CN104119948A - Method for removing impurities from biodiesel - Google Patents
Method for removing impurities from biodiesel Download PDFInfo
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- CN104119948A CN104119948A CN201310144074.8A CN201310144074A CN104119948A CN 104119948 A CN104119948 A CN 104119948A CN 201310144074 A CN201310144074 A CN 201310144074A CN 104119948 A CN104119948 A CN 104119948A
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- biofuel
- molecular sieve
- wood chip
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Abstract
The invention discloses a method for removing impurities from biodiesel. The method is characterized in that biodiesel contacts with an adsorbent composition, the adsorbent composition contains wood chips and a molecular sieve, and a weight ratio of the wood chips to the molecular sieve is 1:0.04-6. The method can realize the removal of glycerin impurities in the biodiesel by using the adsorbent composition containing the wood chips.
Description
Technical field
The present invention relates to a kind of method of biofuel imurity-removal.
Background technology
Biofuel can be by grease and C
1-C
6monohydroxy-alcohol carry out transesterification reaction and make.But only through transesterification reaction, can't produce the biofuel that can use.Because, in the product mixtures obtaining in transesterification reaction, except main fatty acid monoester (being biofuel), also contain various impurity, as mono-glycerides, two sweet esters, glycerine, and unreacted alcohol and grease (being triglyceride level).These impurity can make biofuel product can not meet the national standard of biofuel (BD100) > > (GB/T20828-2007) for the blending of < < diesel-fuel, affect the normal use of biofuel.Therefore, the biofuel obtaining through transesterification reaction need to be carried out to the refinement treatment of imurity-removal, to produce the biofuel that meets national standard.
In prior art, make the method washing with water remove impurity.Although the method is easy, produce that water loss is large, the problem of diesel emulsion and wastewater treatment.
CN1863892A discloses a kind of method of refining biodiesel, and the method comprises: described biodiesel fuel is contacted with at least one sorbent material.Wherein disclose operable sorbent material and comprised Magnesium Silicate q-agent, magnesium aluminum silicate, Calucium Silicate powder, water glass, gac, silica gel, trimagnesium phosphate, metal hydroxides, metal oxide, metal carbonate, alkali metal bicarbonate salt, concentrated crystal soda, metal silicate, bleaching clay, Fuller's earth, POLARGEL NF and aluminum oxide.The impurity that can remove has soap, unreacted catalyzer, sulphur, phosphorus, calcium, iron, monoglyceride, triglyceride, acidic cpd, triglyceride level, chlorophyll, water, sediment and residual methanol.This invention can remove the glycerine in biofuel, but the method is discontinuous operating method, yet needs separation and processes the defect of spent sorbents filter cake.
CN101939068A discloses the method for purification of fatty acid alkane ester (FAAE), comprising: with the one or more adsorption columns that contain sorbing material, process lipid acid alkane ester (FAAE) and remove one or more impurity from lipid acid alkane ester (FAAE).The impurity of removing can have soap, metal, free glycerine, steroline and free lipid acid (FFA), and the sorbing material of use can be selected from the bleaching clay of carbon, silicon-dioxide, zeolite, metal silicate, bleaching clay and activation.Wherein sorbing material is mainly used in reducing soap content, makes spent ion exchange resin can reduce glycerol content.But it is easily saturated by the metal in biofuel and must discarded defect that spent ion exchange resin is existed.
Therefore need a kind of method of new biofuel imurity-removal, overcome the defect of prior art.
Summary of the invention
The object of the invention is to overcome the defect that prior art exists, a kind of method of new biofuel imurity-removal is provided.
The present inventor finds under study for action, uses wood chip and molecular sieve to coordinate as sorbent material, can effectively remove the glycerine impurity in biofuel.
To achieve these goals, the invention provides a kind of method that biofuel imurity-removal is provided, the method comprises biofuel contacted with adsorbent composition, wherein, described adsorbent composition contains wood chip and molecular sieve, and the weight ratio of described wood chip and described molecular sieve is 1:0.04-6.
By method provided by the invention, use the adsorbent composition that contains wood chip can effectively realize the glycerine impurity removing in biofuel.For example, in embodiment 1, the refining biofuel obtaining is water white transparency, and wherein the content of glycerine is < 0.01 quality %, meets national standard.And in comparative example 1, do not use wood chip, in the refining biofuel obtaining, the content of glycerine is 0.04 quality %, does not meet national standard.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of method of biofuel imurity-removal, the method comprises biofuel contacted with adsorbent composition, and wherein, described adsorbent composition contains wood chip and molecular sieve, and the weight ratio of described wood chip and described molecular sieve is 1:0.04-6; The weight ratio of preferred described wood chip and described molecular sieve is 1:0.1-4; More preferably the weight ratio of described wood chip and described molecular sieve is 1:0.5-4.When the adsorbent composition that the weight ratio of using wood chip and molecular sieve is 1:0.5-4 carries out biofuel imurity-removal, biofuel can contact with described adsorbent composition with larger volume space velocity, now, for the described adsorbent composition of unit volume, can there is the ability of larger processing biofuel.
According to the present invention, use the adsorbent composition that contains wood chip and molecular sieve can realize the effect that removes glycerine impurity in biofuel.And the wood chip containing in described adsorbent composition and molecular sieve mix by above-mentioned weight ratio, can obtain the effect of glycerine impurity in better adsorbing and removing biofuel.
In the present invention, wood chip can be sawdust, the wood shavings material producing in wood working process.In the present invention, to the wood chip using, there is no particular limitation, can be the wood chip that various wood working produce, as at least one in pine, China fir, elm and willow.
In the present invention, the wood chip of use is Powdered, and under preferable case, described wood chip is of a size of 18-60 order.
In the present invention, the density of the described wood chip of use can be 0.1-0.6g/cm
3, be preferably 0.1-0.3g/cm
3.In the present invention, the density of described wood chip refers to tap density, can be simply by weighing after the weight that the wood chip of certain volume has, utilize density formula to calculate.Wherein weigh certain volume wood chip can for adopt the standard graduated cylinder of 100ml to weigh and weighing process in through claim the 100ml wood chip of dress for three times after graduated cylinder sidewall knocks jolt ramming.
In the present invention, the described wood chip of use can be for having reduced the wood chip of water content after drying treatment.Under preferable case, the wood chip gross weight of take after drying treatment is benchmark, and the water ratio of described wood chip can be 1-10 % by weight; More preferably water ratio is 3-7 % by weight.Described drying treatment can be drying method and the condition of conventional wood chip dry processing use.
According to the present invention, the molecular sieve containing in described adsorbent composition has adsorption function, and under preferable case, described molecular sieve is Si-Al molecular sieve; Preferred described molecular sieve is at least one in X-type molecular sieve, Y zeolite, beta molecular sieve and mordenite molecular sieve; Further preferred described molecular sieve is X-type molecular sieve.
According to the present invention, with described adsorbent composition, remove the glycerine impurity in described biofuel, can take adsorbent composition to put into biofuel, by being uniformly mixed the effect that removes that realizes, but in operation, need the separated of further adsorbent composition and biofuel, make operation more complicated.Can also use separator column, by adsorbent composition be seated in separator column, form adsorbent bed.The filling of adsorbent composition can be taked layering filling, also can take wood chip to mix rear filling with molecular sieve.Take to mix the more convenient operation of rear filling, preferably take wood chip to mix rear filling with molecular sieve.Under preferable case, described contact is that described biofuel is adsorbent bed by what consist of described adsorbent composition continuously.In the present invention, make biofuel through adsorbent composition, fill form adsorbent bed continuously, can carry out the continuous operation of biofuel adsorbing and removing impurity.
In the present invention, when the separator column that described adsorbent composition has been loaded in use carries out described operating of contacts, can take from biofuel described in adsorbent bed its top feed, in adsorbent bed bottom, collect the way of contact of the refining biodiesel that has removed glycerine impurity; Also can take from biofuel described in adsorbent bed bottom feed, at adsorbent bed top, collect the way of contact of the refining biodiesel that has removed glycerine impurity.For fear of taking from its top feed, while collecting the way of contact of refining biodiesel from bottom, the impact that the factors such as wall stream and adsorbent bed compaction rate contact with adsorbent composition in separator column the biofuel of charging, under preferable case, described contact be described biofuel from described adsorbent bed endfeed, from the way of contact of described adsorbent bed upper end discharging.What in described adsorbent bed upper end, collect is the refining biodiesel that has removed glycerine impurity.Employing is from bottom feed, the way of contact of collecting refining biodiesel from top, biofuel with adsorbent bedly can have more homogeneous, better contact effect, be conducive to carry out better adsorption operations, reach better adsorption effect.
To the biofuel of pending impurity removal, there is no particular limitation in the present invention, can be the biofuel obtaining by transesterification reaction.Under preferable case, described biofuel is for by Vegetable oil lipoprotein, animal grease, not polished fat, waste grease and obtain by transesterification reaction from least one and low-carbon alcohol in the grease of micro-algae.Vegetable oil lipoprotein can be for as soybean oil, rapeseed oil, peanut oil, wunflower seed oil, plam oil, Oleum Cocois and the material that contains fatty group (comprising the tall oil producing in paper-making process) that comes from fruit, stem, leaf, limb and the root of other various farm crop and wild plant.Animal grease can be for as lard, butter, sheep oil, fish oil etc.Polished fat can not be unpurified crude oil.Waste grease can be frying oil, rotten waste oil etc.
In the present invention, biofuel is reacted with low-carbon alcohol by grease to produce and is obtained, under preferable case, and the monohydroxy-alcohol that described low-carbon alcohol is C1-C6; Further preferred described low-carbon alcohol is methyl alcohol.
According to the present invention, through react the biofuel obtaining with low-carbon alcohol, contain the multiple impurity that does not meet national standard (GB/T20828-2007).In the present invention, the total mass of described biofuel of take is benchmark, and in described biofuel, the content of glycerine is 0.02-1 quality %.
The acid number of the biofuel in the present invention can there is no particular limitation, and preferred described acid number is 0.8-12mgKOH/g.
Method provided by the invention can remove the glycerine impurity in biofuel, obtains meeting the refining biodiesel of national standard.Method provided by the invention also can be not limited to remove glycerine in biofuel, pigment, residual grease, methyl alcohol, catalyzer, metal impurities.
According to the present invention, there is no particular limitation for the operable operational condition of described contact, is suitable for described wood chip and completes the glycerine impurity removing in biofuel.Under preferable case, the temperature of described contact is 5-100 ℃, and the pressure of described contact is 0.1-3MPa, and the volume space velocity of described biofuel charging is 0.1-10h
-1; The temperature of preferred described contact is 25-90 ℃, and the pressure of described contact is 0.1-0.7MPa, and the volume space velocity of described biofuel charging is 0.3-6h
-1; Further the temperature of preferred described contact is 30-60 ℃, and the pressure of described contact is 0.1-0.3MPa, and the volume space velocity of described biofuel charging is 0.4-4h
-1.The temperature of described contact refers to adsorbent bed temperature.Described pressure refers to the pressure in separator column, and pressure is absolute pressure.Described volume space velocity refer to the unit time on unit volume sorbent material (hour) in the volume of the biofuel passed through.
Below will describe the present invention by embodiment.In following examples, in biofuel, glycerol content records by ASTM D6584 method; X-type molecular sieve is commercially available to be obtained.
The blending of national standard < < diesel-fuel is not more than 0.020 quality % with the content that limits free glycerol in biofuel (BD100) > > (GB/T20828-2007).
Embodiment 1
Wood chip is packed in separator column after 1:1 mixes with X-type molecular sieve, and wood chip is poplar bits, and density is 0.2g/cm
3, water ratio is 4.9 % by weight, is of a size of 26-60 order.The temperature of contact is 30 ℃, and absolute pressure is 0.11MPa.By the content of glycerine, be the yellow-green colour biofuel crude product (reacted and make with methyl alcohol by waste grease, the acid number of product is 5mgKOH/g) of 0.5 quality %, with volume space velocity 3h
-1from separator column bottom, inject, upwards flow.The biofuel of collecting from the outlet on separator column top is the content < 0.01 quality % of water white transparency, glycerine, reaches BD100 standard.
Embodiment 2
Wood chip is packed in separator column after 1:4 mixes with X-type molecular sieve, and wood chip is pine tree wood chip, and density is 0.3g/cm
3, water ratio is 5.2 % by weight, is of a size of 26-60 order.The temperature of contact is 40 ℃, and absolute pressure is 0.11MPa.By the content of glycerine, be the yellow-green colour biofuel crude product (the same) of 0.5 quality %, with volume space velocity 3.5h
-1from separator column bottom, inject, upwards flow.The biofuel of collecting from the outlet on separator column top is the content < 0.01 quality % of water white transparency, glycerine, reaches BD100 standard.
Embodiment 3
Wood chip is packed in separator column after 1:0.5 mixes with X-type molecular sieve, and wood chip is poplar bits, and density is 0.2g/cm
3, water ratio is 4.9 % by weight, is of a size of 26-60 order.The temperature of contact is 40 ℃, and absolute pressure is 0.11MPa.By the content of glycerine, be the yellow-green colour biofuel crude product (the same) of 0.5 quality %, with volume space velocity 2.6h
-1from separator column bottom, inject, upwards flow.The biofuel of collecting from the outlet on separator column top is the content < 0.01 quality % of water white transparency, glycerine, reaches BD100 standard.
Embodiment 4
Wood chip is packed in separator column after 1:5 mixes with X-type molecular sieve, and wood chip is elm bits, and density is 0.37g/cm
3, water ratio is 7 % by weight, is of a size of 26-60 order.The temperature of contact is 35 ℃, and absolute pressure is 0.11MPa.By the content of glycerine, be the yellow-green colour biofuel crude product (the same) of 0.5 quality %, with volume space velocity 1.2h
-1from separator column bottom, inject, upwards flow.The biofuel of collecting from the outlet on separator column top is the content < 0.01 quality % of water white transparency, glycerine, reaches BD100 standard.
Embodiment 5
Wood chip is packed in separator column after 1:0.1 mixes with X-type molecular sieve, and wood chip is Chinese fir wood chip, and density is 0.13g/cm
3, water ratio is 4 % by weight, is of a size of 26-60 order.The temperature of contact is 20 ℃, and absolute pressure is 0.11MPa.By the content of glycerine, be the yellow-green colour biofuel crude product (the same) of 0.5 quality %, with volume space velocity 2.3h
-1from separator column bottom, inject, upwards flow.The biofuel of collecting from the outlet on separator column top is the content < 0.01 quality % of water white transparency, glycerine, reaches BD100 standard.
Comparative example 1
According to the method for embodiment 4, different, in separator column, only pack X-type molecular sieve into, Intake Quantity is identical with the total amount of the wood chip using in embodiment 4 and X-type molecular sieve.
The content that the biofuel of collecting from the outlet on separator column top is glycerine is 0.04 quality %, does not reach BD100 standard.
By above-mentioned experimental result, can be found out, use the adsorbent composition contain wood chip to carry out biofuel while removing glycerine impurity, can realize the glycerine removing in biofuel, the content that obtains glycerine meets the biofuel of national standard.As in embodiment 1-5, in the refining biofuel obtaining, the content of glycerine is < 0.01 quality % particularly.And in comparative example 1, do not use wood chip, in the refining biofuel obtaining, the content of glycerine is 0.04 quality %.
Meanwhile, while adopting the adsorbent composition that contains wood chip, can also remove the pigment in biofuel, obtain water white biofuel liquid.
Claims (11)
1. a method for biofuel imurity-removal, the method comprises biofuel is contacted with adsorbent composition, it is characterized in that, and described adsorbent composition contains wood chip and molecular sieve, and the weight ratio of described wood chip and described molecular sieve is 1:0.04-6.
2. method according to claim 1, wherein, the weight ratio of described wood chip and described molecular sieve is 1:0.1-4.
3. method according to claim 2, wherein, the weight ratio of described wood chip and described molecular sieve is 1:0.5-4.
4. method according to claim 1, wherein, described molecular sieve is Si-Al molecular sieve.
5. method according to claim 1, wherein, described contact is that described biofuel is adsorbent bed by what consist of described adsorbent composition continuously.
6. method according to claim 5, wherein, described contact be described biofuel from described adsorbent bed endfeed, from the way of contact of described adsorbent bed upper end discharging.
7. according to the method described in any one in claim 1-6, wherein, the total mass of described biofuel of take is benchmark, and in described biofuel, the content of glycerine is 0.02-1 quality %.
8. according to the method described in any one in claim 1-6, wherein, described biofuel is for by Vegetable oil lipoprotein, animal grease, not polished fat, waste grease and react and obtain with low-carbon alcohol from least one in the grease of micro-algae.
9. method according to claim 8, wherein, the monohydroxy-alcohol that described low-carbon alcohol is C1-C6.
10. method according to claim 1, wherein, the temperature of described contact is 5-100 ℃, and the pressure of described contact is 0.1-3MPa, and the volume space velocity of described biofuel charging is 0.1-10h
-1, described pressure is absolute pressure.
11. methods according to claim 10, wherein, the temperature of described contact is 25-90 ℃, and the pressure of described contact is 0.1-0.7MPa, and the volume space velocity of described biofuel charging is 0.3-6h
-1, described pressure is absolute pressure.
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| CN107513471A (en) * | 2016-06-15 | 2017-12-26 | 中国石油化工股份有限公司 | A kind of method that dissociative glycerin is removed from biodiesel coarse product |
| CN108816192A (en) * | 2018-05-08 | 2018-11-16 | 南京大学昆山创新研究院 | A kind of preparation method of novel thick diesel decoloring agent |
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