CN101445742A - Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil - Google Patents
Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil Download PDFInfo
- Publication number
- CN101445742A CN101445742A CNA2008101637401A CN200810163740A CN101445742A CN 101445742 A CN101445742 A CN 101445742A CN A2008101637401 A CNA2008101637401 A CN A2008101637401A CN 200810163740 A CN200810163740 A CN 200810163740A CN 101445742 A CN101445742 A CN 101445742A
- Authority
- CN
- China
- Prior art keywords
- oil
- acid
- reaction
- oil phase
- acid value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000003225 biodiesel Substances 0.000 title claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 58
- 230000032050 esterification Effects 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 171
- 239000004519 grease Substances 0.000 claims description 24
- 239000002551 biofuel Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 12
- 150000002632 lipids Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 239000003921 oil Substances 0.000 abstract description 118
- 235000019198 oils Nutrition 0.000 abstract description 118
- 239000002699 waste material Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 3
- 239000008158 vegetable oil Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010985 leather Substances 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 238000003307 slaughter Methods 0.000 abstract description 2
- 239000010775 animal oil Substances 0.000 abstract 4
- 230000003197 catalytic effect Effects 0.000 abstract 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000010794 food waste Substances 0.000 abstract 1
- 238000012994 industrial processing Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- 230000009466 transformation Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 244000057114 Sapium sebiferum Species 0.000 description 5
- 235000005128 Sapium sebiferum Nutrition 0.000 description 5
- 238000005815 base catalysis Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- 235000021588 free fatty acids Nutrition 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009874 alkali refining Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021191 food habits Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention provides a method utilizing high acid value oil as raw material for preparing biodiesel. Various animal and vegetable oil, the acid value of which is larger than 3.0mg KOH/g oil, oilstock, soapstock and acidic oil in a vegetable oil refining process, various food waste oil (restaurant waste oil, hogwash oil, trench waste oil, and the like) and various waste animal oil in industrial processing (waste animal oil in leather processing, waste animal oil in slaughtering process, and the like) are used as raw materials to obtain biodiesel products by filtration for removing solid impurities, vacuum dehydration, stratified graded acid catalytic esterification, alkali catalytic transesterification and vacuum distillation. The method utilizing the high acid value oil as the raw material for preparing the biodiesel has the beneficial effect that the production process can be applied to raw materials with different acid values to produce biodiesel products with high purity by changing the operational series of the stratified graded acid catalytic esterification reaction and has the advantages of simple process, low energy consumption, high conversion rate and small device. And continuous production can be realized.
Description
(1) technical field
The present invention relates to a kind of is through layering, graded esterified depickling feedstock production method of bio-diesel oil with high-acid value grease.
(2) background technology
A large amount of wastes of the worsening shortages of fossil fuel and fossil fuel discharging are the two large problems that present energy industry exists to the influence of environment, biofuel because of its near in addition be better than the performance of petrifaction diesel and to the friendly attention that is subjected to countries in the world of the cleaning of environment.Countries in the world find in greatly developing the process of biofuel, and the bottleneck of restriction biofuel development is that the wretched insufficiency of raw material and cost of material are too high.
Countries in the world utilize different raw material production biofuel.The U.S. mainly utilizes superfluous soybean oil; Europe and North America mainly utilize superfluous rapeseed oil; The species resource advantage of Malaysia's performance self is mainly utilized plam oil; India mainly utilizes non-edible woody oleiferous plants such as curcas oil; The main haco oil that utilizes surplus of Japan.China's agricultural is ploughed very in short supply and populous, the edible oil materials wretched insufficiency, and the development biofuel must be accomplished " do not strive grain with the people, do not strive ground with grain ".According to population feature and the food habits and the raising of people's living standard in recent years of China, the consumption of each vegetable oil of China is very big, produces a large amount of waste grease (comprising frying oil, sewer oil, swill wet goods), acidifying oil foot etc. thereupon.According to incompletely statistics, only the waste grease of more than 100 annual dischargings of big-and-middle-sized key city catering trade of China has caused serious environmental to pollute and the wasting of resources just near 2,000,000 tons.More very the person has a large amount of waste cooking oils to flow into food products market again by various illegal channels, goes on people's dining table, to the people's healthy and safe formation significant damage.With waste grease and acidifying oil foot is the raw material production biofuel, can alleviate the deficiency of biodiesel raw material, and efficent use of resources is turned waste into wealth; Can block waste grease again and flow into edible oil market.
The production method of biofuel mainly contains homogeneous acid, base catalysis method, solid acid, base catalysis method, enzyme process, supercritical methanol technology.Wherein, homogeneous phase base catalysis stearic exchange process production biofuel has normal pressure, temperature of reaction low (generally about 60 ℃), methanol usage few (molar ratio of methanol to oil is generally 6:1), reaction times short (being generally 60min), transformation efficiency height (more than 95%), be easy to characteristics such as industrial realization, therefore, the production method of the biofuel of using in the world at present is exchanged for the master with homogeneous phase base catalysis stearic.Yet the acid number that homogeneous phase base catalysis stearic exchange student produces thing diesel oil requirement stock oil is lower than 3.0mgKOH/g oil, otherwise, free fatty acids in the stock oil can react with alkaline catalysts, not only generate fatty acid soaps, and spent catalyst, the speed and the transformation efficiency of reduction transesterification reaction.The fatty acid soaps that generates has reduced bio-diesel yield on the one hand, on the other hand because it has emulsifying effect, the last handling process difficulty is increased.Therefore, high-acid value grease must will remove free fatty acids wherein earlier before base-catalyzed transesterification.
Lipin deacidifying method commonly used has: solvent extration, distillation depickling method, alkali-refining deacidification method, the pre-esterification deacidification method of acid catalysis etc.Alkali-refining deacidification is an acid stripping method commonly used in the oil and fat chemical, and this method efficient is low, process is loaded down with trivial details, loss is big.The solvent extration deacidification efficiency is low, solvent load big, the glyceryl ester loss is big.Distillation depickling method energy consumption is bigger.At present, the most frequently used acid stripping method is the pre-esterification process of acid catalysis in the biofuel commercial process.The key issue of acid catalysis pre-esterification reactor is the water-soluble in reaction system of esterification generation, and esterification is reversible reaction, and the water that exists in the reaction system can stop the carrying out of esterification, thereby reduces the transformation efficiency of esterification.How fast, the water that removes simply, effectively in the esterification system is the gordian technique that improves the esterification transformation efficiency.At present, the effective ways of industrial raising esterification transformation efficiency mainly are high temperature gas phase methods, adopt flash distillation, remove the moisture of esterification generation by the method for methyl alcohol band water.The high temperature gas phase method methanol usage is big, the vaporization energy consumption is big, temperature of reaction is high, poor stability, and after methyl alcohol and the water vapor, sulfuric acid is serious to greasy carbonization, and product colour is darker.
(3) summary of the invention
The present invention is directed to the low problem of dehydration esterification reaction difficulty, esterification yield and the shortcoming of above-mentioned prior art, proposed the technology and the technology of layering, graded esterified depickling, be specially the high-acid value grease layering, graded esterified depickling prepares method of bio-diesel oil.
Technical scheme of the present invention is as follows:
High-acid value grease layering, graded esterified depickling prepare method of bio-diesel oil, specifically comprise:
(1) high-acid value grease is removed solid impurity after filtration, dewaters to water content below 0.06%;
(2) high-acid value grease after handling and methyl alcohol and acid catalyst enter esterifier and carry out pre-esterification reactor; Wherein, the mol ratio of lipid acid is 1～30:1 in the high-acid value grease after methyl alcohol and the processing, acid catalyst quality consumption is 0.5%～5.0% of lipid acid quality in the high-acid value grease after handling, and temperature of reaction is controlled at 20～150 ℃, reaction times 1min～240min; Described acid catalyst is preferably hydrochloric acid, sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid etc. for this area routine is used for all kinds of inorganic/organic acid of grease esterification.
(3) after pre-esterification reactor finishes, enter the quantizer layering and remove methanol/catalyzer phase, obtain the oil phase that acid number reduces;
(4) if the oil phase acid number that obtains of step (3) greater than 3.0mg KOH/g oil, the process of repeating step (2) and (3) then, through repeatedly layering, fractionated esterification, until the oil phase acid number that obtains less than 3.0mg KOH/g oil;
(5) if glyceride content is less in the oil phase that step (4) obtains, then directly enter rectifier unit, under distillation pressure 20～1000Pa, distill, collect 170～300 ℃ of cuts, obtain meeting the biofuel of national standard.
If it is bigger that step (4) obtains in the oil phase glyceride content, then earlier after transesterification reaction, enter rectifier unit again and distill, also can comprise step of transesterification between promptly described step (4) and the step (5): acid number is reduced to oil phase below the 3.0mg KOH/g oil mix the adding transesterification reactor with methyl alcohol and alkaline catalysts and carry out transesterification reaction; Wherein, the mol ratio of glyceryl ester is 3～30:1 in methyl alcohol and the described oil phase, alkaline catalysts quality consumption be in the described oil phase glyceryl ester quality 0.5%～5.0%, temperature of reaction is controlled at 20～150 ℃, reaction times 1min～240min; Transesterification reaction finishes, and material enters quantizer layering deglycerizin/catalyzer phase, and the biofuel crude product that obtains enters rectifier unit again, distills under distillation pressure 20～1000Pa, collects 170～300 ℃ of cuts, obtains meeting the biofuel of national standard.
The used high-acid value grease of the present invention is the various animal-plant oil of acid number greater than 3.0mg KOH/g oil, and the oil foot in the vegetables oil treating process, soap stock, acidifying oil; Various edible waste oil (waste cooking oil, hogwash fat, trench wet goods), the various discarded animal grease in the industrial processes process (the useless animal grease in the leather processing procedure, the useless animal grease in the slaughtering process etc.).
The used esterifier of the present invention can be various esterification reaction equipments such as stirring tank, Hydrodynamic cavitation reactor, impact flow reactor, static mixing reactor.
The used transesterification reactor of the present invention can be various transesterification reaction equipment such as stirring tank, Hydrodynamic cavitation reactor, impact flow reactor, static mixing reactor.
Used quantizer can be settling tank, disc centrifuge or wet cyclone among the present invention.When using settling tank: the residence time of material in settling tank is greater than 30min; Use disc centrifuge: the rotating speed of whizzer is greater than 1000rpm.
Preferably, the condition of the pre-esterification reactor in the described step (2) is: the mol ratio of lipid acid is preferably 3:1～6:1 in methyl alcohol and the stock oil, acid catalyst quality consumption be in the stock oil lipid acid quality 1.5～2%, temperature of reaction is preferably 60 ℃, reaction times 5min～60min; Described acid catalyst is hydrochloric acid, sulfuric acid, phosphoric acid or p-methyl benzenesulfonic acid.
Among the present invention, methyl alcohol/catalyzer that the hierarchical layered pre-esterification reactor obtains is mutually reusable: the methyl alcohol/catalyzer previous stage esterification that is used for mutually capable of circulation that obtains behind back one-level esterification, the quantizer.
Characteristics of the present invention are:
(1) the present invention adopts clarification/isolating method of centrifugal/spinning liquid to remove the moisture that generates in the esterification reaction process, improves the esterification transformation efficiency.Compare with the method for methyl alcohol band water, it is few that the technology that the present invention adopts has methanol usage, the characteristics that energy consumption is low, grease is difficult for carbonization, product colour is shallow etc.
(2) the present invention can adapt to the stock oil of different acid numbers by the progression of regulating esterification.
(3) after the pre-esterification of acid catalysis, not only can remove the newly-generated moisture content of esterification but also can remove acid catalyst in the oil phase by sedimentation/centrifugal stratified method, thereby the preceding greasy washing depickling of base-catalyzed transesterification, vacuum hydro-extraction process have been avoided, thereby avoid washing greasy hydrolysis in the deacidification, reduce the discharging of acid waste water and the energy consumption of dehydration.
Beneficial effect of the present invention is mainly reflected in: adopt production technique of the present invention, can adapt to different raw materials, produce highly purified biofuel product, and technology is simple, energy consumption is low, speed is fast, transformation efficiency is high, equipment is little, and can realizes serialization production.
(4) description of drawings
Fig. 1 is a process flow sheet of the present invention;
Esterification of Fig. 2 hierarchical layered and single-stage esterification are to the comparison of lipin deacidifying effect; Annotate: first point is the acid number that material is crossed the oil phase of moment behind the cavitation element among the figure.
(5) embodiment
The present invention is described further (but protection scope of the present invention is not limited in this) below in conjunction with specific embodiment, and the effect of hierarchical layered esterification deacidification and the effect of hierarchical layered esterification deacidification are not compared.
Embodiment 1:
One-level esterification, layering:
1500 grams after filtration, the Chinese tallow tree skin oil (acid number 30mgKOH/g oil) after the dehydration adds in the storage tank of strap clamp cover, and be preheating to 60 ℃, add methanol solution 75 grams that are dissolved with 7.5 grams, 98% vitriol oil then, go into waterpower cavitation esterifier with pump delivery, react 20min down at 60 ℃, reaction solution enters clarifying tank, after clarifying tank stops 1hour, methanol/catalyzer phase is removed in layering, obtain oil phase 1501 grams, measuring the oil phase acid number according to GB GB/T5530-85 is 13.68mgKOH/g oil, and recording the oil phase moisture content with the Ka Shi moisture content tester is 3.0ug/uL.
Secondary esterification, layering:
With 1501 gram process one-level esterifications, the oil phase that obtains after the layering adds and has in the storage tank of chuck, and be preheating to 60 ℃, add methanol solution 75 grams that are dissolved with the 7.5 gram vitriol oils then, go into waterpower cavitation esterifier with pump delivery, react 20min down at 60 ℃, reaction solution enters clarifying tank, after clarifying tank stops 1hour, layering obtains 85 gram methanol/catalyst layers and (is labeled as #1, circulation is used for embodiment 2), and 1498 gram oil reservoirs, measuring the oil reservoir acid number according to GB GB/T5530-85 is 5.21mgKOH/g oil, recording the oil reservoir moisture content with the Ka Shi moisture content tester is 2.9ug/uL.Three grades of esterifications, layering:
With 1498 gram process secondary esterifications, the oil phase that obtains after the layering adds and has in the storage tank of chuck, and be preheating to 60 ℃, add methanol solution 75 grams that are dissolved with the 7.5 gram vitriol oils then, go into waterpower cavitation esterifier with pump delivery, react 20min down at 60 ℃, reaction solution enters clarifying tank, after clarifying tank stops 1hour, layering obtains 83 gram methanol/catalyst layers and (is labeled as #2, circulation is used for embodiment 2), and 1500 gram oil reservoirs, measuring the oil reservoir acid number according to GB GB/T5530-85 is 1.93mgKOH/g oil, recording the oil reservoir moisture content with the Ka Shi moisture content tester is 2.9ug/uL.Transesterify:
1500 grams are joined in the storage tank that has chuck through the Chinese vegetable tallow after three grades of layerings, the graded esterified depickling, and be preheating to 60 ℃, add methanol solution 300 grams that are dissolved with 12 gram KOH then, go into hydraulic cavitation transesterification reactor with pump delivery, behind 60 ℃ of following circulation 60min, reaction solution enters clarifying tank, after clarifying tank stops 1hour, glycerine/catalyst layer is removed in layering, obtains oil phase 1550 grams.
After 1550 gram oil phases remove methyl alcohol, after pickling, washing, dehydration, obtain 1498 gram biofuel products.
The product acid number of surveying according to GB GB/T5530-85 is a 0.69mg KOH/g oil, and (C16～C24) content is 99.9% to record fatty acid methyl ester in the product according to European biofuel standard EN 14103.
Embodiment 2:
One-level esterification, layering:
1500 grams after filtration, Chinese tallow tree skin oil after the dehydration (acid number 30mgKOH/g oil) adds in the storage tank of strap clamp cover, and be preheating to 60 ℃, add 85 gram methyl alcohol/catalyst layer (#1 then, obtain after the esterification of the second stage among the embodiment 1), go into waterpower cavitation esterifier with pump delivery, react 20min down at 60 ℃, reaction solution enters clarifying tank, after clarifying tank stops 1hour, methanol/catalyzer phase is removed in layering, obtain oil phase 1502 grams, measuring the oil phase acid number according to GB GB/T5530-85 is 16.47mgKOH/g oil, and recording the oil phase moisture content with the Ka Shi moisture content tester is 3.0ug/ul.Secondary esterification, layering:
With 1502 gram process one-level esterifications, the oil phase that obtains after the layering adds and has in the storage tank of chuck, and be preheating to 60 ℃, add methyl alcohol/catalyst layer (#2 then, obtain after the third stage esterification among the embodiment 1), go into waterpower cavitation esterifier with pump delivery, react 20min down at 60 ℃, reaction solution enters clarifying tank, after clarifying tank stops 1hour, layering obtains 85 gram methanol/catalyst layers, and 1500 gram oil reservoirs, measuring the oil reservoir acid number according to GB GB/T5530-85 is 8.48mgKOH/g oil, recording the oil reservoir moisture content with the Ka Shi moisture content tester is 2.9ug/uL.Three grades of esterifications, layering:
The oil phase adding that obtains after 1500 gram process secondary esterifications, the layering is had in the storage tank of chuck, and be preheating to 60 ℃, add methanol solution 75 grams that are dissolved with the 7.5 gram vitriol oils then, go into waterpower cavitation esterifier with pump delivery, react 20min down at 60 ℃, reaction solution enters clarifying tank, after clarifying tank stops 1hour, layering obtains 83 gram methanol/catalyst layers, and 1500 the gram oil reservoir, measuring the oil reservoir acid number according to GB GB/T5530-85 is 2.9mgKOH/g oil, and recording the oil reservoir moisture content with the Ka Shi moisture content tester is 2.9ug/uL.
Transesterify:
1500 grams are joined in the storage tank that has chuck through the Chinese vegetable tallow after three grades of layerings, the graded esterified depickling, and be preheating to 60 ℃, add methanol solution 300 grams that are dissolved with 12 gram KOH then, go into hydraulic cavitation transesterification reactor with pump delivery, behind 60 ℃ of following circulation 60min, reaction solution enters clarifying tank, after clarifying tank stops 1hour, glycerine/catalyst layer is removed in layering, obtains oil phase 1552 grams.
After 1552 gram oil phases remove methyl alcohol, after pickling, washing, dehydration, obtain 1499 gram biofuel products.
The product acid number of surveying according to GB GB/T5530-85 is a 0.72mg KOH/g oil, and (C16～C24) content is 99.9% to record fatty acid methyl ester in the product according to European biofuel standard EN 14103.
Embodiment 3:
One-level esterification, layering:
1500 gram acidifying oil (acid number 170mgKOH/g oil, glue content about 10%) add in the storage tank of strap clamp cover, and be preheating to 60 ℃, add methanol solution 900 grams that are dissolved with the 30 gram vitriol oils then, go into the waterpower cavitation reactor with pump delivery, behind reaction 30min under 60 ℃, reaction solution is centrifugal layering under 3000rpm, remove methanol/catalyst layer, obtain oil phase 1647 grams, measuring the oil phase acid number according to GB GB/T5530-85 is 50.1mgKOH/g oil, and recording the oil phase moisture content with the Ka Shi moisture content tester is 3.5ug/uL.
Secondary esterification, layering:
1647 grams are joined in the storage tank of strap clamp cover through one-level layerings, oil phase after graded esterified, and be preheating to 60 ℃, add methanol solution 900 grams that are dissolved with the 30 gram vitriol oils then, go into waterpower cavitation esterifier with pump delivery, behind reaction 30min under 60 ℃, reaction solution is centrifugal layering under 3000rpm, remove methanol/catalyst layer, obtain oil phase 1489.2 grams, measuring the oil reservoir acid number according to GB GB/T5530-85 is 10.2mgKOH/g oil, and recording the oil phase moisture content with the Ka Shi moisture content tester is 3.2ug/uL.
Three grades of esterifications, layering:
1489.2 grams are joined in the storage tank of strap clamp cover through secondary layerings, oil phase after graded esterified, and be preheating to 60 ℃, add methanol solution 900 grams that are dissolved with the 30 gram vitriol oils then, go into waterpower cavitation esterifier with pump delivery, behind reaction 30min under 60 ℃, reaction solution is centrifugal layering under 3000rpm, remove methanol/catalyst layer, obtain oil phase 1400.2 grams, measuring the oil phase acid number according to GB GB/T5530-85 is 2.8mgKOH/g oil, and recording the oil phase moisture content with the Ka Shi moisture content tester is 2.9ug/uL.
Transesterify:
Because stock oil mainly contains have an appointment 85% lipid acid, 10% colloid in the present embodiment, and glyceride content is very low.So raw material have through three grades of layerings, graded esterified after, do not carry out transesterify, and directly refining by vacuum distilling.
Vacuum distilling:
With above-mentioned remove methyl alcohol through the oil phase after three secondary clearings, the pre-esterification of classification 1400 gram after, in 5mmHg, 170～240 ℃ of following underpressure distillation of still temperature, obtain the water white product of 1344 grams.The product acid number of surveying according to GB GB/T5530-85 is a 0.64mg KOH/g oil, and (C16～C24) content is 92% to record fatty acid methyl ester in the product according to European biofuel standard EN 14103.The comparison of deacidification effect:
Fig. 2 has compared the effect of Chinese vegetable tallow (the stock oil acid number is a 30mgKOH/g oil) free fatty acid esterification, lipin deacidifying under hierarchical layered esterification and single-stage esterification operational condition.Table 1 has marked experiment condition.
Table 1: experiment condition
| The experiment title | Esterification progression | The methyl alcohol proterties | The fresh methanol consumption | The sulfuric acid consumption |
| Experiment 1 | One-level | Fresh methanol | Oil is heavy by 15% | Oil is heavy by 1.5% |
| Experiment 2 | Three grades | The first step: the fresh methanol second stage: the fresh methanol third stage: fresh methanol | Every grade of consumption: the heavy 5% total consumption of oil: oily heavy by 15% | Every grade of consumption: the heavy 0.5% total consumption of oil: oily heavy by 1.5% |
| Experiment 3 | Three grades | The first step: recycle methanol (test 2 substratifications after the methyl alcohol phase) second stage: recycle methanol (test 2 third stage layerings after the methyl alcohol phase) third stage: fresh methanol | Total consumption: oil heavy 5% | Total consumption: oil heavy 0.5% |
Fig. 2 and table 1 show, than single-stage esterification operation, by layering, fractionated esterification process, not only can reduce the acid number of oil phase greatly, and can reduce the consumption of methyl alcohol and acid catalyst greatly.
Claims (7)
1. a high-acid value grease layering, graded esterified depickling prepare method of bio-diesel oil, and described method comprises:
(1) high-acid value grease is removed solid impurity after filtration, dewaters to water content below 0.06%;
(2) high-acid value grease after handling and methyl alcohol and acid catalyst enter esterifier and carry out pre-esterification reactor; Wherein, the mol ratio of lipid acid is 1～30:1 in the high-acid value grease after methyl alcohol and the processing, acid catalyst quality consumption is 0.5%～5.0% of lipid acid quality in the high-acid value grease after handling, and temperature of reaction is controlled at 20～150 ℃, reaction times 1min～240min;
(3) after pre-esterification reactor finishes, enter the quantizer layering and remove methanol/catalyzer phase, obtain the oil phase that acid number reduces;
(4) if the oil phase acid number that obtains of step (3) greater than 3.0mg KOH/g oil, the process of repeating step (2) and (3) then, until the oil phase acid number that obtains less than 3.0mg KOH/g oil;
(5) the oil phase acid number that obtains of step (4) enters rectifier unit less than 3.0mg KOH/g oil, distills under distillation pressure 20～1000Pa, collects 170～300 ℃ of cuts, obtains described biofuel.
2. the method for claim 1 is characterized in that also comprising step of transesterification between described step (4) and the step (5): acid number is reduced to oil phase below the 3.0mg KOH/g oil mix with methyl alcohol and alkaline catalysts and add transesterification reactor and carry out transesterification reaction; Wherein, the mol ratio of glyceryl ester is 3～30:1 in methyl alcohol and the described oil phase, alkaline catalysts quality consumption be in the described oil phase glyceryl ester quality 0.5%～5.0%, temperature of reaction is controlled at 20～150 ℃, reaction times 1min～240min; Transesterification reaction finishes, and material enters quantizer layering deglycerizin/catalyzer phase, and the biofuel crude product that obtains enters rectifier unit again.
3. method as claimed in claim 1 or 2 is characterized in that acid catalyst described in the step (2) is one of following: hydrochloric acid, sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid.
4. the method for claim 1 is characterized in that alkaline catalysts described in the step (5) is one of following: NaOH, KOH, CH
3ONa, CH
3OK.
5. the method for claim 1 is characterized in that quantizer is settling tank, disc centrifuge or wet cyclone in step (2) and the step (6), and when using settling tank, the residence time of material in settling tank is greater than 30min; When using disc centrifuge, the rotating speed of whizzer is greater than 1000rpm.
6. the method for claim 1 is characterized in that esterifier in the described step (2) is one of following: stirring tank, Hydrodynamic cavitation reactor, ultrasonic reactor, impact flow reactor, static mixing reactor.
7. the method for claim 1, the condition that it is characterized in that the pre-esterification reactor in the described step (2) is: the mol ratio of lipid acid is 3:1～6:1 in methyl alcohol and the stock oil, acid catalyst quality consumption be in the stock oil lipid acid quality 1.5～2%, temperature of reaction is 60 ℃, reaction times 5min～60min; Described acid catalyst is hydrochloric acid, sulfuric acid, phosphoric acid or p-methyl benzenesulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101637401A CN101445742A (en) | 2008-12-30 | 2008-12-30 | Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101637401A CN101445742A (en) | 2008-12-30 | 2008-12-30 | Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101445742A true CN101445742A (en) | 2009-06-03 |
Family
ID=40741622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101637401A Pending CN101445742A (en) | 2008-12-30 | 2008-12-30 | Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101445742A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781610A (en) * | 2010-03-16 | 2010-07-21 | 刘宽 | Continuous esterification and ester exchange process used for producing biodiesel |
| CN101921659A (en) * | 2009-06-15 | 2010-12-22 | 高资明 | Method for preparing fatty acid methyl ester from high fatty-acid grease by using recycled methanol |
| CN101955848A (en) * | 2010-09-27 | 2011-01-26 | 温州中科新能源科技有限公司 | Process for preparing biodiesel from waste oil with high acid value |
| WO2011109945A1 (en) * | 2010-03-08 | 2011-09-15 | 中山大学 | Biodiesel and preparation method thereof |
| CN102229864A (en) * | 2011-04-28 | 2011-11-02 | 辽宁省能源研究所 | Method for producing biodiesel with hogwash oil of high acid value |
| CN102584585A (en) * | 2012-01-11 | 2012-07-18 | 河北欣奇典生物科技有限公司 | Method for deacidifying alpha-ethylli-nolenate solvent |
| CN102649920A (en) * | 2012-05-07 | 2012-08-29 | 唐山金利海生物柴油股份有限公司 | Device and method for continuously preparing biodiesel under intermediate-temperature and medium-pressure condition |
| CN102041177B (en) * | 2009-10-18 | 2013-01-16 | 陕西春光生物能源开发有限公司 | Method for preparing biodiesel |
| CN103382417A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Biodiesel transesterification technology |
| CN103382416A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Biodiesel esterification reaction technology |
| CN103409242A (en) * | 2012-11-09 | 2013-11-27 | 广州市南洋国际工程技术服务公司 | Recycling process for alkali refining by-product, namely soapstock in refining vegetable oil and reactor |
| CN103820224A (en) * | 2014-03-13 | 2014-05-28 | 安徽天意环保科技有限公司 | Biodiesel and preparation method thereof |
| US8816105B2 (en) | 2010-02-08 | 2014-08-26 | Upm-Kymmene Corporation | Method and apparatus for purifying crude tall oil |
| CN105462693A (en) * | 2015-11-27 | 2016-04-06 | 宁波滨海石化有限公司 | Swill-cooked dirty oil pre-esterification process |
| CN105542970A (en) * | 2016-01-20 | 2016-05-04 | 定陶县地元生化制品有限公司 | Method and device for continuously producing biological diesel oil |
| CN111019720A (en) * | 2019-12-31 | 2020-04-17 | 浙江卓尚环保能源有限公司 | Green production process of biodiesel |
| CN111423936A (en) * | 2020-02-12 | 2020-07-17 | 常州市金坛区维格生物科技有限公司 | Method for reducing acid of waste oil at low temperature |
| CN112175744A (en) * | 2020-09-28 | 2021-01-05 | 湖北天基生物能源科技发展有限公司 | Method for preparing biodiesel from high-acid-value kitchen waste grease |
| CN112708507A (en) * | 2020-11-11 | 2021-04-27 | 广东电网有限责任公司 | Acid reduction process for preparing kitchen waste grease-based natural ester insulating oil |
| CN113462422A (en) * | 2021-07-09 | 2021-10-01 | 中国林业科学研究院林产化学工业研究所 | One-step preparation process of biodiesel by bifunctional catalysis of high-acid-value grease and continuous device |
-
2008
- 2008-12-30 CN CNA2008101637401A patent/CN101445742A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921659A (en) * | 2009-06-15 | 2010-12-22 | 高资明 | Method for preparing fatty acid methyl ester from high fatty-acid grease by using recycled methanol |
| CN101921659B (en) * | 2009-06-15 | 2012-10-17 | 高资明 | Method for preparing fatty acid methyl ester from high fatty-acid grease by using recycled methanol |
| CN102041177B (en) * | 2009-10-18 | 2013-01-16 | 陕西春光生物能源开发有限公司 | Method for preparing biodiesel |
| US8816105B2 (en) | 2010-02-08 | 2014-08-26 | Upm-Kymmene Corporation | Method and apparatus for purifying crude tall oil |
| WO2011109945A1 (en) * | 2010-03-08 | 2011-09-15 | 中山大学 | Biodiesel and preparation method thereof |
| CN101781610A (en) * | 2010-03-16 | 2010-07-21 | 刘宽 | Continuous esterification and ester exchange process used for producing biodiesel |
| CN101955848A (en) * | 2010-09-27 | 2011-01-26 | 温州中科新能源科技有限公司 | Process for preparing biodiesel from waste oil with high acid value |
| CN102229864A (en) * | 2011-04-28 | 2011-11-02 | 辽宁省能源研究所 | Method for producing biodiesel with hogwash oil of high acid value |
| CN102229864B (en) * | 2011-04-28 | 2013-03-27 | 辽宁省能源研究所 | Method for producing biodiesel with hogwash oil of high acid value |
| CN102584585A (en) * | 2012-01-11 | 2012-07-18 | 河北欣奇典生物科技有限公司 | Method for deacidifying alpha-ethylli-nolenate solvent |
| CN102649920A (en) * | 2012-05-07 | 2012-08-29 | 唐山金利海生物柴油股份有限公司 | Device and method for continuously preparing biodiesel under intermediate-temperature and medium-pressure condition |
| CN103409242A (en) * | 2012-11-09 | 2013-11-27 | 广州市南洋国际工程技术服务公司 | Recycling process for alkali refining by-product, namely soapstock in refining vegetable oil and reactor |
| CN103409242B (en) * | 2012-11-09 | 2014-11-12 | 广州市南洋国际工程技术服务公司 | Recycling process for alkali refining by-product, namely soapstock in refining vegetable oil and reactor |
| CN103382416A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Biodiesel esterification reaction technology |
| CN103382417A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Biodiesel transesterification technology |
| CN103382417B (en) * | 2013-01-14 | 2015-12-23 | 江苏悦达卡特新能源有限公司 | A kind of technique of biofuel transesterification reaction |
| CN103382416B (en) * | 2013-01-14 | 2015-12-23 | 江苏悦达卡特新能源有限公司 | A kind of technique of biodiesel esterification |
| CN103820224A (en) * | 2014-03-13 | 2014-05-28 | 安徽天意环保科技有限公司 | Biodiesel and preparation method thereof |
| CN105462693A (en) * | 2015-11-27 | 2016-04-06 | 宁波滨海石化有限公司 | Swill-cooked dirty oil pre-esterification process |
| CN105542970A (en) * | 2016-01-20 | 2016-05-04 | 定陶县地元生化制品有限公司 | Method and device for continuously producing biological diesel oil |
| CN111019720A (en) * | 2019-12-31 | 2020-04-17 | 浙江卓尚环保能源有限公司 | Green production process of biodiesel |
| CN111423936A (en) * | 2020-02-12 | 2020-07-17 | 常州市金坛区维格生物科技有限公司 | Method for reducing acid of waste oil at low temperature |
| CN112175744A (en) * | 2020-09-28 | 2021-01-05 | 湖北天基生物能源科技发展有限公司 | Method for preparing biodiesel from high-acid-value kitchen waste grease |
| CN112708507A (en) * | 2020-11-11 | 2021-04-27 | 广东电网有限责任公司 | Acid reduction process for preparing kitchen waste grease-based natural ester insulating oil |
| CN113462422A (en) * | 2021-07-09 | 2021-10-01 | 中国林业科学研究院林产化学工业研究所 | One-step preparation process of biodiesel by bifunctional catalysis of high-acid-value grease and continuous device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101445742A (en) | Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil | |
| Adewale et al. | Recent trends of biodiesel production from animal fat wastes and associated production techniques | |
| CN101906355B (en) | Method for preparing biodiesel by utilizing food waste recycling oil | |
| Sulaiman et al. | Reactive extraction of solid coconut waste to produce biodiesel | |
| CN101161784B (en) | Method for extracting conversion biodiesel from oil pressing cake | |
| CN101591574B (en) | Method for preparing biodiesel by zirconia solid base catalyst | |
| CN101012388A (en) | Method of manufacturing biological diesel oil from hogwash oil | |
| Veljković et al. | Waste Vegetable oils, fats, and cooking oils in biodiesel production | |
| CN102816645A (en) | Continuous preparation method of biodiesel | |
| CN100510009C (en) | Preparing process for biodiesel oil | |
| CN101294097B (en) | Multifunctional reaction still for preparing biological diesel oil and operation method thereof | |
| Yu et al. | Synthesis of biodiesel from an oil fraction separated from food waste leachate | |
| CN101338214A (en) | Method for preparing biodiesel using acidizing oil as raw material under normal pressure | |
| CN100523131C (en) | Esterification reaction technique of preparing biodiesel by waste oil | |
| CN101294098A (en) | Method for preparing biological diesel oil by using inversed micelle catalyst | |
| CN100365100C (en) | Method of preparing biological diesel oil by methanol critical low alkali process | |
| CN101531913A (en) | Method for preparing biodiesel | |
| CN201695009U (en) | Biodiesel oil production line | |
| CN101423767A (en) | Method for preparing biodiesel by alcohol extraction and solid base catalysis two-step method | |
| CN101892128A (en) | Method for catalytic production of branching biological diesel by resin | |
| CN101475822B (en) | Method for synthesizing biodiesel by shell powder supported solid acid-base catalysis | |
| CN101392181A (en) | Novel method for preparing biodiesel by in situ extraction of rice oil | |
| CN202610209U (en) | High acid value oil and fat preparation biodiesel device | |
| Kazancev et al. | Application of enzymatic process for biodiesel synthesis from vegetable oil with high fatty acid content using butanol | |
| CN103374462B (en) | Preparation method of biodiesel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090603 |