CN105482894A - Adsorption deacidification method for biodiesel - Google Patents
Adsorption deacidification method for biodiesel Download PDFInfo
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Abstract
The present invention relates to an adsorption deacidification method for biodiesel. The method comprises the following steps: (1) adsorption resins are used to fill a fixed bed to obtain a fixed bed adsorption-separation column; (2) biodiesel with unqualified acid value is subjected to adsorption deacidification through the adsorption-separation column to obtain biodiesel with qualified acid value; (3) alcohol desorption agents are used for eluting the saturated adsorption-separation column; and (4) the alcohol desorption agents in the fixed bed are completely eluted, and then the adsorption-separation column can be reused. At least one of step (3) and step (4) is carried out under microwave irradiation. Biodiesel products with the acid value less than 0.50 mgKOH/g can be obtained by the method, which can meet requirements of the existing BD100 and a new generation of national standard; the microwave-assisted desorption or/and dealcoholization can greatly enhance the efficiency of the desorption process or/and the dealcoholization process; and the method is simple in operation, free of pollutant emission, and green and environmentally friendly.
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 Microwave assisted 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) with the fractionation by adsorption post that alcohols desorbing agent wash-out is saturated; (4) remove totally by the alcohols desorbing agent in fixed bed, fractionation by adsorption post can be used again, and wherein, at least one step in step (3) and (4) is carried out under microwave exposure.
Specifically, method provided by the invention is: (1) loaded resin: first load 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 microwave exposure, 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 microwave exposure, 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.
Microwave exposure of the present invention fractionation by adsorption post is placed in microwave field to carry out Microwave assisted desorption or/and auxiliary dealcoholysis.
According to the inventive method, single microwave irradiation time is 2 ~ 30s, is preferably 2 ~ 10s, and twice microwave exposure interval time is 5 ~ 300s, is preferably 15 ~ 60s.Interval time between twice microwave exposure is to dispel the heat in time and protecting microwave oven.Microwave exposure total time is 5 ~ 600min, is preferably 10 ~ 120min.Microwave exposure total time (being called working time in embodiment) be microwave irradiation time and interval time sum.
According to the inventive method, microwave output power needs to regulate according to desorption treatment capacity, and testing laboratory can adopt 300 ~ 900W, and commerical test suitably can increase microwave output power.
During the inventive method step (3) employing Microwave assisted desorption process, step (4) can adopt microwave-assisted dealcoholysis or not adopt microwave-assisted dealcoholysis; During the inventive method step (4) employing microwave-assisted dealcoholysis process, step (3) can adopt Microwave assisted desorption or not adopt Microwave assisted desorption.
According to the inventive method, if step (3) and/or (4) adopt microwave exposure, a surge tank must be connected after fractionation by adsorption post, the moment superpressure and the liquid of ejection produced during in order to cushion microwave exposure.
The service temperature of step of the present invention (3) and (4) is room temperature-130 DEG C, and preferable temperature is room temperature.
The alcohols desorbing agent of step of the present invention (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 liquid hourly space velocity of step of the present invention (3) and (4) is 0.2 ~ 10h
-1, be preferably 0.6 ~ 5.0h
-1.
The working pressure of step of the present invention (3) and (4) 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 of the present invention, 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 under microwave-assisted, 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.
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) Microwave assisted 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 microwave-assisted 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: connect a surge tank after fractionation by adsorption post, the moment superpressure and the liquid of ejection produced during in order to cushion microwave exposure.With nitrogen, the oil plant in fractionation by adsorption post is ejected before desorption as far as possible, guarantee only there is a small amount of liquid material in fractionation by adsorption post.Fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 30s.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 4.5h, meoh eluate acid number is 0.09mgKOH/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 microwave-assisted, 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 use the desorption process of microwave-assisted biofuel adsorption deacidification.
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: as far as possible ejected by the oil plant in fractionation by adsorption post with nitrogen before desorption, guarantees only there is a small amount of liquid material in fractionation by adsorption post.Fractionation by adsorption post is placed in microwave field and carries out desorption, single ripple irradiation time is 10s, and twice microwave exposure interval time is 60s.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 8.0h, meoh eluate acid number is 0.07mgKOH/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 microwave-assisted, 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 microwave-assisted 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: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 2s, and twice microwave exposure interval time is 15s.First with nitrogen, liquid ethanol is ejected about 45mL, then under microwave-assisted effect, removed by ethanol clean with nitrogen purging, after running about 3.5h, in tail gas, ethanol content is 286ppm as far as possible.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 microwave-assisted, 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 running 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 microwave 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: fractionation by adsorption device is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s.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 6.5h, meoh eluate acid number is 0.06mgKOH/g, completes the desorption of free fatty acids.
Dealcoholysis: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s.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 3.5h with vacuum pump, in tail gas, methanol content is 156ppm.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 microwave-assisted, 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 microwave-assisted, 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 microwave power 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: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s, and microwave power is 900W.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 95ppm.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 under lower microwave power.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: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s, and microwave power is 300W.Enter methyl alcohol, temperature is 30 DEG C, and pressure is 0.1 ~ 0.2MPa, and flow is 20.0g/h, and liquid hourly space velocity is 0.66h
-1, run 8.0h, meoh eluate acid number is 0.10mgKOH/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: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s, and microwave power is 400W.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 1.20mgKOH/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: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s, and microwave power is 500W.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, methanol solution acid number is 1.50mgKOH/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: 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: fractionation by adsorption post is placed in microwave field and carries out desorption, single microwave irradiation time is 3s, and twice microwave exposure interval time is 20s, and microwave power is 400W.First with nitrogen, liquid methanol is ejected about 45mL, then removed by methyl alcohol clean with nitrogen purging as far as possible, after about 3.5h, in tail gas, methanol content is 180ppm.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) with the fractionation by adsorption post that alcohols desorbing agent wash-out is saturated; (4) remove totally by the alcohols desorbing agent in fixed bed, fractionation by adsorption post can be used again, and wherein, at least one step in step (3) and (4) is carried out under microwave exposure.
2. in accordance with the method for claim 1, wherein, the polymeric adsorbent of the basic group that has been load of the polymeric adsorbent described in step (1), described basic group be selected from hydroxyl, primary amine, secondary amine, tertiary amine and quaternary ammonium group one or more.
3. the acid number of the defective biofuel of acid number in accordance with the method for claim 1, wherein, described in 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 the acid number in accordance with the method for claim 1, wherein, described in 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, described microwave exposure fractionation by adsorption post is placed in microwave field to carry out Microwave assisted desorption or/and auxiliary dealcoholysis.
8. in accordance with the method for claim 1, wherein, single microwave irradiation time is 2 ~ 30s, and twice microwave exposure interval time is 5 ~ 300s, and microwave exposure total time is 5 ~ 600min.
9. in accordance with the method for claim 1, wherein, single microwave irradiation time is 2 ~ 10s, and twice microwave exposure interval time is 15 ~ 60s, and microwave exposure total time is 10 ~ 120min.
10. in accordance with the method for claim 1, wherein, microwave output power is 300-900W.
11. in accordance with the method for claim 1, and wherein, the service temperature of step (3) and (4) is room temperature ~ 130 DEG C.
12. in accordance with the method for claim 1, and wherein, the alcohols desorbing agent described in step (3) is at least one in C1-C8 fatty alcohol.
13. in accordance with the method for claim 1, and wherein, the alcohols desorbing agent described in step (3) is selected from methyl alcohol and/or ethanol.
14. in accordance with the method for claim 1, and wherein, the liquid hourly space velocity of step (3) and (4) is 0.2 ~ 10h
-1, working pressure is 0.1 ~ 1.0MPa.
15. in accordance with the method for claim 1, and wherein, the liquid hourly space velocity of step (3) and (4) is for being 0.6 ~ 5.0h
-1, working pressure is 0.1 ~ 0.30MPa.
16. in accordance with the method for claim 1, wherein, in step (3), when the acid number of the alcohols elutriant flowed out from adsorption column is less than 0.15mgKOH/g, stops wash-out.
17. 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 under microwave exposure, continuation inactive gas purges to alcohol content in tail gas lower than 500ppm, or adopt the mode of vacuum extraction, the alcohols desorbing agent in fixed bed is removed totally, completes dealcoholysis.
18. in accordance with the method for claim 17, wherein, described inactive gas is selected from nitrogen, air, helium, neon or argon gas, and purging temperature is room temperature ~ 130 DEG C, the vacuum tightness of vacuum extraction is 0.02 ~ 0.10MPa, and the time of vacuum extraction is 0.2 ~ 10h.
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