CN105273838A - Biodiesel adsorption deacidification method - Google Patents
Biodiesel adsorption deacidification method Download PDFInfo
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- CN105273838A CN105273838A CN201410283294.3A CN201410283294A CN105273838A CN 105273838 A CN105273838 A CN 105273838A CN 201410283294 A CN201410283294 A CN 201410283294A CN 105273838 A CN105273838 A CN 105273838A
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Abstract
The invention discloses a biodiesel adsorption deacidification method. The biodiesel adsorption deacidification method comprises following steps: (1) a static bed is filled with an adsorption resin so as to obtain a static bed adsorption separation column; (2) biodiesel with unqualified acid value is subjected to adsorption deacidification using the static bed adsorption separation column so as to obtain biodiesel with qualified acid value; (3) the saturated static bed adsorption separation column is eluted with an alcohol desorption agent under ultrasonic assisting; and (4) under ultrasonic assisting, the alcohol desorption agent is completely removed, and the static bed adsorption separation column can be recycled. The biodiesel adsorption deacidification method is capable of obtaining biodiesel products with an acid value smaller than 0.50mg KOH/g, and satisfying conventional BD100 and new national standard requirements; ultrasonic-assisted desorption or/and dealcoholization are capable of increasing desorption or/and dealcoholization efficiency; operation is simple; no pollutant is discharged; and the biodiesel adsorption deacidification method is green and friendly to the environment.
Description
Technical field
The present invention relates to a kind of method of biofuel adsorption deacidification.
Background technology
Biofuel have nontoxic, without sulphur, sufficient combustion, the characteristic such as biodegradable, lubricity is excellent, minimizing atmospheric pollution and greenhouse gas emission are significant.What consume along with fossil energy increases the continuous minimizing with reserves day by day, and the environment brought goes from bad to worse and the aggravation of Greenhouse effect, and reproducible clean energy biofuel is just subject to extensive concern.
Biofuel is carried out transesterification reaction by natural fats and oils and monohydroxy-alcohol and is obtained, and the product of transesterification reaction, except fatty acid ester, also may contain Tegin 55G, two sweet fat, glycerin by-products, free fatty acids, and unreacted alcohol and glyceride stock.In recent years, adopt waste grease such as waste cooking oil, acidification oil to be that raw material is prepared biofuel and become study hotspot, the acid number difference of these greases is very large, and some acidification oil acid numbers even can reach 170mgKOH/g.When using preparing biological diesel fuel by high-acid-value grease, product acid number is generally greater than even much larger than BD100 acid number standard (≤0.80mgKOH/g).In order to make product acid number reach standard-required, depickling process can be carried out to raw material or product.
Alkali cleaning is classical deacidifying process, the alkaline solutions such as lot of domestic and international research sodium hydroxide and free fatty acids carry out neutralization reaction, gained fatty acid sodium salt is separated from oil product, the lipid acid dissociated is obtained through acidifying, reaction process can complete instantaneously, but easily produces emulsion in reaction process.And alkali lye runs off in a large number in company with converted products, sodium hydroxide solution can not regenerate.
By esterification, the free fatty acids in biodiesel oil product being converted into fatty acid methyl ester is a kind of method preferably, but when the acid number of biofuel is more close to 0.80mgKOH/g, esterification depickling is more difficult, thus causes the energy consumption of technique higher.
CN101993776A provides a kind of method of deacidifying biodiesel, comprise the following steps: make to treat that depickling biofuel mixes with the de-acidying agent containing water-soluble alcohol, water-soluble amine and water, isolate oil phase and aqueous phase after layering, oil phase obtains the qualified biofuel of acid number after refining.The shortcoming of the method is: 1 loss causing free fatty acids.2 produce the waste water containing organic amine and soap.
CN101289627A mono-kind reduces the method for acid number of biodiesel, it is characterized in that: crude fatty acid methyl ester is carried out rectifying, the acid lowering agent accounting for smart fatty acid methyl ester gross weight 0.02 ~ 4% is added after rectifying, stirring reaction 0.2 ~ 0.5 hour at 60 ~ 80 DEG C, sedimentation releases lower floor's acid lowering agent in 2 hours, be put into finished pot after upper strata acid number is qualified, acid lowering agent can be reused, and product is cycloalkanoimide.The shortcoming of the method is: 1 loss causing free fatty acids.2 amine acid lowering agents easily remain in biodiesel oil product.
CN101735845A relates to a kind of method of separating and purifying biodiesel.Comprise the following steps: 1) with thin-film evaporator, degassed and distillation procedure is carried out to biodiesel coarse product, obtain the biofuel of methyl ester content more than 96%; 2) to step 1) product after separating treatment carries out alkaline soil depickling, obtains the purified biofuel that acid number meets national standard.The shortcoming of the method is: 1, free fatty acids loss, can not be processed into biofuel.2, alkaline soil can not regenerate.
CN101550364A relates to a kind of method fully utilizing high acid value oil plant and prepare biofuel, is with high acid value oil plant through methyl alcohol multistage (n >=1) extracting operation, obtains methanol phase and low acid number glyceryl ester phase in operating process.Wherein in grease, most of free fatty acids is dissolved in methanol phase, through preparation of biodiesel by acid catalysts after enrichment; And low acid number glyceryl ester prepares biofuel through base catalysis.The shortcoming of the method is: 1, running cost is higher.2, product purification can not be used for.
US249366 adopts in excess base the acid number reduced with free fatty acids in high-acid value grease, and carry out esterification reaction of organic acid, the soap that alkali and free fatty acids are formed adds sulfuric acid after esterification, carry out being obtained by reacting free fatty acids, this part free fatty acids is under acid catalysis, carry out esterification again, obtain material and obtain methyl esters through neutralization, filtration and rectifying.The shortcoming of the method is: 1, adopt excess base and sulfuric acid, production cost is higher.2, the by product vitriol of low value is created.
For promoting the quality product of biofuel further, integrate with international standard, the standard modification that China plans biofuel BD100 is acid number≤0.50mgKOH/g, and this increases the difficulty of deacidifying biodiesel further.Therefore, exploitation is needed to reduce acid number of biodiesel to below 0.80mgKOH/g, the even acid stripping method of below 0.50mgKOH/g.
Summary of the invention
The present invention proposes a kind of method of biofuel adsorption deacidification, particularly ultrasonic assistant desorption process or/and the method for dealcoholysis process.
The method of biofuel adsorption deacidification provided by the invention, comprising: (1) loads fixed bed with polymeric adsorbent, is fixed a fractionation by adsorption post; (2) underproof for acid number biofuel is carried out adsorption deacidification by fractionation by adsorption post, obtain the biofuel that acid number is qualified; (3) under ultrasonic assistant effect, with the fractionation by adsorption post that alcohols desorbing agent wash-out is saturated; (4) under ultrasonic assistant effect, remove totally by the alcohols desorbing agent in fixed bed, fractionation by adsorption post can be used again.
Specifically, method provided by the invention is: (1) first loads fixed bed with polymeric adsorbent, obtains ADSORPTION IN A FIXED BED separator column; (2) adsorption deacidification: by underproof for acid number biofuel by adsorption column, obtains the biofuel that acid number is qualified, reaches the object of adsorption deacidification.When defective from the acid number of fractionation by adsorption post biofuel out, the absorption of fractionation by adsorption post is saturated, stops biofuel charging, carries out desorption; (3) desorption: under ultrasonic assistant effect, is saturated the fractionation by adsorption post of free fatty acids with alcohols desorbing agent wash-out, complete fractionation by adsorption post desorption when desorption liquid acid number is reduced to below 0.15mgKOH/g; (4) dealcoholysis: under ultrasonic assistant effect, first ejects the alcohol in fractionation by adsorption post with inactive gas as far as possible, then adopts the mode vacuumized to be removed totally by alcohol as far as possible, or with the clean remaining alcohol of nitrogen purging, completes fractionation by adsorption column regeneration.
The polymeric adsorbent of the polymeric adsorbent of step described in the inventive method (1) basic group that has been load, described basic group can be strong basicity group, also can be weakly alkaline group, one or more in preferred hydroxyl, primary amine, secondary amine, tertiary amine and quaternary ammonium group etc.
The acid number of the defective biofuel of acid number of step described in the inventive method (2) is 0.5 ~ 5.0mgKOH/g, is preferably 0.8 ~ 2.0mgKOH/g.
The biofuel that the acid number of step described in the inventive method (2) is qualified refers to that acid number is less than 0.80mgKOH/g (BD100 standard), is preferably less than the biofuel of 0.50mgKOH/g (new national standard).
The adsorption deacidification temperature of step described in the inventive method (2) is room temperature ~ 100 DEG C, is preferably room temperature ~ 60 DEG C.
The liquid hourly space velocity of step described in the inventive method (2) is 0.2 ~ 10h
-1, be preferably 0.6 ~ 5.0h
-1.
The working pressure of step described in the inventive method (2) is 0.1 ~ 5.0MPa, is preferably 0.1 ~ 0.30MPa.
Ultrasonic assistant desorption process of the present invention, or/and dealcoholysis process, can take two kinds of modes: ultrasonic probe is placed in the pipe core of fractionation by adsorption device by (1); (2) ultrasonic generator is placed in the pipe outer (in other words fractionation by adsorption device being placed in ultrasonic field) of fractionation by adsorption device.
Ultrasonic wave generally refers to the sound wave of range of frequency at 20K ~ 10MHZ, in actual applications because effect is similar, usually frequency is more than or equal to the sound wave of 15kHz also referred to as ultrasonic wave.Hyperacoustic operating frequency described in the inventive method is 15 ~ 500kHz, preferably 18 ~ 100kHz.
Hyperacoustic power described in the inventive method needs to regulate according to desorption treatment capacity, and testing laboratory can adopt 100-900W, preferred 100-600W, and commerical test suitably can increase ultrasonic power.
Ultrasonication time of the present invention and intermittent time are respectively (1-10) s/ (1-10) s, are preferably (2-6) s/ (2-6) s, and object is protection ultrasonic probe.
The alcohols desorbing agent of step described in the inventive method (3) is C1-C8 fatty alcohol, such as methyl alcohol, ethanol, propyl alcohol, the butanols, amylalcohol, hexanol, enanthol, octanol etc. of positive structure or isomery, particular methanol and/or ethanol.
The eluting temperature of step described in the inventive method (3) is room temperature ~ 100 DEG C, is preferably room temperature ~ 60 DEG C.
The liquid hourly space velocity of step described in the inventive method (3) is 0.2 ~ 10h
-1, be preferably 0.6 ~ 5.0h
-1.
The working pressure of step described in the inventive method (3) is 0.1 ~ 1.0MPa, is preferably 0.1 ~ 0.30MPa.
When the acid number of the alcohols elutriant flowed out from adsorption column is less than 0.15mgKOH/g, during preferred 0.10mgKOH/g, illustrate that the basic desorption of free fatty acids is complete, can wash-out be stopped.
According to the inventive method, the elutriant that step (3) obtains realizes alcohols desorbing agent and being separated of fatty acid methyl ester solution containing free fatty acids by distillation or underpressure distillation.Reclaim the desorption that the alcohol obtained can be used for next time after distillation or underpressure distillation, the fatty acid methyl ester solution containing free fatty acids can return biofuel preparation section, as the raw material of preparation biofuel.
When using methyl alcohol for desorbing agent, elutriant without fractionation by distillation methyl alcohol, can directly return biofuel preparation section, and methyl alcohol participates in the alcoholysis reaction of preparation biofuel directly, thus reduces energy consumption.
When using the alcohol beyond methyl alcohol or ethanol as desorbing agent, after completing desorption operation, needing first with methyl alcohol or washing with alcohol adsorption column, by alcohols material wash-out residual in fractionation by adsorption post out, then carrying out follow-up nitrogen and eject and vacuum pumping.
Step of the present invention (4) is preferably carried out as follows: first with inactive gas, the alcoholic solution of liquid state is ejected fractionation by adsorption post, then continuation inactive gas purges to alcohol content in tail gas lower than 500ppm, or adopt the mode of vacuum extraction, alcohols desorbing agent in fixed bed is removed totally, completes dealcoholysis.Wherein, described inactive gas can be nitrogen, air, helium, neon, argon gas, preferred nitrogen, and purging temperature is room temperature ~ 130 DEG C, is preferably room temperature ~ 70 DEG C.The vacuum tightness of described vacuum extraction is 0.02 ~ 0.10MPa, and be preferably 0.05 ~ 0.10MPa, the time of vacuum extraction is 0.2 ~ 10h, is preferably 0.5 ~ 3.0h.
When step (3) uses alcohol beyond methyl alcohol or ethanol for desorbing agent, before step (4) dealcoholysis, with methyl alcohol or these desorbing agents of ethanol replacement, then dealcoholysis operation should be carried out.
Before step described in the inventive method (3) desorption, the mode of inactive gas purging and/or vacuum extraction can also be adopted to be discharged by the oil plant in fractionation by adsorption post between sorbent material as far as possible, to reduce the treatment capacity of follow-up desorption, the oil plant of discharge needs to re-start adsorption deacidification process.Inactive gas purges identical with step (4) with the applicable elements of vacuum extraction.
During the inventive method step (3) employing ultrasonic assistant desorption process, step (4) can adopt ultrasonic assistant dealcoholysis or not adopt ultrasonic assistant dealcoholysis.
During the inventive method step (4) employing ultrasonic assistant dealcoholysis process, step (3) can adopt ultrasonic assistant desorption or not adopt ultrasonic assistant desorption.
The inventive method adopts ultrasonic assistant desorption or/and dealcoholysis process, ultrasonic wave on desorption process or/and dealcoholysis process has following impact: (1) shockwave and microjet have desorb and cleanup action to solid surface, can remove surface reaction thing or intermediate and catalyst surface passivation layer.(2) effect of dispersion reaction system is had.(3) promote that solvent gos deep into solid interior, produce and be so-calledly mingled with reaction.Therefore, ultrasonic wave for the desorption process of biofuel adsorption deacidification or/and dealcoholysis process has good promoter action.
Method tool provided by the invention has the following advantages: (1) can obtain the biodiesel oil product that acid number is less than 0.50mgKOH/g, can meet existing BD100 and require and Standard of new generation.(2) ultrasonic assistant desorption is or/and dealcoholysis can increase substantially desorption process or/and dealcoholysis process efficiency.(3) free-fat acid solution can turn back to preparation biofuel operation and prepares biofuel after being separated with alcohol.(4) simple realization polymeric adsorbent repeated regeneration, and polymeric adsorbent long service life, and achieve recycling of desorbing agent.(5) energy consumption is low, and material consumption is low, and gas consumption is few, and efficiency is high, easy and simple to handle, non-pollutant discharge, environmental protection.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but not thereby limiting the invention.
In embodiment, polymeric adsorbent KIP211 is quaternary ammonium salt strong basicity polymeric adsorbent, and effluent Bei Kairui Chemical Co., Ltd. produces.Polymeric adsorbent of the present invention also can select other strong basicity or the weak-base ion-exchange resin of the triumphant auspicious Chemical Manufacture in Hebei, as KIP200, KIP201, KIP202, KIP203, KIP204, KIP205, KIP206, KIP207, KIP208, KIP209, KIP210 etc. of KIP series, also the strong basicity that Nankai University can be selected to produce or weak-base ion-exchange resin, as D301R, D301G, D370, D371, D392, D380, D382 etc., the deacidite of the deacidite of external import and other producer domestic can also be selected.
Embodiment 1
The present embodiment illustrates that the present invention can use the desorption process of ultrasonic assistant biofuel adsorption deacidification.
Filling ADSORPTION IN A FIXED BED separator column: load 30g quaternary ammonium salt strong basicity polymeric adsorbent KIP211 (functional group is-NR3OH, R is hydrocarbon group) in fixed-bed reactor, reactor is connected on micro-negative test device.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 70 DEG C, pressure 0.20 ~ 0.30MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 16h, product acid number is 0.04mgKOH/g, obtains the biodiesel oil product that acid number is qualified.Run 26h, product acid number is 0.82mgKOH/g, stops charging.16 quality index of the biodiesel oil product obtained are all qualified.
Desorption: adopt ultrasonic probe to carry out in the pipe core mode of fractionation by adsorption post, hyperacoustic operating frequency is 20kHz, and ultrasonic power is 500W, and ul-trasonic irradiation time and intermittent time are respectively 5s/6s.Enter methyl alcohol, temperature is 50 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, when running 5.0h, meoh eluate acid number is 0.08mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: first with nitrogen, liquid methanol is ejected about 45mL, then methyl alcohol is removed clean with nitrogen purging as far as possible, after about 4h, in tail gas, methanol content is 320ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
By methanol solution 50-80 DEG C of underpressure distillation, obtain methyl alcohol and the fatty acid methyl ester solution containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Comparative example 1
Desorption and regeneration step does not adopt ultrasonic assistant, and all the other steps are identical with embodiment 1 with consumption, as follows:
Desorption: enter methyl alcohol, temperature is 50 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, when running 7.0h, meoh eluate acid number is 0.10mgKOH/g, completes the desorption of free fatty acids.
Embodiment 2
The present embodiment illustrates that the present invention can adopt the mode of fractionation by adsorption device in ultrasonic wave field to implement.
Adopt the ADSORPTION IN A FIXED BED separator column of embodiment 1.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 30 DEG C, pressure 0.8 ~ 1.0MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 16h, product acid number is 0.10mgKOH/g.Run 26h, product acid number is 0.85mgKOH/g, stops charging.
Desorption: adopt the mode of ultrasonic generator outside fractionation by adsorption post to carry out, hyperacoustic operating frequency is 40kHz, and ultrasonic power is 200W, and ul-trasonic irradiation time and intermittent time are respectively 3s/10s.Enter methyl alcohol, temperature is 30 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 20.0g/h, and liquid hourly space velocity is 0.66h
-1, run 9.0h, meoh eluate acid number is 0.06mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: first with nitrogen, liquid methanol is ejected about 45mL, at this moment still have some methyl alcohol to remain in fractionation by adsorption post, under vacuum tightness is 0.90 normal atmosphere, vacuumize 1.0h with vacuum pump, in tail gas, methanol content is 242ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: distilled at 60-90 DEG C by meoh eluate, obtains methyl alcohol and the fatty acid methyl ester solution containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Comparative example 2
Desorption and regeneration step does not adopt ultrasonic assistant, and all the other steps are identical with embodiment 2 with consumption, as follows:
Desorption: enter methyl alcohol, temperature is 30 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 20.0g/h, and liquid hourly space velocity is 0.66h
-1, run 12.0h, meoh eluate acid number is 0.10mgKOH/g, completes the desorption of free fatty acids.
Embodiment 3
The present embodiment illustrates that the present invention can adopt the dealcoholysis process of ultrasonic assistant biofuel.
Adopt the ADSORPTION IN A FIXED BED separator column of embodiment 1.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 70 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 16h, product acid number is 0.04mgKOH/g.Run 26h, product acid number is 0.95mgKOH/g, stops charging.
Desorption: enter ethanol to fixed-bed reactor, temperature is 60 DEG C, pressure 0.20 ~ 0.30MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 7.0h, ethanol eluate acid number is 0.10mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: adopt ultrasonic probe to carry out in the pipe core mode of fractionation by adsorption post, hyperacoustic operating frequency is 20kHz, and ultrasonic power is 300W, and ul-trasonic irradiation time and intermittent time are respectively 3s/6s.First with nitrogen, liquid ethanol is ejected about 45mL, then removed by ethanol clean with nitrogen purging as far as possible, after about 4h, in tail gas, ethanol content is 268ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Ethanol is separated with free fatty acids: distilled at 80-100 DEG C by ethanol eluate, obtains ethanol and the fatty acid methyl ester solution containing free fatty acids.Ethanol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Comparative example 3
Dealcoholysis step does not adopt ultrasonic assistant, and all the other steps are identical with embodiment 3 with consumption, as follows:
Dealcoholysis: first with nitrogen, liquid ethanol is ejected about 45mL, then ethanol is removed clean with nitrogen purging as far as possible, after about 5h, in tail gas, ethanol content is 302ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Embodiment 4
The present embodiment illustrates that the present invention in ultrasonic wave assisted desorption process and dealcoholysis process simultaneously, and can carry out multiple adsorb desorption manipulation to implement.
Adopt the ADSORPTION IN A FIXED BED separator column of embodiment 1.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 45 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 16h, product acid number is 0.04mgKOH/g, obtains the biodiesel oil product that acid number is qualified.Run 26h, product acid number is 0.82mgKOH/g, stops charging.
Desorption: hyperacoustic operating frequency is 20kHz, ultrasonic power is 300W, and ul-trasonic irradiation time and intermittent time are respectively 2s/6s.Enter methyl alcohol, temperature is 45 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 6.0h, meoh eluate acid number is 0.05mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: hyperacoustic operating frequency is 20kHz, ultrasonic power is 300W, and ul-trasonic irradiation time and intermittent time are respectively 2s/6s.First with nitrogen, methyl alcohol is ejected about 45mL, at this moment still have some methyl alcohol to remain in fractionation by adsorption post, under vacuum tightness is 0.50 normal atmosphere, vacuumize 4.0h with vacuum pump, in tail gas, methanol content is 135ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: by meoh eluate 50-80 DEG C of underpressure distillation, obtains methyl alcohol and the fatty acid methyl ester containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Under ultrasonic assistant, repeatedly carry out absorption and the desorption manipulation of biofuel, carry out 10 operations, have no adsorption deacidification performance and reduce.Therefore, adsorption deacidification agent of the present invention and adsorption deacidification technique very reliable.
Comparative example 4
Desorption and dealcoholysis step do not adopt ultrasonic assistant, and all the other steps are identical with embodiment 4, as follows:
Desorption: enter methyl alcohol, temperature is 45 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 8.0h, meoh eluate acid number is 0.08mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: first with nitrogen, methyl alcohol is ejected about 45mL, at this moment still have some methyl alcohol to remain in fractionation by adsorption post, then under vacuum tightness is 0.50 normal atmosphere, vacuumize 5.0h with vacuum pump, in tail gas, methanol content is 178ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Embodiment 5
The present embodiment illustrates that the present invention can adopt higher ultrasonic frequency to assist dealcoholysis.
Adopt the ADSORPTION IN A FIXED BED separator column of embodiment 1.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 40 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 10.0g/h, and liquid hourly space velocity is 0.33h
-1, run 51h, product acid number is 0.29mgKOH/g.Run 55h, product acid number is 0.65mgKOH/g, stops charging.
Desorption: enter methyl alcohol, temperature is 30 DEG C, pressure 0.8 ~ 1.0MPa, and flow is 20.0g/h, and liquid hourly space velocity is 0.66h
-1, run 12.0h, meoh eluate acid number is 0.10mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: hyperacoustic operating frequency is 80kHz, ultrasonic power is 300W, and ul-trasonic irradiation time and intermittent time are respectively 3s/6s.Ejected by methyl alcohol with nitrogen, at this moment still have some methyl alcohol to remain in fractionation by adsorption post, under vacuum tightness is 0.80 normal atmosphere, vacuumize 2.0h with vacuum pump, in tail gas, methanol content is 124ppm.Methyl alcohol is removed clean with nitrogen purging more as far as possible.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: distilled at 60-90 DEG C by meoh eluate, obtains methyl alcohol and the fatty acid methyl ester containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Embodiment 6
The present embodiment illustrates that the present invention can implement at 30 DEG C.Adopt the ADSORPTION IN A FIXED BED separator column of embodiment 1.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 30 DEG C, pressure 0.8 ~ 1.0MPa, and flow is 150.0g/h, and liquid hourly space velocity is 5.00h
-1, run 4.0h, product acid number is 0.13mgKOH/g.Run 6.0h, product acid number is 0.56mgKOH/g, stops charging.
Desorption: hyperacoustic operating frequency is 20kHz, ultrasonic power is 300W, and ul-trasonic irradiation time and intermittent time are respectively 2s/6s.Enter methyl alcohol, temperature is 30 DEG C, pressure 0.1 ~ 0.2MPa, and flow is 20.0g/h, and liquid hourly space velocity is 0.66h
-1, run 10.0h, meoh eluate acid number is 0.12mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: methyl alcohol is ejected about 45mL with nitrogen, then removed by methyl alcohol clean with nitrogen purging, after about 4h, in tail gas, methanol content is 380ppm as far as possible.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: distilled at 60-90 DEG C by meoh eluate, obtains methyl alcohol and the fatty acid methyl ester containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Embodiment 7
The present embodiment illustrates and the present invention can adopt tertiary amines weakly alkaline polymeric adsorbent D301R (Nankai University's resin, function base is-N (CH
3)
2) implement.
Filling ADSORPTION IN A FIXED BED separator column: 30g alkaline adsorption resin D301R in fixed-bed reactor, is connected to reactor on micro-negative test device.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 70 DEG C, pressure 0.20 ~ 0.30MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 14h, product acid number is 0.10mgKOH/g, obtains the biodiesel oil product that acid number is qualified.Run 22h, product acid number is 0.80mgKOH/g, stops charging.
Desorption: hyperacoustic operating frequency is 20kHz, ultrasonic power is 900W, and ul-trasonic irradiation time and intermittent time are respectively 1s/5s.Enter methyl alcohol, temperature is 50 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, when running 2.5h, meoh eluate acid number is 2.20mgKOH/g, proceeds desorption; When running 5.0h, methanol solution acid number is 0.08mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: first with nitrogen, liquid methanol is ejected about 45mL, then methyl alcohol is removed clean with nitrogen purging as far as possible, after about 4h, in tail gas, methanol content is 420ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: by meoh eluate 50-80 DEG C of underpressure distillation, obtains methyl alcohol and the fatty acid methyl ester containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Embodiment 8
The present embodiment illustrates and the present invention can adopt primary amine class weakly alkaline polymeric adsorbent D380 (Nankai University's resin, function base is-NH
2) implement.
Filling ADSORPTION IN A FIXED BED separator column: 30g alkaline adsorption resin D370 in fixed-bed reactor, is connected to reactor on micro-negative test device.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 70 DEG C, pressure 0.20 ~ 0.30MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 12h, product acid number is 0.08mgKOH/g, obtains the biodiesel oil product that acid number is qualified.Run 18h, product acid number is 0.75mgKOH/g, stops charging.
Desorption: hyperacoustic operating frequency is 20kHz, ultrasonic power is 500W, and ul-trasonic irradiation time and intermittent time are respectively 2s/10s.Enter methyl alcohol, temperature is 50 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, when running 2.0h, methanol solution acid number is 2.20mgKOH/g, proceeds desorption; When running 5.0h, methanol solution acid number is 0.10mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: first with nitrogen, liquid methanol is ejected about 45mL, then methyl alcohol is removed clean with nitrogen purging as far as possible, after about 4h, in tail gas, methanol content is 420ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: by methanol solution 50-80 DEG C of underpressure distillation, obtains methyl alcohol and the fatty acid methyl ester containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Embodiment 9
The present embodiment illustrates and the present invention can adopt secondary amine weakly alkaline polymeric adsorbent D382 (Nankai University's resin, function base is-NHCH
3) implement.
Filling ADSORPTION IN A FIXED BED separator column: 30g alkaline adsorption resin D370 in fixed-bed reactor, is connected to reactor on micro-negative test device.
Adsorption deacidification: the biofuel micro pump charging by acid number being 1.65mgKOH/g, enters ADSORPTION IN A FIXED BED separator column, and temperature is 70 DEG C, pressure 0.20 ~ 0.30MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, run 10h, product acid number is 0.16mgKOH/g, obtains the biodiesel oil product that acid number is qualified.Run 13h, product acid number is 0.83mgKOH/g, stops charging.
Desorption: hyperacoustic operating frequency is 20kHz, ultrasonic power is 300W, and ul-trasonic irradiation time and intermittent time are respectively 2s/6s.Enter methyl alcohol, temperature is 50 DEG C, pressure 0.2 ~ 0.3MPa, and flow is 40.0g/h, and liquid hourly space velocity is 1.33h
-1, when running 1.5h, methanol solution acid number is 1.80mgKOH/g, proceeds desorption; When running 3.0h, methanol solution acid number is 0.10mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: first with nitrogen, liquid methanol is ejected about 45mL, then methyl alcohol is removed clean with nitrogen purging as far as possible, after about 4h, in tail gas, methanol content is 220ppm.Fractionation by adsorption post can carry out adsorption deacidification next time.
Methyl alcohol is separated with free fatty acids: by methanol solution 50-80 DEG C of underpressure distillation, obtains methyl alcohol and the fatty acid methyl ester containing free fatty acids.Methyl alcohol can be used for desorption next time, and free-fat acid solution returns biofuel preparation section, as the raw material of preparation biofuel.
Claims (18)
1. a method for biofuel adsorption deacidification, comprising: (1) loads fixed bed with polymeric adsorbent, is fixed a fractionation by adsorption post; (2) underproof for acid number biofuel is carried out adsorption deacidification by fractionation by adsorption post, obtain the biofuel that acid number is qualified; (3) under ultrasonic assistant effect, with the fractionation by adsorption post that alcohols desorbing agent wash-out is saturated; (4) under ultrasonic assistant effect, remove totally by the alcohols desorbing agent in fixed bed, fractionation by adsorption post can be used again.
2. in accordance with the method for claim 1, wherein, the polymeric adsorbent of the polymeric adsorbent of step (1) basic group that has been load, described basic group be selected from hydroxyl, primary amine, secondary amine, tertiary amine and quaternary ammonium group one or more.
3. in accordance with the method for claim 1, wherein, the acid number of the defective biofuel of acid number of step (2) is 0.5 ~ 5.0mgKOH/g.
4. in accordance with the method for claim 1, wherein, the adsorption deacidification temperature of step (2) is room temperature ~ 100 DEG C, and liquid hourly space velocity is 0.2 ~ 10h
-1, working pressure is 0.1 ~ 5.0MPa.
5. in accordance with the method for claim 1, wherein, the adsorption deacidification temperature of step (2) is room temperature ~ 60 DEG C, and liquid hourly space velocity is 0.6 ~ 5.0h
-1, working pressure is 0.1 ~ 0.30MPa.
6. the biofuel that in accordance with the method for claim 1, wherein, the acid number of step (2) is qualified refers to that acid number is less than the biofuel of 0.80mgKOH/g.
7. in accordance with the method for claim 1, wherein, step (3) or (4) described ultrasonic assistant effect, take two kinds of modes: ultrasonic probe is placed in the pipe core of fractionation by adsorption device by (1); Or ultrasonic generator is placed in outside the pipe of fractionation by adsorption device by (2).
8. according to the method described in claim 1 or 7, wherein, described hyperacoustic operating frequency is 15 ~ 500kHz, and described hyperacoustic power is 100-900W, and described ultrasonication time and intermittent time are respectively (1-10) s/ (1-10) s.
9. according to the method described in claim 1 or 7, wherein, described hyperacoustic operating frequency is 18 ~ 100kHz, and described hyperacoustic power is 100-600W, and described ultrasonication time and intermittent time are respectively (2-6) s/ (2-6) s.
10. in accordance with the method for claim 1, wherein, the alcohols desorbing agent of step (3) is at least one in C1-C8 fatty alcohol.
11. according to the method described in claim 1 or 10, wherein, the alcohols desorbing agent of step (3) is selected from methyl alcohol, ethanol, propyl alcohol, the butanols of positive structure or isomery, amylalcohol, hexanol, enanthol, octanol.
12. in accordance with the method for claim 1, and wherein, the eluting temperature of described step (3) is room temperature ~ 100 DEG C, and liquid hourly space velocity is 0.2 ~ 10h
-1, working pressure is 0.1 ~ 1.0MPa.
13. in accordance with the method for claim 1, and wherein, the eluting temperature of described step (3) is room temperature ~ 60 DEG C, and liquid hourly space velocity is 0.6 ~ 5.0h
-1, working pressure is 0.1 ~ 0.30MPa.
14. in accordance with the method for claim 1, wherein, step (4) is carried out as follows: first with inactive gas, the alcoholic solution of liquid state is ejected fractionation by adsorption post, then continuation inactive gas purges to alcohol content in tail gas lower than 500ppm, or adopt the mode of vacuum extraction, alcohols desorbing agent in fixed bed is removed totally, completes dealcoholysis.
15. in accordance with the method for claim 14, and wherein, described inactive gas is selected from nitrogen, air, helium, neon or argon gas, and purging temperature is room temperature ~ 130 DEG C.
16. in accordance with the method for claim 14, and wherein, the vacuum tightness of described vacuum extraction is 0.02 ~ 0.10MPa, and the time of vacuum extraction is 0.2 ~ 10h.
17. in accordance with the method for claim 1, wherein, before step (3) desorption, also adopts the mode of inactive gas purging and/or vacuum extraction to be discharged by the oil plant in fractionation by adsorption post between sorbent material as far as possible.
18. in accordance with the method for claim 1, and wherein, during step (3) employing ultrasonic assistant desorption process, step (4) can adopt ultrasonic assistant dealcoholysis or not adopt ultrasonic assistant dealcoholysis; During step (4) employing ultrasonic assistant dealcoholysis process, step (3) can adopt ultrasonic assistant desorption or not adopt ultrasonic assistant desorption.
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