CN101481297A - Method for refining biodiesel by-product glycerol - Google Patents
Method for refining biodiesel by-product glycerol Download PDFInfo
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- CN101481297A CN101481297A CNA2008101637416A CN200810163741A CN101481297A CN 101481297 A CN101481297 A CN 101481297A CN A2008101637416 A CNA2008101637416 A CN A2008101637416A CN 200810163741 A CN200810163741 A CN 200810163741A CN 101481297 A CN101481297 A CN 101481297A
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- glycerine
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- exchange resin
- organic solvent
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 239000006227 byproduct Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 239000003225 biodiesel Substances 0.000 title claims abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 18
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 235000011187 glycerol Nutrition 0.000 claims description 110
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002551 biofuel Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000002283 diesel fuel Substances 0.000 claims description 7
- 239000004519 grease Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 21
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000003480 eluent Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000009967 tasteless effect Effects 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000008162 cooking oil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000012609 strong anion exchange resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention provides a refining method of a biodiesel byproduct glycerol. The method comprises the following steps: taking the byproduct glycerol phase obtained in biodiesel preparation by virtue of oil transesterification as a raw material, firstly adding an organic solvent the mass of which is 0.01-20 times of that of the glycerol phase to dissolve the glycerol phase, adjusting pH of the dissolved liquid to 1-7 with acid, filtering off solid matters from the dissolved liquid after precipitates are separated out, taking the obtained filtrate to remove the organic solvent, keeping standing and layering, taking the lower-layer crude glycerol to dissolve with water the volume of which is 0.01-2.0 times of that of the crude glycerole, refining the crude glycerol with base ion-exchange resin and acid ion exchange resin sequentially, eluting with water, decompressing, distilling and dehydrating the obtained eluent to obtain the refined glycerol. The refining method has the advantages of simple process, available operation basically under normal temperature and normal pressure, low equipment requirement and low cost, high purity of the prepared glycerol up to 99.5%, high total yield up to 85%, so the method is favorable for industrial production.
Description
(1) technical field
The present invention relates to a kind of process for purification of biological diesel oil byproduct glycerin.
(2) background technology
At present, along with the aggravation of fossil energy imbalance between supply and demand and the enhancing of environmental requirement, biofuel just is being subjected to the attention of more and more national as a kind of renewable, environment-friendly fuel.Yet along with deepening continuously and industrialized realization of biodiesel manufacture technical study, the utilization of its by-product glycerin is badly in need of solving.Two-phase up and down takes place to produce in the process of transesterification reaction production biofuel in triglyceride level in the animal and plant grease and methanol solution under potassium hydroxide catalysed, on mainly be biofuel mutually, be a kind of high viscosity, brown mutually down, have grease to distinguish the flavor of, contain the thick liquid that enriches glycerine, its composition is very complicated.The Wu Miaoxin of Jiangsu Polytechnic University analyzes the biofuel lower floor by product of oneself preparation, and glycerol content is about 45%, and methanol content is about 28%, and fatty acid soaps content also contains a small amount of grease, free alkali etc. in addition about 22%.Because used oil lipid species difference, biofuel lower floor by product shade differs, and various component concentrations also have difference.The difficulty of recovery, refining glycerine is bigger from biofuel lower floor by product.On the other hand, glycerine is a kind of important basic organic, and purposes is very extensive in industry, medicine and daily life, at present nearly 1700 multiple uses.China's glycerine is in the situation that supply falls short of demand always, and especially the glycerine (glycerol content is more than 99.5%) of high purities such as food grade, medical grade, cosmetics-stage almost all relies on import.Recovery, refining glycerine will be alleviated China's glycerine situation that supply falls short of demand from the by product of production biofuel, improve the production of biodiesel economic benefit of enterprises simultaneously, reduce environmental pollution.
Traditional glycerin purification method mainly contains two kinds of underpressure distillation and ion-exchanges.
Under normal pressure, the boiling point of glycerine is up to 290 ℃, distills under high vacuum, relatively lower temp in industrial common employing to obtain pure glycerin.This method main drawback is the vacuum tightness height, and energy consumption is big, and simultaneous temperature is still too high, and the easy polymerization of still liquid glycerine produces side reaction, influences purity, color and luster and the yield of glycerine; And in vacuum distillation process along with the continuous gasification of glycerine, remaining organic impurity constantly concentrates, coking, finally cause glycerine to be wrapped in interior can't the gasification, tightly bond with distillation wall and heating coil after the remaining organic impurity coking, not only reduced distillation yield, and the residue after the coking is removed comparatively difficulty.Because biofuel in the biofuel lower floor by product, fatty acid soaps are to the parcel of glycerine, test shows the vacuum tightness of biofuel lower floor by product at 150Pa, directly underpressure distillation under 200 ℃ of still temperature, glycerine can not be vaporized, must carry out pre-treatment to biofuel lower floor by product and obtain raw glycerine, underpressure distillation just can obtain refining glycerine again.
Ion exchange method has important application in glycerine production, major part is edible, medical glycerine all is to obtain by ion exchange resin is refining at last.About 1978, the relevant producer in Sichuan, institute's test are passed through three groups of multiple-hearths and a mixed bed (732# strongly acidic cation-exchange and 717# strong basic type anion-exchange resin) at normal temperatures with 80% raw glycerine, through concentrating, made the chemical pure glycerine more than 98% again.Recently, Li Yun and Jian Li etc. also study ion-exchange purification glycerine; Simple beautiful grade is also studied ion exclusion method separation saponification glycerine simultaneously.Contain impurity such as higher fatty acid soaps, free alkali, pigment in the biological diesel oil byproduct, directly cross ion exchange resin, exchange capacity is big, resin will reach capacity and inactivation very soon, the resin frequent regeneration can produce a large amount of acidic and alkaline waste waters, obtains making with extra care after ion exchange resin behind the raw glycerine so must carry out pre-treatment to biofuel lower floor by product.
(3) summary of the invention
The object of the invention provides a kind of process for purification of biological diesel oil byproduct glycerin, and this method is simple to operate, utilizes the inventive method that biological diesel oil byproduct is made with extra care, and glycerine purity reaches more than 99.5%, and the glycerine total recovery can reach more than 85%.
A kind of process for purification of biological diesel oil byproduct glycerin, described method comprises: the by-product glycerin that obtains with the grease preparing biodiesel by ester exchange is raw material mutually, adding quality earlier is the organic solvent dissolution of 0.01～20 times of glycerine phase quality, be 1～7 with acid for adjusting pH again, wait to precipitate and separate out, the solids removed by filtration material, get after filtrate evaporation removes organic solvent, standing demix, take off the water dissolution that layer raw glycerine volume is 0.01～20 times of raw glycerine volume, use deacidite successively, acidic ion exchange resin is refining, and the water wash-out, the elutriant dehydration by evaporation obtains glycerine.
The by-product glycerin phase raw material of indication of the present invention can come from the lower floor by-product glycerin phase of various greases through obtaining in the base-catalyzed transesterification production biofuel process.
The raw glycerine raw material that the embodiment of the invention is got is from the by product raw glycerine phase in the rapeseed oil system biofuel process, and the by-product glycerin phase in the waste cooking oil system biofuel process.The stock oil of preparing biodiesel by ester exchange comprises oil foot, soap stock, the acidifying wet goods in various animal-plant oil, industrial waste grease, waste cooking oil, the oil and fat refining process; The used basic catalyst of preparing biodiesel by ester exchange comprises various liquid bases, for example sodium hydroxide, potassium hydroxide, sodium methylate etc.
The mutually used organic solvent of dissolving by-product glycerin can dissolve the organic solvent of glycerine for this area routine, comprises alcohols, for example methyl alcohol, ethanol etc.; Ketone, for example acetone etc.; Ester class, for example ethyl acetate etc.; Alkane, for example heptane, hexane etc.
Regulate various inorganic/organic acid that the used acid of pH comprises that this area is commonly used, routine sulfuric acid, hydrochloric acid, acetic acid etc.
The present invention drips inorganic/organic acid at biofuel lower floor by-product glycerin in mutually, promptly can play demulsification, and the biofuel that is wrapped in the glycerine is separated with glycerine; Can generate lipid acid with fatty acid soaps reaction again, and remove mutually from glycerine.Add organic solvent at lower floor's by-product glycerin in mutually, make acid and the salt that fatty acid soaps/free alkali reaction generates, and other contamination precipitation separates out, thereby be separated with glycerine.The present invention makes glycerine purity from bringing up to below 45% about 90% by in acid/organic solvent and desalination, take off assortedly, again by the further desalination of the method for ion-exchange, decolouring, deodorization, thereby reaches the purpose of purification of glycerin.
The used ion exchange resin of the present invention has anionite-exchange resin and Zeo-karb.The main effect of ion-exchange is to remove glycerine residual salt, lipid acid, pigment, smell etc. in mutually.
The used anionite-exchange resin of the present invention can be strongly basic anion exchange resin, can be weak base anion-exchange resin also, is preferably the D201 resin.
The used Zeo-karb of the present invention can be a storng-acid cation exchange resin, can be weakly acidic cation-exchange resin also, is preferably the D001 resin.
Among the present invention, the anionite-exchange resin volumetric usage is 0.1～2.0 times of raw glycerine volume, elution speed 2.0～3.5mL/min.The Zeo-karb volumetric usage is 0.1～2.0 times of raw glycerine volume, elution speed 2.0～3.5mL/min.
Among the present invention, wash ion exchange resin with water usually when wash-out finishes, water lotion is incorporated elutriant into.
Beneficial effect of the present invention is mainly reflected in: technology is simple, operation substantially at normal temperatures and pressures, and low for equipment requirements, cost is lower, makes glycerine purity and reaches more than 99.5%, and total recovery can reach more than 85%, is beneficial to suitability for industrialized production.
(4) description of drawings
Fig. 1 is a process flow sheet of the present invention.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
It is as follows that rapeseed oil prepares the biofuel process:
500kg vegetable seed crude oil (acid number 3.0mgKOH/g oil) joins 1m
3Reactor in, after the dehydration of high temperature (about 90 ℃), vacuum (absolute pressure 90000Pa), add the solution that 108kg methyl alcohol and 5kg potassium hydroxide are made into, the ON cycle pump loops back the inflow reactor after making the reaction feed liquid through the Hydrodynamic cavitation device.Behind the reaction 30min, remove methyl alcohol, standing demix, the upper strata is biological diesel product, lower floor is the by-product glycerin phase.Take off the raw material of layer by-product glycerin as refining glycerine.
The preparing biodiesel by food and beverage waste oil process is as follows:
100g waste cooking oil (acid number 59mgKOH/g oil), mix with 21g methyl alcohol and 2g sulfuric acid, at 60 ℃ of following stirring reaction 2hour, standing demix, get oil phase and mix, at 60 ℃ of following stirring reaction 1hour, standing demix with 21g methyl alcohol and 0.72gKOH, the upper strata is biological diesel product, and lower floor is the by-product glycerin phase.Take off the raw material of layer by-product glycerin as refining glycerine.
Embodiment 1:
Take by weighing 500 the gram about vegetable seed crude oil system biofuel lower floor by-product glycerin in the beaker of 1000ml, after adding the dilution of 250g methyl alcohol, add the vitriol oil and regulate pH=7, the adularescent precipitation is separated out, filter, filtrate removes standing demix behind the methyl alcohol, and lower floor is the raw glycerine after the desalination, and this glycerine is faint yellow thick.The ratio of desalinization of this technology is 89.05%, and glycerine purity brings up to 89.23% from 45%.Get above-mentioned raw glycerine 100ml, add the 50ml deionized water and be diluted to aqueous glycerin solution; The chromatography column that to get two internal diameters be 18mm adds D201 strong basic ion exchange resin and D001 strong-acid ion exchange resin after 120ml handles respectively; Above-mentioned aqueous glycerin solution passes through D201 and D001 ion exchange column successively with the flow of 2.5ml/min, collects effluent liquid; After wash-out finished, water washed D201 and D001 ion exchange column successively with the flow of 2.5ml/min, collected and the merging effluent liquid.Obtain colourless, tasteless thick liquid behind the effluent liquid decompression dehydration, glycerine purity is 99.8%.This technology glycerine total recovery is 88.4%.
Embodiment 2:
Take by weighing 466.4g waste oil system biofuel lower floor glycerine phase by product in the 1000ml beaker, add 238.5g acetone, regulate pH=5 with hydrochloric acid, centrifugal the removing of solid that generates, filtrate removes static layering behind the acetone, lower floor is the raw glycerine after the desalination, and this glycerine is that light brown is thick, and glycerine purity is 80%.Get above-mentioned raw glycerine 100ml, add the 50ml deionized water and be diluted to aqueous glycerin solution; The chromatography column that to get two internal diameters be 18mm adds D201 strong basic ion exchange resin and D001 strong-acid ion exchange resin after 200ml handles respectively; Above-mentioned aqueous glycerin solution passes through D201 and D001 ion exchange column successively with the flow of 2.5ml/min, collects effluent liquid; After wash-out finished, water washed D201 and D001 ion exchange column successively with the flow of 2.5ml/min, collected and the merging effluent liquid.Obtain colourless, tasteless thick liquid behind the effluent liquid decompression dehydration, glycerine purity is 99.5%.This technology glycerine total recovery is 85.4%.
Embodiment 3:
Take by weighing 500 the gram about vegetable seed crude oil system biofuel lower floor by-product glycerin in the beaker of 1000ml, after adding the dilution of 5g methyl alcohol, add hydrochloric acid and regulate pH=1, the adularescent precipitation is separated out, filter, filtrate removes standing demix behind the methyl alcohol, and lower floor is the raw glycerine after the desalination, and this glycerine is faint yellow thick.The ratio of desalinization of this technology is 80%, and glycerine purity brings up to 79% from 45%.Get above-mentioned raw glycerine 50ml, add the 1000ml deionized water and be diluted to aqueous glycerin solution; The chromatography column that to get two internal diameters be 18mm adds D201 strong basic ion exchange resin and D001 strong-acid ion exchange resin after 250ml handles respectively; Above-mentioned aqueous glycerin solution passes through D201 and D001 ion exchange column successively with the flow of 2.5ml/min, collects effluent liquid; After wash-out finished, water washed D201 and D001 ion exchange column successively with the flow of 2.5ml/min, collected and the merging effluent liquid.Obtain colourless, tasteless thick liquid behind the effluent liquid decompression dehydration, glycerine purity is 99.5%.This technology glycerine total recovery is 86.7%.
Embodiment 4:
Take by weighing 100 the gram about vegetable seed crude oil system biofuel lower floor by-product glycerin in the beaker of 1000ml, after the agitation and dropping vitriol oil is regulated pH=1, add 2000 gram normal hexanes, the adularescent precipitation is separated out, filter, filtrate removes standing demix behind the normal hexane, and lower floor is the raw glycerine after the desalination, and this glycerine is faint yellow thick.The ratio of desalinization of this technology is 75%, and glycerine purity brings up to 85% from 45%.Get above-mentioned raw glycerine 50ml, add the 1000ml deionized water and be diluted to aqueous glycerin solution; The chromatography column that to get two internal diameters be 18mm adds D201 strong basic ion exchange resin and D001 strong-acid ion exchange resin after 250ml handles respectively; Above-mentioned aqueous glycerin solution passes through strong anion-exchange resin (D201) and strong-acid cation-exchange resin (D001) successively with the flow of 2.5ml/min, collects effluent liquid; Obtain colourless, tasteless thick liquid behind the effluent liquid decompression dehydration, glycerine purity is 99.5%.This technology glycerine total recovery is 86.3%.
Claims (7)
1. the process for purification of a biological diesel oil byproduct glycerin, described method comprises: the by-product glycerin that obtains with the grease preparing biodiesel by ester exchange is raw material mutually, adding quality earlier is the organic solvent dissolution of 0.01～20 times of glycerine phase quality, be 1～7 with acid for adjusting pH again, wait to precipitate and separate out, the solids removed by filtration material, get after filtrate evaporation removes organic solvent, standing demix, take off the water dissolution that layer raw glycerine volume is 0.01～20 times of raw glycerine volume, use deacidite successively, acidic ion exchange resin is refining, and the water wash-out, the elutriant dehydration by evaporation obtains glycerine.
2. the method for claim 1, it is characterized in that: used by-product glycerin phase raw material is the lower floor glycerine phase of grease in basic catalyst catalytic transesterification production biofuel process.
3. method as claimed in claim 2 is characterized in that: the used basic catalyst of described preparing biodiesel by ester exchange is sodium hydroxide, potassium hydroxide or sodium methylate.
4. it is characterized in that according to claim 1: described organic solvent is one of following: methyl alcohol, ethanol, acetone, ethyl acetate, heptane, hexane.
5. the method for claim 1 is characterized in that: regulating the used acid of pH is sulfuric acid, hydrochloric acid or acetic acid.
6. the method for claim 1, it is characterized in that: described deacidite volumetric usage is 0.1～50 times of raw glycerine volume.
7. the method for claim 1, it is characterized in that: described acidic ion exchange resin volumetric usage is 0.1～50 times of raw glycerine volume.
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| CNA2008101637416A CN101481297A (en) | 2008-12-30 | 2008-12-30 | Method for refining biodiesel by-product glycerol |
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| CNA2008101637416A CN101481297A (en) | 2008-12-30 | 2008-12-30 | Method for refining biodiesel by-product glycerol |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234566A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Method for separating free glycerin from biodiesel |
| EP2474597A4 (en) * | 2009-08-31 | 2013-04-24 | Oneworld Corp | Process for production of liquefied material from glycerin-type solid material |
| CN105753697A (en) * | 2016-03-01 | 2016-07-13 | 中国药科大学 | Synthetic method for benzenediol monocarboxylic ester |
| WO2017119007A1 (en) | 2016-01-07 | 2017-07-13 | Institute Of Chemical Technology | Process for purification and refining of glycerol |
| CN107011121A (en) * | 2017-05-26 | 2017-08-04 | 龙岩卓越新能源股份有限公司 | The processing unit of biodiesel byproduct crude glycerin |
| WO2017174775A1 (en) * | 2016-04-07 | 2017-10-12 | A & C Freeman | Process for recovery of glycerol from biodiesel production streams |
| CN109294726A (en) * | 2018-11-15 | 2019-02-01 | 绩溪瀚徽农业开发有限公司 | A kind of processing refinement method of rapeseed oil |
| CN109721471A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A method of the Purifing of Glycerol from the by-product of production biodiesel |
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2008
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| CN109721471A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A method of the Purifing of Glycerol from the by-product of production biodiesel |
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| CN109294726A (en) * | 2018-11-15 | 2019-02-01 | 绩溪瀚徽农业开发有限公司 | A kind of processing refinement method of rapeseed oil |
| CN111233625A (en) * | 2020-03-26 | 2020-06-05 | 安徽顺鑫盛源生物食品有限公司 | Glycerol precipitation method in preparation of collagen peptide milk powder |
| CN115611707A (en) * | 2022-09-30 | 2023-01-17 | 上海中器环保科技有限公司 | Purification process of biodiesel byproduct crude glycerol |
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