wherein the total feeding speed of the fatty acid methyl ester layer and the new methanol-catalyst mixture is 32.5-65ml/min, and discharging after 10-20 minutes, namely finishing the reaction.
Example 1:
the preparation method of the soybean oil methyl ester comprises the following steps:
the two stirring reaction towers are heated in a constant-temperature water bath of a super constant-temperature water bath at 60 ℃. Taking soybean oil, and preheating the soybean oil to 60 ℃ by using a water bath kettle. Methanol and KOH are mixed according to the mass ratio of 300:14, and the obtained methanol-KOH solution is preheated to 60 ℃ by a water bath kettle.
1) In the first-stage stirring reaction tower, soybean oil and a methanol-KOH solution are simultaneously fed, wherein the feeding speed of the soybean oil is 56.6ml/min, and the feeding speed of the methanol-KOH solution is 8.4 ml/min. And (3) turning on an external motor while feeding to drive the stirring shaft and the stirring blades to rotate at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 10min, discharging at the top of the tower, allowing the feed liquid to enter a static separation tank for standing and layering, allowing the crude glycerol in the static separation tank to enter a first-stage stirring reaction tower without refluxing, and reacting for 30min until the yield of the soybean oil methyl ester discharged at the top of the tower is about 83%.
2) After reacting for 30min according to the operation process of the step 1), continuously repeating the operation process of the step 1), collecting the crude glycerol precipitated at the bottom of the static separation tank in a glycerol storage tank, returning the crude glycerol to the first-stage stirring reaction tower again at the speed of 10.5ml/min for reaction, recycling the catalyst KOH and methanol dissolved in the glycerol, and discharging an oil phase product at the upper layer of the static separation tank outwards.
And 2) when the reaction is carried out for 1 hour according to the operation process, the yield of the soybean oil methyl ester discharged from the top of the first-stage stirring reaction tower is about 88 percent. According to the analysis of the reaction equation, although the backflow of the crude glycerol is not beneficial to the forward progress of the reaction, the forward progress of the reaction is greatly promoted by the catalyst and the methanol in the crude glycerol, and the grease is not saponified by the catalyst brought by the backflow of the crude glycerol because the amount of the methanol and the catalyst in the feed is small.
3) After the operation process of the step 2) is stably operated for 1h, introducing an upper oil phase product discharged from the static separation tank into the bottom of the second-stage stirring reaction tower at a speed of 37ml/min, simultaneously introducing a methanol-KOH solution preheated to 60 ℃ into the bottom of the second-stage stirring reaction tower at a speed of 6.5ml/min, and stirring while feeding at a rotating speed of 500 r/min. Stirring, mixing and reacting for about 15min, discharging at the top of the tower, feeding the feed liquid into a product collecting tank, layering, conveying the coarse soybean oil methyl ester on the upper layer into a biodiesel collecting tank, and separating and carrying out rotary evaporation to obtain the soybean oil methyl ester. Through detection and analysis, the yield of the soybean oil methyl ester can reach 97.5 percent. The content of each component in the soybean oil methyl ester is measured and shown in table 1.
Figure DEST_PATH_IMAGE002
Example 2:
the preparation method of methyl linoleate comprises the following steps:
the two stirring reaction towers are heated in a constant-temperature water bath of a super constant-temperature water bath at 60 ℃. Preheating linoleic acid triglyceride to 60 ℃ in a water bath kettle. Methanol and KOH are mixed according to the mass ratio of 20:1, and the obtained methanol-KOH solution is preheated to 60 ℃ by a water bath kettle.
1) In the first-stage stirring reaction tower, the linoleic acid triglyceride and the methanol-KOH solution are simultaneously fed, the feeding speed of the linoleic acid triglyceride is 59.1ml/min, and the feeding speed of the methanol-KOH solution is 7.3 ml/min. And (3) turning on an external motor while feeding to drive the stirring shaft and the stirring blades to rotate at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 9.8min, discharging from the tower top, and allowing the feed liquid to enter a static separation tank for standing and layering. Crude glycerin in the static separation tank firstly enters a first-stage stirring reaction tower without refluxing, and the yield of discharged methyl linoleate at the top of the tower is about 82% when the reaction is carried out for 30 min.
2) After reacting for 30min according to the operation process of the step 1), continuously repeating the operation process of the step 1), collecting the crude glycerol precipitated at the bottom of the static separation tank in a glycerol storage tank, returning the crude glycerol to the first-stage stirring reaction tower again at the speed of 7.5ml/min for reaction, recycling the catalyst KOH and methanol dissolved in the glycerol, and discharging an oil phase product at the upper layer of the static separation tank outwards.
And 2) when the reaction is carried out for 1 hour according to the operation process, the yield of the methyl linoleate discharged from the top of the first-stage stirring reaction tower is about 87%.
3) After the operation process of the step 2) is stably operated for 1h, introducing an upper oil phase product discharged from the static separation tank into the bottom of the second-stage stirring reaction tower at the speed of 27.6ml/min, simultaneously introducing a methanol-KOH solution preheated to 60 ℃ into the bottom of the second-stage stirring reaction tower at the speed of 4.9ml/min, and stirring while feeding at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 20min, discharging from the tower top, feeding the feed liquid into a product collecting tank, layering, conveying the upper layer crude methyl linoleate into a biodiesel collecting tank, and separating and rotary steaming to obtain the methyl linoleate. Through detection and analysis, the yield of the methyl linoleate can reach 97.2%. The content of each component in the methyl linoleate is detected as shown in table 2.
Figure DEST_PATH_IMAGE004
Example 3
The preparation method of the methyl palmitate comprises the following steps:
the two stirring reaction towers are heated in a constant-temperature water bath of a super constant-temperature water bath at 60 ℃. Preheating industrial palm oil to 60 ℃ in a water bath kettle. Methanol and KOH are mixed according to the mass ratio of 350:14, and the obtained methanol-KOH solution is preheated to 60 ℃ by a water bath kettle.
1) In the first-stage stirring reaction tower, industrial palm oil and a methanol-KOH solution are simultaneously fed, wherein the feeding speed of the industrial palm oil is 55.6ml/min, and the feeding speed of the methanol-KOH solution is 10.8 ml/min. And (3) turning on an external motor while feeding to drive the stirring shaft and the stirring blades to rotate at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 10min, discharging from the tower top, and allowing the feed liquid to enter a static separation tank for standing and layering. Crude glycerin in the static separation tank firstly enters a first-stage stirring reaction tower without refluxing, and the yield of the methyl palmitate discharged from the top of the tower is about 82 percent when the reaction is carried out for 30 min.
2) After reacting for 30min according to the operation process of the step 1), continuously repeating the operation process of the step 1), collecting the crude glycerol precipitated at the bottom of the static separation tank in a glycerol storage tank, returning the crude glycerol to the first-stage stirring reaction tower 16 at the speed of 9ml/min for reaction, recycling the catalyst KOH and methanol dissolved in the glycerol, and discharging an oil phase product at the upper layer of the static separation tank outwards.
And 2) when the reaction is carried out for 1 hour according to the operation process, the yield of the methyl palmitate discharged from the top of the first-stage stirring reaction tower is about 86%.
3) After the operation process of the step 2) is stably operated for 1h, introducing an upper oil phase product discharged from the static separation tank into the bottom of the second-stage stirring reaction tower at a speed of 31ml/min, simultaneously introducing a methanol-KOH solution preheated to 60 ℃ into the bottom of the second-stage stirring reaction tower at a speed of 5.3ml/min, and stirring while feeding at a rotating speed of 500 r/min. Stirring, mixing and reacting for about 18min, discharging from the tower top, feeding the feed liquid into a product collecting tank, layering, conveying the upper layer crude methyl palmitate into a biodiesel collecting tank, and separating and rotary steaming to obtain the methyl palmitate. Through detection and analysis, the yield of the methyl palmitate can reach 96.8%, and the content of each component in the detected methyl palmitate is shown in table 3.
Figure DEST_PATH_IMAGE006
Comparative example 1:
the preparation method of the soybean oil methyl ester comprises the following steps:
the two stirring reaction towers are heated in a constant-temperature water bath of a super constant-temperature water bath at 60 ℃. Taking soybean oil, and preheating the soybean oil to 60 ℃ by using a water bath kettle. Methanol and KOH are mixed according to the mass ratio of 300:14, and the obtained methanol-KOH solution is preheated to 60 ℃ by a water bath kettle.
1) In the first-stage stirring reaction tower, soybean oil and a methanol-KOH solution are simultaneously fed, wherein the feeding speed of the soybean oil is 56.6ml/min, and the feeding speed of the methanol-KOH solution is 8.4 ml/min. And (3) turning on an external motor while feeding to drive the stirring shaft and the stirring blades to rotate at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 10min, discharging from the tower top, and allowing the feed liquid to enter a static separation tank for standing and layering. The crude glycerol precipitated at the bottom of the static separation tank was collected in a glycerol storage tank. Through detection and analysis, the yield of the soybean oil methyl ester discharged from the tower top is about 83 percent.
2) After the operation process of the step 1) is stably operated for 1h, introducing an upper oil phase product discharged from the static separation tank into the bottom of the second-stage stirring reaction tower at a speed of 37ml/min, simultaneously introducing a methanol-KOH solution preheated to 60 ℃ into the bottom of the second-stage stirring reaction tower at a speed of 6.5ml/min, and stirring while feeding at a rotating speed of 500 r/min. Stirring, mixing and reacting for about 15min, discharging from the tower top, feeding the feed liquid into a product collecting tank, layering, conveying the crude biodiesel on the upper layer into a biodiesel collecting tank, separating liquid, and performing rotary evaporation to obtain the soybean oil methyl ester. Through detection and analysis, the yield of the soybean oil methyl ester is about 95.5 percent.
Comparative example 2:
the preparation method of the soybean oil methyl ester comprises the following steps:
the two stirring reaction towers are heated in a constant-temperature water bath of a super constant-temperature water bath at 60 ℃. Taking soybean oil, and preheating the soybean oil to 60 ℃ by using a water bath kettle. Methanol and KOH are mixed according to the mass ratio of 300:14, and the obtained methanol-KOH solution is preheated to 60 ℃ by a water bath kettle.
1) In the first-stage stirring reaction tower, soybean oil and a methanol-KOH solution are simultaneously fed, wherein the feeding speed of the soybean oil is 56.6ml/min, and the feeding speed of the methanol-KOH solution is 19.8 ml/min. And (3) turning on an external motor while feeding to drive the stirring shaft and the stirring blades to rotate at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 8.6min, and discharging from the top of the tower.
2) Directly introducing the discharged material at the top of the first-stage stirring reaction tower into the bottom of the second-stage stirring reaction tower 17 without treatment, and stirring while feeding at the rotating speed of 500 r/min. Stirring, mixing and reacting for about 9min, discharging from the tower top, feeding the feed liquid into a product collecting tank, layering, conveying the crude biodiesel on the upper layer into a biodiesel collecting tank, separating liquid, and performing rotary evaporation to obtain the soybean oil methyl ester. Through detection and analysis, the yield of the soybean oil methyl ester is about 94.8 percent.
From the specific examples 1-3, it can be seen that, compared with the general preparation of biodiesel by ester exchange, the technology for continuously preparing biodiesel by multi-tower series connection provided by the invention is green and environment-friendly, has a simple process, and can achieve a high conversion rate of about 97.5%. The multistage stirring tower reactor strengthens the reaction process, shortens the reaction time, improves the utilization rate of raw materials by feeding the catalyst and the methanol twice, avoids the saponification of the grease due to excessive catalyst, improves the conversion rate by separating the glycerol, recovers the methanol and recycles the catalyst, saves the production cost and is suitable for industrial production.
As can be seen from comparative example 1, although separation of glycerin is effective in increasing the conversion rate, since crude glycerin is not refluxed into the first-stage reaction tower, the catalyst and methanol in crude glycerin are not utilized, resulting in a slow reaction rate and ultimately affecting the product yield of the second-stage reaction tower, the product yield is not as good as that of specific example 1 at the same reaction time.
As can be seen from comparative example 2, without separation of glycerol, two stirred reaction columns were connected in series and the product yield was inferior to that of example 1 under the same conditions. And because raw oil and methanol-catalyst solution are fed at one time, the grease is easy to be saponified by excessive catalyst.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (8)

1. A method for continuously preparing biodiesel by multiple towers in series connection is characterized by comprising the following steps:
1) preparing an alkaline alcohol solution, and dividing the alkaline alcohol solution into two parts for feeding: preheating a first part of alkaline alcohol solution and raw oil to 55-65 ℃, then respectively introducing the preheated alkaline alcohol solution and the raw oil into the bottom of a first-stage stirring reaction tower (16) through a delivery pump, carrying out stirring reaction, allowing a first-stage reaction product flowing out of the upper part of the first-stage stirring reaction tower (16) to enter a static separation tank (13) for standing and layering, collecting crude glycerin precipitated at the bottom of the static separation tank (13) in a glycerin storage tank (12), discharging the crude glycerin into two parts, delivering one part to a post-treatment process, and delivering the other part to the bottom of the first-stage stirring reaction tower (16) for reuse in reaction;
2) preheating the oil phase product on the upper layer of the static separation tank (13) and the second part of alkaline alcohol solution to 55-65 ℃, then respectively introducing the oil phase product and the second part of alkaline alcohol solution into the bottom of the second-stage stirring reaction tower (17) through a delivery pump, carrying out stirring reaction, finally allowing the reacted feed liquid to flow out of the top of the second-stage stirring reaction tower (17) and enter a product collection tank (14) for standing and layering, delivering the crude biodiesel on the upper layer into a biodiesel collection tank (15), and carrying out rotary evaporation and purification on the crude biodiesel to obtain the product.
2. The method for continuously preparing biodiesel by multiple towers connected in series according to claim 1, wherein the reaction temperature in the step 1) is the same as that in the step 2), and is 55-65 ℃, preferably 60 ℃; the raw oil is vegetable oil, the alkaline alcohol solution is methanol solution dissolved with an alkaline catalyst, the alkaline catalyst is at least one of NaOH, KOH, sodium methoxide and potassium methoxide, and NaOH or KOH is preferred; the mass concentration of the alkali catalyst in the alkali alcohol solution is 3.5-5%.
3. The method for continuously preparing biodiesel by multiple towers connected in series according to claim 1, wherein in the step 1), the mass flow rate ratio of the raw oil introduced into the bottom of the first-stage stirring reaction tower (16) to the alkaline alcohol solution is 100: 10-20, preferably 100: 12-20; the mass flow rate ratio of the raw oil introduced into the bottom of the primary stirring reaction tower (16) to the crude glycerol recycled for reaction is 100: 12-19; the residence time of the reaction liquid in the first-stage stirring reaction tower (16) is 8-12 min, preferably 8.5-10 min.
4. The method for continuously preparing biodiesel by multiple towers connected in series according to claim 1, wherein in the step 2), the mass flow rate ratio of the oil-phase product introduced into the bottom of the secondary stirring reaction tower (17) to the alkaline alcohol solution is 100: 15-18, preferably 100: 17-18; the residence time of the reaction liquid in the secondary stirring reaction tower (17) is 10-25 min, preferably 15-20 min.
5. A device for continuously preparing biodiesel by adopting a multi-tower series connection based on the method of claim 1 is characterized by comprising two stages of stirring reaction towers, a glycerin storage tank (12), a static separation tank (13), a product collection tank (14) and a biodiesel collection tank (15), wherein each stage of stirring reaction tower is formed by connecting a plurality of small reaction tanks (4) in series from bottom to top, a bottom plate (18) is arranged between every two adjacent small reaction tanks (4), a circular hole (19) is formed in the center of the bottom plate (18), a stirring shaft (2) is vertically arranged in each stage of stirring reaction tower in a penetrating manner, the stirring shaft (2) is arranged in the circular hole (19) in the center of the bottom plate (18), and the upper end of the stirring shaft (2) penetrates out of the top of the stirring reaction tower and is connected with a motor; in the stirring reaction tower, at least one layer of stirring paddle (3) is fixedly arranged on the stirring shaft (2) in each small reaction tank (4);
preheating raw oil, a first part of alkaline alcohol solution and crude glycerol, and introducing the preheated raw oil, the first part of alkaline alcohol solution and the crude glycerol into the bottom of the lowermost small reaction tank (4) of the first-stage stirring reaction tower (16) for reaction, wherein a liquid outlet of the uppermost small reaction tank (4) of the first-stage stirring reaction tower (16) is connected with a feed inlet of a static separation tank (13) through a pipeline; the static separation tank (13) plays a role in layering, the bottom outlet of the static separation tank (13) is connected with the glycerin storage tank (12) through a crude glycerin recovery pump (8) by a pipeline, the bottom outlet of the glycerin storage tank (12) is divided into two paths, one path is discharged to a post-treatment process through the pipeline, and the other path is connected with the bottom inlet of the lowest small reaction tank (4) of the first-stage stirring reaction tower (16) through a crude glycerin feeding pump (7) by the pipeline;
the upper oil phase product flowing out of the upper part of the static separation tank (13) and the second part of alkaline alcohol solution are introduced into the bottom of the lowest small reaction tank (4) of the second-stage stirring reaction tower (17) for reaction, and the liquid outlet of the topmost small reaction tank (4) of the second-stage stirring reaction tower (17) is connected with the feed inlet of the crude product collection tank (14) through a pipeline.
6. The apparatus for the continuous preparation of biodiesel by multiple towers connected in series according to claim 5, wherein the diameter of the circular holes (19) is larger than that of the stirring shaft (2), and the clearance space between the circular holes (19) and the stirring shaft (2) forms a liquid flow channel between two adjacent small reaction tanks (4).
7. The apparatus for the continuous preparation of biodiesel by multiple towers connected in series as claimed in claim 5, wherein each small reaction tank (4) is a hollow cylinder structure, one end of which is provided with an opening, the other end of which is closed by a bottom plate (18), and the centers of the bottom plates (18) of the other small reaction tanks (4) except the lowest small reaction tank (4) are provided with the circular holes (19);
wherein, the both ends outside of small-size reaction tank (4) all is provided with circular clamp (5), and circular clamp (5) between two adjacent small-size reaction tank (4) tip are in the same place through bolt fixed connection, compress tightly two small-size reaction tank (4) and fix together.
8. The apparatus for the continuous preparation of biodiesel by multi-tower series connection according to claim 7, wherein the small-sized reaction tank (4) is provided with circular grooves (20) at both end portions thereof; when the two small reaction tanks (4) are pressed and fixed together, the circular grooves (20) at the ends of the two small reaction tanks (4) are matched and embedded with polytetrafluoroethylene gaskets for sealing and leakage prevention.
CN202110820399.8A 2021-07-20 2021-07-20 Method and device for continuously preparing biodiesel by multiple towers in series connection Pending CN113499749A (en)

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* Cited by examiner, † Cited by third party
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CN201832634U (en) * 2010-09-26 2011-05-18 铜陵钱陵化工设备制造有限公司 Multi-section reaction tower
CN102776075A (en) * 2011-05-12 2012-11-14 种传学 Interactive turbulent flow reaction device
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