CN105273838B - A kind of biodiesel adsorption deacidification method - Google Patents
A kind of biodiesel adsorption deacidification method Download PDFInfo
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- CN105273838B CN105273838B CN201410283294.3A CN201410283294A CN105273838B CN 105273838 B CN105273838 B CN 105273838B CN 201410283294 A CN201410283294 A CN 201410283294A CN 105273838 B CN105273838 B CN 105273838B
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Abstract
A kind of method of biodiesel adsorption deacidification, comprising: (1) load fixed bed with absorption resin, obtain ADSORPTION IN A FIXED BED splitter；(2) the underproof biodiesel of acid value is subjected to adsorption deacidification by adsorbing separation column, obtains the biodiesel of acid value qualification；(3) under ultrasonic wave booster action, with the adsorbing separation column of alcohols desorbing agent elution saturation；(4) under ultrasonic wave booster action, the alcohols desorbing agent in fixed bed is removed to clean, adsorbing separation column, that is, reusable.Method provided by the invention can get the biodiesel oil product that acid value is less than 0.50mgKOH/g, existing BD100 can be met to require and national standard of new generation, ultrasonic wave assisted desorption or/and dealcoholysis can increase substantially desorption process or/and dealcoholysis process efficiency, it is easy to operate, non-pollutant discharge, it is environmentally protective.
Description
Technical field
The present invention relates to a kind of methods of biodiesel adsorption deacidification.
Background technique
Biodiesel have it is nontoxic, without sulphur, the characteristics such as burning is abundant, biodegradable, greasy property is excellent, to reducing sky
Gas pollution and greenhouse gas emission are of great significance.With fossil energy consumption increasingly increase with the continuous reductions of reserves,
And the aggravation of brought environment worsening and greenhouse effects, reproducible clean energy resource biodiesel are just closed extensively
Note.
Biodiesel can carry out ester exchange reaction by natural oil and monohydric alcohol and be made, the product grease removal of ester exchange reaction
Outside fat acid esters, it is also possible to former containing monoglyceride, two sweet rouge, glycerin by-products, free fatty acid and unreacted pure and mild grease
Material.In recent years, using waste grease such as waste cooking oil, acidification oil to prepare biodiesel for raw material becomes research hotspot, these oil
The acid value difference of rouge is very big, and some acidification oil acid values are even up to 170mgKOH/g.Use preparing biological diesel fuel by high-acid-value grease
When, product acid value is generally higher than even much larger than BD100 acid value standard (≤0.80mg KOH/g).In order to reach product acid value
Standard requirements can carry out depickling processing to raw material or product.
Alkali cleaning is classical deacidifying process, and the aqueous slkalis such as lot of domestic and international research sodium hydroxide are carried out with free fatty acid
Neutralization reaction, gained fatty acid sodium salt are separated from oil product, acidified to obtain free fatty acid, and reaction process can be in wink
Between complete, but be easy to produce emulsion during the reaction.And lye is largely lost in company with converted products, sodium hydroxide
Solution cannot regenerate.
It is a kind of preferable for converting fatty acid methyl ester for the free fatty acid in biodiesel oil product by esterification
Method, but when the acid value of biodiesel is closer to 0.80mgKOH/g, esterification depickling is more difficult, so as to cause technique
Energy consumption it is higher.
CN101993776A provides a kind of method of deacidifying biodiesel, comprising the following steps: makes to depickling biology bavin
Oil is mixed with the deacidification agent containing water-soluble alcohol, water-soluble amine and water, and fuel-displaced phase and water phase are separated after layering, and oil obtains after mutually refining
To the biodiesel of acid value qualification.The disadvantages of this method are: 1 causes the loss of free fatty acid.2 generate containing organic amine and soap
Waste water.
A kind of method for reducing acid number of biodiesel of CN101289627A, it is characterised in that: carry out crude fatty acid methyl ester
The acid lowering agent for accounting for smart fatty acid methyl ester total weight 0.02~4% is added after rectifying, is stirred to react at 60~80 DEG C for rectifying
0.2~0.5 hour, 2 hours releasing lower layer acid lowering agents are settled, are put into finished pot after upper layer acid value is qualified, acid lowering agent can repeat
It uses, product is cycloalkanoimide.The disadvantages of this method are: 1 causes the loss of free fatty acid.2 amine acid lowering agents easily remain
In biodiesel oil product.
CN101735845A is related to a kind of method of separating and purifying biodiesel.The following steps are included: 1) use thin film evaporation
Device is de-gassed to biodiesel coarse product and distillation procedure, obtains biodiesel of the methyl ester content 96% or more；2) to step
Product after rapid 1) separating treatment carries out alkaline soil depickling, obtains acid value purified biodiesel that meet national standards.It should
The shortcomings that method is: 1, free fatty acid loses, and cannot be processed into biodiesel.2, alkaline soil cannot regenerate.
CN101550364A is related to a kind of method of comprehensive utilization high acid value oil plant preparation biodiesel, is with high acid value oil
Material through multistage (n >=1) extracting operation of methanol, in operating process methanol phase and low acid value glyceride phase.Wherein big portion in grease
Point free fatty acid is dissolved in methanol phase, it is enriched after through preparation of biodiesel by acid catalysts；And low acid value glyceride is mutually urged through alkali
Change preparation biodiesel.The disadvantages of this method are: 1, operating cost is higher.2, it cannot be used for product purification.
US249366 reduces the acid value in high-acid value grease using excessive alkali neutralization free fatty acid, and carries out esterification
Sulfuric acid is added in the soap that reaction, alkali and free fatty acid are formed after esterification, is reacted to obtain free fatty acid, the trip of this part
It from fatty acid under acid catalysis, then is esterified, obtains neutralized material, filtering and rectifying and obtain methyl esters.This method
The disadvantage is that: 1, using excess base and sulfuric acid, production cost is higher.2, the by-product sulfate of low value is produced.
It for the product quality for further promoting biodiesel, integrates with international standard, China plans biodiesel BD100's
Standard modification is acid value≤0.50mgKOH/g, this further increases the difficulty of deacidifying biodiesel.Therefore, it is necessary to develop drop
Low acid number of biodiesel is to 0.80mgKOH/g hereinafter, even 0.50mgKOH/g acid stripping method below.
Summary of the invention
A kind of method that the present invention proposes biodiesel adsorption deacidification, especially ultrasonic wave assisted desorption process or/and de-
The method of alcohol process.
The method of biodiesel adsorption deacidification provided by the invention, comprising: (1) load fixed bed with absorption resin, obtain
ADSORPTION IN A FIXED BED splitter；(2) the underproof biodiesel of acid value is subjected to adsorption deacidification by adsorbing separation column, obtains acid value
Qualified biodiesel；(3) under ultrasonic wave booster action, with the adsorbing separation column of alcohols desorbing agent elution saturation；(4) super
Under sound wave booster action, the alcohols desorbing agent in fixed bed is removed to clean, adsorbing separation column, that is, reusable.
Specifically, method provided by the invention is: (1) loading fixed bed with absorption resin first, obtain fixed bed and inhale
Attached splitter；(2) adsorption deacidification: by the underproof biodiesel of acid value by adsorption column, obtaining the biodiesel of acid value qualification,
Achieve the purpose that adsorption deacidification.When the acid value of the biodiesel come out from adsorbing separation column is unqualified, the absorption of adsorbing separation column
Saturation stops biodiesel charging, is desorbed；(3) it is desorbed: under ultrasonic wave booster action, being eluted with alcohols desorbing agent full
With the adsorbing separation column of free fatty acid, taken off when desorption liquid acid value is reduced to 0.15mgKOH/g adsorbing separation column accomplished below
It is attached；(4) dealcoholysis: under ultrasonic wave booster action, the alcohol in adsorbing separation column is ejected as far as possible with inactive gas first, then adopts
Alcohol is removed completely as far as possible with the mode vacuumized, or purges clean remaining alcohol with nitrogen, completes adsorbing separation column regeneration.
The absorption resin of step described in the method for the present invention (1) is the absorption resin for having loaded basic group, the basic group
Group can be strong basicity group, be also possible to alkalescent group, preferably in hydroxyl, primary amine, secondary amine, tertiary amine and quaternary ammonium group etc.
It is one or more.
The acid value of the unqualified biodiesel of acid value of step described in the method for the present invention (2) is 0.5~5.0mgKOH/g, preferably
For 0.8~2.0mgKOH/g.
The biodiesel of the acid value qualification of step described in the method for the present invention (2) refers to that acid value is less than 0.80mgKOH/g
(BD100 standard), the biodiesel of preferably smaller than 0.50mgKOH/g (new national standard).
The adsorption deacidification temperature of step described in the method for the present invention (2) is room temperature~100 DEG C, preferably room temperature~60 DEG C.
The liquid hourly space velocity (LHSV) of step described in the method for the present invention (2) is 0.2~10h-1, preferably 0.6~5.0h-1。
The operating pressure of step described in the method for the present invention (2) is 0.1~5.0MPa, preferably 0.1~0.30MPa.
Ultrasonic wave assisted desorption process or/and dealcoholysis process of the present invention, can take two ways: (1) will be ultrasonic
Wave probe is placed in the central tube of adsorbing separation device；(2) supersonic generator is placed in outside the pipe of adsorbing separation device and (in other words will
Adsorbing separation device is placed in ultrasonic field).
Ultrasonic wave generally refers to frequency range in the sound wave of 20K~10MHZ, in practical applications because effect is similar, leads to
Often the sound wave frequency more than or equal to 15kHz is also referred to as ultrasonic wave.The working frequency of ultrasonic wave described in the method for the present invention is 15
~500kHz, preferably 18~100kHz.
The power of ultrasonic wave described in the method for the present invention needs to be adjusted according to desorption treating capacity, and 100- can be used in laboratory
900W, preferably 100-600W, commerical test can suitably increase ultrasonic power.
Ultrasonication time of the present invention and intermittent time are respectively (1-10) s/ (1-10) s, preferably (2-6) s/
(2-6) s, it is therefore an objective to protect ultrasonic probe.
The alcohols desorbing agent of step described in the method for the present invention (3) is C1-C8 fatty alcohol, such as methanol, ethyl alcohol, propyl alcohol, just
The butanol of structure or isomery, amylalcohol, hexanol, enanthol, octanol etc., preferably methanol and/or ethyl alcohol.
The eluting temperature of step described in the method for the present invention (3) is room temperature~100 DEG C, preferably room temperature~60 DEG C.
The liquid hourly space velocity (LHSV) of step described in the method for the present invention (3) is 0.2~10h-1, preferably 0.6~5.0h-1。
The operating pressure of step described in the method for the present invention (3) is 0.1~1.0MPa, preferably 0.1~0.30MPa.
When the acid value of the alcohols eluent flowed out from adsorption column is less than 0.15mgKOH/g, when preferably 0.10mgKOH/g,
Illustrate that free fatty acid is desorbed completely substantially, can stop eluting.
According to the method for the present invention, the eluent that step (3) obtains can realize alcohols desorbing agent by distilling or being evaporated under reduced pressure
With the separation of the fatty acid methyl ester solution containing free fatty acid.The alcohol recycled after distillation or vacuum distillation can be used for next time
Desorption, the fatty acid methyl ester solution containing free fatty acid can return to biodiesel preparation section, as preparation biodiesel
Raw material.
When the use of methanol being desorbing agent, eluent can separate methanol without distillation, and directly return biodiesel prepares work
Sequence, methanol directly participates in the alcoholysis reaction of preparation biodiesel, to reduce energy consumption.
When using the alcohol other than methanol or ethyl alcohol as desorbing agent, after completing that process is desorbed, need first with methanol or
Ethanol washing adsorption column remaining alcohols material will be eluted out in adsorbing separation column, then carry out the ejection of subsequent nitrogen and
Vacuum pumping.
Step (4) of the present invention preferably carries out as follows: ejecting the alcoholic solution of liquid with inactive gas inhale first
Attached splitter then proceedes to purge into tail gas alcohol content lower than 500ppm, or using the side of vacuum extraction with inactive gas
Alcohols desorbing agent in fixed bed is removed clean, completion dealcoholysis by formula.Wherein, the inactive gas can be nitrogen, sky
Gas, helium, neon, argon gas, preferably nitrogen, purging temperature are room temperature~130 DEG C, preferably room temperature~70 DEG C.The vacuum
The vacuum degree of extracting is 0.02~0.10MPa, and preferably 0.05~0.10MPa, the time of vacuum extraction is 0.2~10h, preferably
For 0.5~3.0h.
When step (3) are desorbing agent using the alcohol other than methanol or ethyl alcohol, before step (4) dealcoholysis, it should use methanol
Or ethanol replacement these desorbing agents, then carry out dealcoholysis operation.
It, can also be using inactive gas purging and/or the side of vacuum extraction before step described in the method for the present invention (3) desorption
Oil plant between adsorbent in adsorbing separation column is discharged formula as far as possible, and to reduce the treating capacity of subsequent desorption, the oil plant of discharge needs
Re-start adsorption deacidification processing.Inactive gas purging and the applicable elements of vacuum extraction are identical as step (4).
When the method for the present invention step (3) uses ultrasonic wave assisted desorption process, ultrasonic wave auxiliary dealcoholysis is can be used in step (4)
Or ultrasonic wave is not used to assist dealcoholysis.
When the method for the present invention step (4) is using ultrasonic wave auxiliary dealcoholysis process, ultrasonic wave assisted desorption is can be used in step (3)
Or do not use ultrasonic wave assisted desorption.
The method of the present invention uses ultrasonic wave assisted desorption or/and dealcoholysis process, and ultrasonic wave is to desorption process or/and dealcoholysis
Journey has following influence: (1) shock wave and microjet have desorption and cleaning action to the surface of solids, can remove surface reactant or in
Mesosome and catalyst surface passivation layer.(2) play the role of dispersing reactant system.(3) promote solvent to go deep into solid interior, generate institute
Meaning is mingled with reaction.Therefore, ultrasonic wave has good rush for the desorption process or/and dealcoholysis process of biodiesel adsorption deacidification
Into effect.
Method provided by the invention has the advantages that (1) can get biodiesel of the acid value less than 0.50mgKOH/g and produce
Product can meet existing BD100 and require and national standard of new generation.(2) ultrasonic wave assisted desorption or/and dealcoholysis can increase substantially
Desorption process or/and dealcoholysis process efficiency.(3) free-fat acid solution can return to preparation biodiesel process after separating with alcohol
Prepare biodiesel.(4) simple realization absorption resin repeated regeneration, and resin long service life is adsorbed, and realize desorption
The recycling of agent.(5) low energy consumption, and material consumption is low, and gas consumption is few, high-efficient, easy to operate, and non-pollutant discharge is environmentally protective.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described, but not thereby limiting the invention.
In embodiment, absorption resin KIP211 is quaternary ammonium salt strong basicity absorption resin, by the triumphant auspicious limited public affairs of chemical industry in Hebei
Department's production.The other strong basicities or weakbase ion exchange of the triumphant auspicious Chemical Manufacture in Hebei also may be selected in absorption resin of the present invention
Resin, as KIP200, KIP201 of KIP series, KIP202, KIP203, KIP204, KIP205, KIP206, KIP207,
KIP208, KIP209, KIP210 etc. also can choose the strong basicity or weak-base ion-exchange resin of Nankai University's production, such as
D301R, D301G, D370, D371, D392, D380, D382 etc., it is also an option that the deacidite of external import with
And the deacidite of domestic other producers.
Embodiment 1
This example demonstrates that the present invention can assist the desorption process of biodiesel adsorption deacidification with ultrasonic wave.
It loads ADSORPTION IN A FIXED BED splitter: loading 30g quaternary ammonium salt strong basicity in fixed bed reactors and adsorb resin
KIP211 (functional group is-NR3OH, and R is hydrocarbon group), reactor is connected on micro- negative test device.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 70 DEG C, 0.20~0.30MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 16h, product acid
Value is 0.04mgKOH/g, obtains the biodiesel oil product of acid value qualification.26h is run, product acid value is 0.82mgKOH/g, is stopped
Charging.16 quality index of the biodiesel oil product of acquisition are qualified.
Desorption: the central tube mode using ultrasonic probe in adsorbing separation column carries out, and the working frequency of ultrasonic wave is
20kHz, ultrasonic power 500W, ultrasonic wave action time and intermittent time are respectively 5s/6s.Into methanol, temperature is 50 DEG C,
0.2~0.3MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, when running 5.0h, meoh eluate acid value is
0.08mgKOH/g completes the desorption of free fatty acid.
Dealcoholysis: liquid methanol is ejected into about 45mL with nitrogen first, then is as far as possible removed methanol completely, about with nitrogen purging
After 4h, methanol content is 320ppm in tail gas.Adsorbing separation column can carry out adsorption deacidification next time.
Methanol solution is evaporated under reduced pressure at 50-80 DEG C, obtains methanol and the fatty acid methyl ester solution containing free fatty acid.First
Alcohol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section, the original as preparation biodiesel
Material.
Comparative example 1
Desorption and regeneration step does not use ultrasonic wave to assist, remaining step and dosage are same as Example 1, as follows:
Desorption: into methanol, temperature is 50 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, when running 7.0h, meoh eluate acid value is 0.10mgKOH/g, completes the desorption of free fatty acid.
Embodiment 2
This example demonstrates that the present invention can be implemented in such a way that adsorbing separation device is in ultrasound field.
Using the ADSORPTION IN A FIXED BED splitter of embodiment 1.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 30 DEG C, 0.8~1.0MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 16h, product acid value
For 0.10mgKOH/g.26h is run, product acid value is 0.85mgKOH/g, stops charging.
Desorption: it is carried out in such a way that supersonic generator is on the outside of adsorbing separation column, the working frequency of ultrasonic wave is
40kHz, ultrasonic power 200W, ultrasonic wave action time and intermittent time are respectively 3s/10s.Into methanol, temperature 30
DEG C, 0.2~0.3MPa of pressure, flow 20.0g/h, liquid hourly space velocity (LHSV) 0.66h-1, 9.0h is run, meoh eluate acid value is
0.06mgKOH/g completes the desorption of free fatty acid.
Dealcoholysis: ejecting about 45mL for liquid methanol with nitrogen first, at this moment still have some methanol to remain in adsorbing separation column,
1.0h is vacuumized in the case where vacuum degree is 0.90 atmospheric pressure with vacuum pump, methanol content is 242ppm in tail gas.Adsorbing separation column is
It can carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: meoh eluate is distilled at 60-90 DEG C, is obtained methanol and is contained free-fat
The fatty acid methyl ester solution of acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section,
Raw material as preparation biodiesel.
Comparative example 2
Desorption and regeneration step does not use ultrasonic wave to assist, remaining step and dosage are same as Example 2, as follows:
Desorption: into methanol, temperature is 30 DEG C, 0.2~0.3MPa of pressure, flow 20.0g/h, liquid hourly space velocity (LHSV) 0.66h-1, 12.0h is run, meoh eluate acid value is 0.10mgKOH/g, completes the desorption of free fatty acid.
Embodiment 3
This example demonstrates that the present invention can be using the dealcoholysis process of ultrasonic wave auxiliary biodiesel.
Using the ADSORPTION IN A FIXED BED splitter of embodiment 1.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 70 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 16h, product acid value
For 0.04mgKOH/g.26h is run, product acid value is 0.95mgKOH/g, stops charging.
Desorption: to fixed bed reactors into ethyl alcohol, temperature is 60 DEG C, 0.20~0.30MPa of pressure, flow 40.0g/h,
Liquid hourly space velocity (LHSV) is 1.33h-1, 7.0h is run, ethanol eluate acid value is 0.10mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: the central tube mode using ultrasonic probe in adsorbing separation column carries out, and the working frequency of ultrasonic wave is
20kHz, ultrasonic power 300W, ultrasonic wave action time and intermittent time are respectively 3s/6s.First with nitrogen by liquid second
Alcohol ejects about 45mL, then is as far as possible removed ethyl alcohol completely with nitrogen purging, and after about 4h, ethanol content is 268ppm in tail gas.It inhales
Attached splitter can carry out adsorption deacidification next time.
The separation of ethyl alcohol and free fatty acid: ethanol eluate is distilled at 80-100 DEG C, obtains ethyl alcohol and containing free rouge
The fatty acid methyl ester solution of fat acid.Ethyl alcohol can be used for desorption next time, and free-fat acid solution returns to biodiesel and prepares work
Sequence, the raw material as preparation biodiesel.
Comparative example 3
Dealcoholysis step does not use ultrasonic wave to assist, remaining step and dosage are same as Example 3, as follows:
Dealcoholysis: liquid ethanol is ejected into about 45mL with nitrogen first, then is as far as possible removed ethyl alcohol completely, about with nitrogen purging
After 5h, ethanol content is 302ppm in tail gas.Adsorbing separation column can carry out adsorption deacidification next time.
Embodiment 4
This example demonstrates that the present invention can be in ultrasonic wave while assisted desorption process and dealcoholysis process, and repeatedly inhaled
Attached desorption manipulation is implemented.
Using the ADSORPTION IN A FIXED BED splitter of embodiment 1.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 45 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 16h, product acid value
For 0.04mgKOH/g, the biodiesel oil product of acid value qualification is obtained.Run 26h, product acid value be 0.82mgKOH/g, stop into
Material.
Desorption: when the working frequency of ultrasonic wave is 20kHz, ultrasonic power 300W, ultrasonic wave action time and interval
Between be respectively 2s/6s.Into methanol, temperature is 45 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, and liquid hourly space velocity (LHSV) is
1.33h-1, 6.0h is run, meoh eluate acid value is 0.05mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: when the working frequency of ultrasonic wave is 20kHz, ultrasonic power 300W, ultrasonic wave action time and interval
Between be respectively 2s/6s.Methanol is ejected into about 45mL with nitrogen first, at this moment still there are some methanol to remain in adsorbing separation column, is used
Vacuum pump vacuumizes 4.0h in the case where vacuum degree is 0.50 atmospheric pressure, and methanol content is 135ppm in tail gas.Adsorbing separation column
Carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: meoh eluate is evaporated under reduced pressure at 50-80 DEG C, obtains methanol and containing free
The fatty acid methyl ester of fatty acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section,
Raw material as preparation biodiesel.
Under ultrasonic wave auxiliary, absorption and the desorption manipulation of biodiesel is repeated, carries out 10 operations, has no absorption
Depickling reduced performance.Therefore, adsorption deacidification agent of the invention and adsorption deacidification technique are very reliable.
Comparative example 4
Desorption and dealcoholysis step do not use ultrasonic wave to assist, remaining step is same as Example 4, as follows:
Desorption: into methanol, temperature is 45 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, 8.0h is run, meoh eluate acid value is 0.08mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: methanol is ejected into about 45mL with nitrogen first, at this moment still there are some methanol to remain in adsorbing separation column, then
5.0h is vacuumized in the case where vacuum degree is 0.50 atmospheric pressure with vacuum pump, methanol content is 178ppm in tail gas.Adsorbing separation column is
It can carry out adsorption deacidification next time.
Embodiment 5
This example demonstrates that the present invention can assist dealcoholysis using higher supersonic frequency.
Using the ADSORPTION IN A FIXED BED splitter of embodiment 1.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 40 DEG C, 0.2~0.3MPa of pressure, flow 10.0g/h, liquid hourly space velocity (LHSV) 0.33h-1, run 51h, product acid value
For 0.29mgKOH/g.55h is run, product acid value is 0.65mgKOH/g, stops charging.
Desorption: into methanol, temperature is 30 DEG C, 0.8~1.0MPa of pressure, flow 20.0g/h, liquid hourly space velocity (LHSV) 0.66h-1, 12.0h is run, meoh eluate acid value is 0.10mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: when the working frequency of ultrasonic wave is 80kHz, ultrasonic power 300W, ultrasonic wave action time and interval
Between be respectively 3s/6s.Methanol is ejected with nitrogen, at this moment still there are some methanol to remain in adsorbing separation column, with vacuum pump true
Reciprocal of duty cycle is to vacuumize 2.0h under 0.80 atmospheric pressure, and methanol content is 124ppm in tail gas.Methanol is gone as far as possible with nitrogen purging again
Except clean.Adsorbing separation column can carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: meoh eluate is distilled at 60-90 DEG C, is obtained methanol and is contained free-fat
The fatty acid methyl ester of acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section, as
Prepare the raw material of biodiesel.
Embodiment 6
This example demonstrates that the present invention can be implemented at 30 DEG C.Using the ADSORPTION IN A FIXED BED splitter of embodiment 1.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 30 DEG C, 0.8~1.0MPa of pressure, flow 150.0g/h, liquid hourly space velocity (LHSV) 5.00h-1, run 4.0h, product acid
Value is 0.13mgKOH/g.6.0h is run, product acid value is 0.56mgKOH/g, stops charging.
Desorption: when the working frequency of ultrasonic wave is 20kHz, ultrasonic power 300W, ultrasonic wave action time and interval
Between be respectively 2s/6s.Into methanol, temperature is 30 DEG C, 0.1~0.2MPa of pressure, flow 20.0g/h, and liquid hourly space velocity (LHSV) is
0.66h-1, 10.0h is run, meoh eluate acid value is 0.12mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: ejecting about 45mL for methanol with nitrogen, is then as far as possible removed methanol completely with nitrogen purging, after about 4h,
Methanol content is 380ppm in tail gas.Adsorbing separation column can carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: meoh eluate is distilled at 60-90 DEG C, is obtained methanol and is contained free-fat
The fatty acid methyl ester of acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section, as
Prepare the raw material of biodiesel.
Embodiment 7
This example demonstrates that the present invention can adsorb resin D301R (Nankai University's resin, function using tertiary amines alkalescent
Base is-N (CH3)2) implement.
Load ADSORPTION IN A FIXED BED splitter: the 30g alkaline adsorption resin D301R in fixed bed reactors connects reactor
It is connected on micro- negative test device.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 70 DEG C, 0.20~0.30MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 14h, product acid
Value is 0.10mgKOH/g, obtains the biodiesel oil product of acid value qualification.22h is run, product acid value is 0.80mgKOH/g, is stopped
Charging.
Desorption: when the working frequency of ultrasonic wave is 20kHz, ultrasonic power 900W, ultrasonic wave action time and interval
Between be respectively 1s/5s.Into methanol, temperature is 50 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, and liquid hourly space velocity (LHSV) is
1.33h-1, when running 2.5h, meoh eluate acid value is 2.20mgKOH/g, continues to be desorbed；When running 5.0h, methanol is molten
Liquid acid value is 0.08mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: liquid methanol is ejected into about 45mL with nitrogen first, then is as far as possible removed methanol completely, about with nitrogen purging
After 4h, methanol content is 420ppm in tail gas.Adsorbing separation column can carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: meoh eluate is evaporated under reduced pressure at 50-80 DEG C, obtains methanol and containing free
The fatty acid methyl ester of fatty acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section,
Raw material as preparation biodiesel.
Embodiment 8
This example demonstrates that the present invention can adsorb resin D380 (Nankai University's resin, function using primary amine class alkalescent
Base is-NH2) implement.
Load ADSORPTION IN A FIXED BED splitter: the 30g alkaline adsorption resin D370 in fixed bed reactors connects reactor
Onto micro- negative test device.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 70 DEG C, 0.20~0.30MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 12h, product acid
Value is 0.08mgKOH/g, obtains the biodiesel oil product of acid value qualification.18h is run, product acid value is 0.75mgKOH/g, is stopped
Charging.
Desorption: when the working frequency of ultrasonic wave is 20kHz, ultrasonic power 500W, ultrasonic wave action time and interval
Between be respectively 2s/10s.Into methanol, temperature is 50 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, and liquid hourly space velocity (LHSV) is
1.33h-1, when running 2.0h, methanol solution acid value is 2.20mgKOH/g, continues to be desorbed；When running 5.0h, methanol solution
Acid value is 0.10mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: liquid methanol is ejected into about 45mL with nitrogen first, then is as far as possible removed methanol completely, about with nitrogen purging
After 4h, methanol content is 420ppm in tail gas.Adsorbing separation column can carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: methanol solution is evaporated under reduced pressure at 50-80 DEG C, obtains methanol and containing free rouge
The fatty acid methyl ester of fat acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section, make
For the raw material for preparing biodiesel.
Embodiment 9
This example demonstrates that the present invention can adsorb resin D382 (Nankai University's resin, function base using secondary amine alkalescent
For-NHCH3) implement.
Load ADSORPTION IN A FIXED BED splitter: the 30g alkaline adsorption resin D370 in fixed bed reactors connects reactor
Onto micro- negative test device.
Adsorption deacidification: the biodiesel that acid value is 1.65mgKOH/g is fed with micro pump, is separated into ADSORPTION IN A FIXED BED
Column, temperature are 70 DEG C, 0.20~0.30MPa of pressure, flow 40.0g/h, liquid hourly space velocity (LHSV) 1.33h-1, run 10h, product acid
Value is 0.16mgKOH/g, obtains the biodiesel oil product of acid value qualification.13h is run, product acid value is 0.83mgKOH/g, is stopped
Charging.
Desorption: when the working frequency of ultrasonic wave is 20kHz, ultrasonic power 300W, ultrasonic wave action time and interval
Between be respectively 2s/6s.Into methanol, temperature is 50 DEG C, 0.2~0.3MPa of pressure, flow 40.0g/h, and liquid hourly space velocity (LHSV) is
1.33h-1, when running 1.5h, methanol solution acid value is 1.80mgKOH/g, continues to be desorbed；When running 3.0h, methanol solution
Acid value is 0.10mgKOH/g, completes the desorption of free fatty acid.
Dealcoholysis: liquid methanol is ejected into about 45mL with nitrogen first, then is as far as possible removed methanol completely, about with nitrogen purging
After 4h, methanol content is 220ppm in tail gas.Adsorbing separation column can carry out adsorption deacidification next time.
The separation of methanol and free fatty acid: methanol solution is evaporated under reduced pressure at 50-80 DEG C, obtains methanol and containing free rouge
The fatty acid methyl ester of fat acid.Methanol can be used for desorption next time, and free-fat acid solution returns to biodiesel preparation section, make
For the raw material for preparing biodiesel.
Claims (16)
1. a kind of method of biodiesel adsorption deacidification, comprising: (1) load fixed bed with absorption resin, obtain ADSORPTION IN A FIXED BED
Splitter；(2) the underproof biodiesel of acid value is subjected to adsorption deacidification by adsorbing separation column, obtains the biology of acid value qualification
Diesel oil；(3) under ultrasonic wave booster action, with the adsorbing separation column of alcohols desorbing agent elution saturation；(4) it assists making in ultrasonic wave
Under, the alcohols desorbing agent in fixed bed is removed to clean, adsorbing separation column, that is, reusable.
2. according to the method for claim 1, wherein the absorption resin of step (1) is the absorption tree for having loaded basic group
Rouge, the basic group are selected from one of hydroxyl, primary amine, secondary amine, tertiary amine and quaternary ammonium group or a variety of.
3. according to the method for claim 1, wherein the acid value of the unqualified biodiesel of acid value of step (2) be 0.5~
5.0mgKOH/g。
4. according to the method for claim 1, wherein the adsorption deacidification temperature of step (2) is room temperature~100 DEG C, liquid space-time
Speed is 0.2~10h-1, operating pressure is 0.1~5.0MPa.
5. according to the method for claim 1, wherein the adsorption deacidification temperature of step (2) is room temperature~60 DEG C, liquid hourly space velocity (LHSV)
For 0.6~5.0h-1, operating pressure is 0.1~0.30MPa.
6. according to the method for claim 1, wherein step (3) or (4) described ultrasonic wave booster action take two kinds of sides
Ultrasonic probe is placed in the central tube of adsorbing separation device likes: (1)；Or supersonic generator is placed in adsorbing separation device by (2)
Pipe outside.
7. according to method described in claim 1 or 6, wherein the working frequency of the ultrasonic wave is 15~500kHz, described super
The power of sound wave is 100-900W, and the ultrasonication time and intermittent time are respectively (1-10) s/ (1-10) s.
8. according to method described in claim 1 or 6, wherein the working frequency of the ultrasonic wave is 18~100kHz, described super
The power of sound wave is 100-600W, and the ultrasonication time and intermittent time are respectively (2-6) s/ (2-6) s.
9. according to the method for claim 1, wherein the alcohols desorbing agent of step (3) is at least one in C1-C8 fatty alcohol
Kind.
10. according to method described in claim 1 or 9, wherein the alcohols desorbing agent of step (3) is selected from methanol, ethyl alcohol, propyl alcohol,
Butanol, amylalcohol, hexanol, enanthol, the octanol of positive structure or isomery.
11. according to the method for claim 1, wherein the eluting temperature of the step (3) is room temperature~100 DEG C, liquid space-time
Speed is 0.2~10h-1, operating pressure is 0.1~1.0MPa.
12. according to the method for claim 1, wherein the eluting temperature of the step (3) is room temperature~60 DEG C, liquid space-time
Speed is 0.6~5.0h-1, operating pressure is 0.1~0.30MPa.
13. according to the method for claim 1, wherein step (4) carries out as follows: first will with inactive gas
The alcoholic solution of liquid ejects adsorbing separation column, then proceedes to purge into tail gas alcohol content lower than 500ppm with inactive gas,
Or by the way of vacuum extraction, the alcohols desorbing agent in fixed bed is removed to clean, completion dealcoholysis.
14. according to the method for claim 13, wherein the inactive gas is selected from nitrogen, air, helium, neon
Or argon gas, purging temperature are room temperature~130 DEG C.
15. according to the method for claim 13, wherein the vacuum degree of the vacuum extraction is 0.02~0.10MPa, very
The time that empty pump mentions is 0.2~10h.
16. according to the method for claim 1, wherein before step (3) desorption, also using inactive gas purging and/or very
Oil plant between adsorbent in adsorbing separation column is discharged the mode that empty pump mentions as far as possible.
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| CN101993776A (en) * | 2009-08-27 | 2011-03-30 | 中国石油化工股份有限公司 | Method for deacidifying biodiesel |
| CN103173281A (en) * | 2011-12-21 | 2013-06-26 | 中国石油化工股份有限公司 | Method for reducing acid value of biodiesel crude product and preparation method of biodiesel |
| CN203096026U (en) * | 2013-03-16 | 2013-07-31 | 石盛华 | Deacidification device for pretreatment of biodiesel |
| CN103333719A (en) * | 2013-06-19 | 2013-10-02 | 江苏卡特新能源有限公司 | Production equipment and production technology for biodiesel with low acid value |
| CN203333605U (en) * | 2013-06-19 | 2013-12-11 | 江苏卡特新能源有限公司 | Production equipment for biodiesel with low acid value |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101993776A (en) * | 2009-08-27 | 2011-03-30 | 中国石油化工股份有限公司 | Method for deacidifying biodiesel |
| CN103173281A (en) * | 2011-12-21 | 2013-06-26 | 中国石油化工股份有限公司 | Method for reducing acid value of biodiesel crude product and preparation method of biodiesel |
| CN203096026U (en) * | 2013-03-16 | 2013-07-31 | 石盛华 | Deacidification device for pretreatment of biodiesel |
| CN103333719A (en) * | 2013-06-19 | 2013-10-02 | 江苏卡特新能源有限公司 | Production equipment and production technology for biodiesel with low acid value |
| CN203333605U (en) * | 2013-06-19 | 2013-12-11 | 江苏卡特新能源有限公司 | Production equipment for biodiesel with low acid value |
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