CN1328353C - Technology of preparing biological diesel oil from animal and vegetable oil - Google Patents
Technology of preparing biological diesel oil from animal and vegetable oil Download PDFInfo
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- CN1328353C CN1328353C CNB2005100757506A CN200510075750A CN1328353C CN 1328353 C CN1328353 C CN 1328353C CN B2005100757506 A CNB2005100757506 A CN B2005100757506A CN 200510075750 A CN200510075750 A CN 200510075750A CN 1328353 C CN1328353 C CN 1328353C
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- 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
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- 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
Abstract
The present invention relates to a technique for preparing biological diesel oil from animal oil and vegetable oil, which uses fatty acid and high acid number or neutral animal and plant grease as raw materials for preparing a substitute fuel of petrifaction diesel oil. The steps of esterification, continuous water containing, methanol rectification and gasification are organically combined together to quickly reduce acid and enhance the efficiency of esterification reaction. Methanol is circularly used in a gas form, which increases the utilization rate of the methanol without waste. The specific processes of an ester interchange step is that raw materials are processed by one-time ester exchange reaction; the methanol is firstly recovered when the reaction is over, which can prevent the methanol from influencing the separation of products; then, all the by-product glycerol is separated. Compared with two-time ester exchange reaction, the present invention enhances the equipment efficiency by more than one time; all the conversion rates are above 90%. The biological diesel oil refined by steam distillation enables distillation temperature to reduce, reduces energy consumption, increases heat efficiency, and simultaneously, avoids local overheating in direct heating distillation, so hidden dangers are prevented, the oxidation of products with over high temperature is also prevented.
Description
Technical field the present invention relates to the technology that a kind of animal and vegetable oil prepares biofuel.
The existing biodiesel oil preparing process of background technology, the ester-interchange methods that adopt more, be grease in the presence of basic catalyst (potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate etc. are generally arranged) with methyl alcohol or ethanol generation transesterification reaction (claiming alcoholysis reaction again), generate fatty acid methyl ester or fatty-acid ethyl ester, i.e. biofuel and by-product glycerin.
Require the acid number of raw material must be less than 1.0 in the preparing biodiesel by ester interchange, if acid treatment will fall in high-acid-value material, method has alkali refining method and acid catalyzed esterification method.Loss and the effluent discharge contaminate environment that acid can cause raw material falls in the alkali refining method, and existing acid catalyzed esterification method is repeatedly esterification of intermittent type, troublesome poeration, consuming time, efficient is low.
In adopting preparing biodiesel by ester interchange, key is: 1, improve conversion of raw material; 2, improve the purity of product biofuel.Existing processing method mainly improves conversion of raw material by twice transesterification reaction: at first in first transesterification reactor, be transferred in first glycerin separator behind the reaction certain hour and isolate glycerine, the ester layer is transferred in second transesterification reactor, add new methyl alcohol and catalyzer potassium hydroxide carries out the secondary transesterification reaction, enter again in second glycerin separator and isolate glycerine, this type of processing method operation is loaded down with trivial details, and energy consumption is bigger, and cost is higher.
Existing technology mainly adopts a large amount of water to wash the purity that improves biofuel, can produce a large amount of waste lyes like this.Contain glycerine, soap and catalyzer in these alkali lye,, not only cause environmental pollution, also cause the loss of valuable by product if these alkali lye are not carried out just discharging of appropriate processing.If reclaim, because of being increased energy consumption by big water gaging dilution.
The deficiency that summary of the invention exists at above-mentioned prior art, the present invention proposes the technology that a kind of animal and vegetable oil prepares biofuel, it is to be feedstock production petrifaction diesel alternative fuel with lipid acid, high acid value or neutral animal-plant oil, and the technology that the present invention proposes has following production stage:
(1). vapour phase esterification: 60～70 ℃ of methanol vapor that methanol gasifying device 1 produces are that the speed of 6～8 liters of/minute 100g stock oils enters into the esterifier 5 that stock oil and an acidic catalyst are housed through rectifying columns 2 backs by the feeding amount, in temperature of reaction is to participate in esterification 30～120 minutes under 95～105 ℃ of conditions, the water vapor that reacted methanol vapor and reaction produce turns back in the methanol gasifying device 1 after condensation tower 3 condensations, and an acidic catalyst consumption is 0.2%～1.0% of a stock oil weight;
(2). transesterify: the stock oil of handling through esterification enters transesterification reactor 10,60～80 ℃ of transesterification reaction temperature; Methanol usage be in the stock oil glycerin fatty acid ester weight 20～25%, the basic catalyst consumption is 0.4～1.5% of a stock oil weight, reaction finishes the back and reclaims methyl alcohol earlier, separation of glycerin again, the coarse biodiesel that obtains enters biofuel rectifying reactor 15, and raw glycerine enters the by-product recovery art breading;
(3). biofuel is refining: the water vapor that with temperature is 95～105 ℃ is the speed of 5～6 liters of/minute 100g stock oils by the feeding amount, enter from the bottom of rectifying reactor 15, carry out steam distillation, the liquid phase of biofuel rectifying reactor is 180～280 ℃, gas phase is 120～220 ℃, the biofuel that steams enters after 17 condensations are leant in condensation with water vapor carries out in the biofuel separator 18 separating of biofuel and water, biofuel is removed from separator 18, and the residual residue in the reactor 15 turns back in the biodiesel manufacture technology after the by-product recovery art breading.
Described an acidic catalyst is a sulfuric acid, and this catalyst preparation becomes 2% methanol solution use; The rectifying column reflux ratio is 2.0～2.5; Basic catalyst is potassium hydroxide or sodium hydroxide; Stock oil is oleic acid, catering trade waste oil, Jatropha curcas oil, rapeseed oil, soybean oil, oleum lini, peanut oil or plam oil; The by-product recovery treatment process be the raw glycerine that will produce from ester-exchange reaction in neutralization reactor 20, in pH=3.5～4.5, refluxed 30 minutes under 65～75 ℃ of conditions of temperature, carry out acidification; Carry out separating of acidifying oil and glycerin layer then in acidifying oil separator 21, acidifying oil returns and carries out esterification treatment in the gaseous phase esterification reaction device, carries out the refining biofuel that obtains of steam distillation again; Glycerin layer is carried out basic treatment in alkaline purification reactor 22, hydro-oxidation potassium is to the pH=8, in evaporation concentration reactor 23, carry out concentration then, filter in strainer 24 and obtain raw glycerine and thick vitriolate of tartar, the methyl alcohol that is used for washing vitriolate of tartar reclaims at Methanol Recovery reactor 25.
Advantage of the present invention and positively effect are:
The first, with esterification, be with water, methanol rectification and gasification organically to combine continuously, reach the effect of fast prompt drop acid, improve the efficient of esterification; Methyl alcohol recycles with the form of gas, has improved use ratio of methanol, does not almost have the waste of methyl alcohol; Simultaneously aqueous methanol gasifies in rectifying device, and moisture content stays in the outer auxiliary gasifier of esterification main body system, has improved usage ratio of equipment, reduces facility investment, has avoided the complex operations and the equipment increase that dewater, has shortened the reaction times.
The second, step of transesterification, detailed process is: raw material adopts a transesterification reaction, and reaction finishes, and reclaims methyl alcohol earlier, can avoid methyl alcohol influence separation between product (because of generation product biofuel and glycerine all are dissolved in methyl alcohol); Separate all by-product glycerins again, plant efficiency is enhanced about more than once with comparing of twice transesterification reaction, and transformation efficiency is all more than 90%.Particularly the transformation efficiency of Jatropha curcas oil can reach 96.67%.This shows that in processing method of the present invention, less than 10%, energy consumption but doubles as if the transformation efficiency that carries out transesterification reaction raising for the second time.
Three, by the steam distillation refining biodiesel, distillation temperature is reduced, reduce energy consumption, thermo-efficiency improves, and avoids the local superheating in the direct heating distillation simultaneously, has prevented hidden danger, has prevented that also temperature from crossing high product generation oxidation.
Four, preparation process of the present invention has realized effectively separating of biofuel and unreacting material and relevant foreign material, does not compare with adopting present method purified biodiesel oil preparing process, has obtained highly purified biofuel; By product is glycerine and vitriolate of tartar in the major product production of biodiesel, and the useful by-product recovery of these generations and production of biodiesel technology organically combine, and have improved production efficiency; By comprehensive treating process, can subsidize the production cost of biofuel, reduce total cost of production, obtain or improve overall economic benefit, reach or the cost of convergence petrifaction diesel.
Five, the waste residue treatment process after the present invention has realized the production biofuel and cheap vegetable oil material fruit is got oil combines, and carries out different utilizations according to different material, realizes that industry do not have " three wastes ", has environment friendly.
Six, coarse biodiesel need not be washed, and reduces the energy consumption that glycerine reclaims.
Seven, institute's employing equipment has versatility, reduces equipment investment cost.
Eight, transesterification reaction among the present invention and existing technology can only be handled acid number and is no more than 1.0 stock oil bigger difference is arranged, and the present invention's acid number to raw material in transesterification reaction requires to be loosened to 5.0, has so just shortened and has fallen the acid time, has improved efficient.
Description of drawings
The preparation production of biodiesel process flow diagram that Fig. 1 proposes for the present invention.
Fig. 2 is a by-product recovery process flow diagram of the present invention.
Among Fig. 1: 1-methanol gasifying device, 2-rectifying column, 3,9, the 17-condensation tower, the 4-interchanger, 5-esterifier, 6-sulfuric acid storage tank, 7,13-mixing tank, 8-stock oil storage tank, 10-transesterification reactor, 11-methyl alcohol storage tank, 12-potassium hydroxide, 14-glycerin separator, 15-biofuel rectifying reactor, the 16-steam generator, 18-biofuel separator, 19-impeller pump.
The preparation production technique that the present invention proposes is that the technological process of raw material is " vapour phase esterification → steam distillation " with lipid acid; Is that the technological process of raw material is " vapour phase esterification → transesterify → steam distillation " with acid number greater than 5.0 high acid value vegetable and animals oils; Is " transesterify → steam distillation " with acid number less than the technological process that 5.0 low acid number or neutral vegetable and animals oils are raw material.
Below in conjunction with accompanying drawing the present invention is elaborated.
1. vapour phase esterification
In Fig. 1, the methanol vapor that is produced by methanol gasifying device 1 enters into after by rectifying column 2 (methyl alcohol that assurance recycles is not moisture) and stock oil is housed and an acidic catalyst vitriolic esterifier 5 participates in esterification, adopt pump 19 to force to stir, the water (with vapor form) that reaction remaining methanol vapor in back and reaction produce comes out from reactor 5, after condensation tower 3 condensations, turn back in the gasifier 1, realize the recycle of methanol vapor and will react the water that produces and take out of continuously, reach continuously esterification fast and fall sour purpose.
Being the rectification process that directly enters biofuel behind the thick product separation catalyst sulfuric acid that obtains of raw material with lipid acid, is to enter ester exchange process behind the thick product separation catalyst sulfuric acid that obtains of raw material with acid number greater than 5.0 high acid value vegetable and animals oils.Processing condition are as follows:
1. temperature of reaction: esterifier is 95～105 ℃; The methanol vapor vapour generator is 60～70 ℃.
2. methanol rectification post reflux ratio: 2.0～2.5.
3. methanol vapor feeding amount: 6～8 liters of/minute 100g stock oils.
4. an acidic catalyst sulfuric acid consumption is 0.2%～1.0% of a stock oil weight, and sulfuric acid is mixed with 2% methanol solution earlier, determines the ratio of the shared stock oil of sulfuric acid according to the acid number difference.
5. reaction times: 30～120 minutes, the required reaction times difference of the raw material of different acid numbers was determined the reaction times by the reduction situation of acid number in the assaying reaction process.
2. transesterify
Carry out in transesterification reactor shown in Figure 1 10, reaction finishes the back and reclaims methyl alcohol by reactor 10 earlier, separation of glycerin in glycerin separator 14 again, and the coarse biodiesel that obtains enters the rectification process of biofuel, and raw glycerine enters by-product recovery technology.Processing condition are as follows:
1. transesterification reaction temperature: 60～80 ℃.
2. transesterify number of times: once.
3. reaction times: 60～120 minutes, the different required reaction times differences of the neutral grease content in the raw material.
4. methanol usage be in the stock oil glycerin fatty acid ester weight 20～25%.
5. the basic catalyst consumption is 0.4～1.5% of a stock oil weight.
Condensation tower 4 is contained between esterifier 5 and the transesterification reactor 10.
3. biofuel is refining
In reactor shown in Figure 1 15～18, carry out, the water vapor that produces in the steam generator 16 enters from the bottom of rectifying reactor 15, carry out steam distillation, the biofuel that steams enters in the biofuel separator 18 after 17 condensations are leant in condensation with water vapor, in 18, carry out separating of biofuel and water, water is from bottom Returning reactor 16, and biofuel is removed from reactor 18, and the residual residue in the reactor 15 turns back in the biodiesel manufacture technology through by-product recovery technology.Processing condition are as follows:
1. temperature: the biodiesel reactor liquid phase is 180～280 ℃, and gas phase is 120～220 ℃; Steam generator is 95～105 ℃.
2. water vapor feeding amount: 5～6 liters of/minute 100g stock oils, when changing, the stock oil consumption does corresponding the adjustment.
4. by-product recovery
As shown in Figure 2, the raw glycerine that produces from ester-exchange reaction in the biodiesel manufacture carries out acidification in neutralization reactor 20, in pH=3.5～4.5, refluxed 30 minutes under 65～75 ℃ of conditions of temperature, in acidifying oil separator 21, carry out separating of acidifying oil and glycerin layer then, acidifying oil returns and carries out esterification treatment in the gaseous phase esterification reaction device, carries out the refining biofuel that obtains of steam distillation again.Glycerin layer in the raw glycerine storage tank 27 is carried out basic treatment by being pumped in the alkaline purification reactor 22, the hydro-oxidation potassium solution is to the pH=8, in evaporation concentration reactor 23, carry out concentration then, filter in strainer 24 and obtain raw glycerine and thick vitriolate of tartar, the methyl alcohol that is used for washing vitriolate of tartar reclaims at Methanol Recovery reactor 25 after prolong 26 condensations.
Embodiment
Embodiment 1 oleic acid production biofuel
1. processing parameter
1. vapour phase esterification
Temperature of reaction: esterifier is 100 ± 5 ℃; The methanol vapor producer is 65 ℃.Methanol vapor feeding amount: 7 liters/minute.Methanol rectification post reflux ratio: 2.5.Reaction times: 60 minutes.
2. biofuel extraction temperature: biofuel still kettle liquid phase is 180～200 ℃, and gas phase is 145～155 ℃; Steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5 liters/minute.
2. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: analytical pure oleic acid 100g, methyl alcohol 100g, 98% sulfuric acid 1.0g
Output: biofuel 98.86g (Witconol 2301 content is 99.64%), residue 0.98g reclaims methyl alcohol 79g, reclaim(ed) sulfuric acid 0.95g.
Embodiment 2 swill oil production biofuel
1. raw material basic condition: the basic condition of raw material swill oil sees Table 1.
2. processing parameter
1. vapour phase esterification
Temperature of reaction: esterifier is 100 ± 5 ℃; The methanol vapor producer is 65 ℃.Methanol vapor feeding amount: 6.5 liters/minute.Methanol rectification post reflux ratio: 2.5.Reaction times: 120 minutes.
2. transesterify
Temperature of reaction: 65 ℃.Transesterify number of times: once.Reaction times: 60 minutes
3. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃; Steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5 liters/minute.
4. by-product recovery
Glycerine and vitriolate of tartar reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: dewater and impurity after swill oil 100g, (100g is used for gaseous phase esterification reaction to methyl alcohol 103.5g, 3.5g be used for transesterification reaction), (0.4g is used for gaseous phase esterification reaction to 98% sulfuric acid 1.2g, 0.8g be used for by-product recovery), potassium hydroxide 0.7g (0.4g is used for transesterification reaction, and 0.3g is used for by-product recovery)
Output: biofuel 93.57g, raw glycerine 1.60g (glycerol content is 81.24%), vitriolate of tartar 1.8g, residue 6.0g reclaims methyl alcohol 85g.
4. the main quality index of product
Adopt the main quality index of the swill oil biofuel that Technology of the present invention prepares to see Table 2.
Embodiment 3 Jatropha curcas oil production biofuel
1. raw material basic condition: the basic condition of raw material Jatropha curcas oil sees Table 1.
2. processing parameter
1. vapour phase esterification
Temperature of reaction: esterifier is 100 ± 5 ℃; The methanol vapor producer is 65 ℃.Methanol vapor feeding amount: 6 liters/minute.Methanol rectification post reflux ratio: 2.0～2.5.Reaction times: 60 minutes.
2. transesterify
Temperature of reaction: 65 ℃.Transesterify number of times: once.Reaction times: 120 minutes.
3. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃; Steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5 liters/minute.
4. by-product recovery
Glycerine and vitriolate of tartar reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: Jatropha curcas oil 100g, (100g is used for gaseous phase esterification reaction to methyl alcohol 120g, 20g is used for transesterification reaction), (0.2g is used for gaseous phase esterification reaction to 98% sulfuric acid 1.05g, 0.85g be used for by-product recovery), potassium hydroxide 1.2g (1.0g is used for transesterification reaction, and 0.2g is used for by-product recovery).
Output: biofuel 96.28g, raw glycerine 9.42g (glycerol content is 79.10%), vitriolate of tartar 1.7g, residue 2.6g (the fatty acid glycerine ester content is 33.34%) reclaims methyl alcohol 107g.
4. the main quality index of product
Adopt the main quality index of the Jatropha curcas oil biofuel that Technology of the present invention prepares to see Table 2.
Embodiment 4 rapeseed oil production biofuel
1. raw material basic condition: the basic condition of raw material rapeseed oil sees Table 1.
2. processing parameter
1. transesterify
Temperature of reaction: 75 ℃.Transesterify number of times: once.Reaction times: 120 minutes.
2. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃; Steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5.5 liters/minute.
3. by-product recovery
Glycerine and vitriolate of tartar reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: rapeseed oil 100g, methyl alcohol 25g, potassium hydroxide 1.2g (1.0g is used for transesterification reaction, and 0.2g is used for by-product recovery), 98% sulfuric acid 1.0g (being used for by-product recovery),
Output: biofuel 95.98g, raw glycerine 9.95g (glycerol content is 80.25%), vitriolate of tartar 1.7g, residue 2.78g (the fatty acid glycerine ester content is 74.29%) reclaims methyl alcohol 13.2g.
4. the main quality index of product
Adopt the main quality index of the rapeseed oil biofuel that Technology of the present invention prepares to see Table 2.
Embodiment 5 soybean oil production biofuel
1. raw material basic condition: the basic condition of raw soybeans oil sees Table 1.
2. processing parameter
1. transesterify
Temperature of reaction: 60 ℃.Transesterify number of times: once.Reaction times: 90 minutes.
2. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃; Steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5.5 liters/minute.
3. by-product recovery
Glycerine and vitriolate of tartar reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: soybean oil 100g, methyl alcohol 20g, potassium hydroxide 1.5g (1.2g is used for transesterification reaction, and 0.3g is used for by-product recovery), 98% sulfuric acid 1.1g (being used for by-product recovery),
Output: biofuel 96.79g, raw glycerine 9.67g (glycerol content is 80.07%), vitriolate of tartar 1.7g, residue 2.6g (the fatty acid glycerine ester content is 67.78%) reclaims methyl alcohol 7.75g.
4. the main quality index of product
Adopt the main quality index of the soybean oil biofuel that Technology of the present invention prepares to see Table 2.
Embodiment 6 oleum lini production biofuel
1. raw material basic condition: the basic condition of raw material oleum lini sees Table 1.
2. processing parameter
1. transesterify
Temperature of reaction: 65 ℃.Transesterify number of times: once.Reaction times: 90 minutes.
2. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃: steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5.5 liters/minute.
3. by-product recovery
Glycerine and vitriolate of tartar reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: oleum lini 100g, methyl alcohol 20g, potassium hydroxide 1.1g (1.0g is used for transesterification reaction, and 0.1g is used for by-product recovery), 98% sulfuric acid 0.95g (being used for by-product recovery),
Output: biofuel 96.66g, raw glycerine 9.67g (glycerol content is 80.02%), vitriolate of tartar 1.4g, residue 2.83g (the fatty acid glycerine ester content is 71.99%) reclaims methyl alcohol 6.8g.
4. the main quality index of product
Adopt the main quality index of the oleum lini biofuel that Technology of the present invention prepares to see Table 2.
Embodiment 7 peanut oil production biofuel
1. raw material basic condition: the palmitic basic condition of stock oil sees Table 1.
2. processing parameter
1. transesterify
Temperature of reaction: 60 ℃.
Transesterify number of times: once
Reaction times: 90 minutes
2. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃; Steam generator is 100 ± 5 ℃.
Water vapor feeding amount: 5.5 liters/minute.
3. by-product recovery
Glycerine and sodium sulfate reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: peanut oil 100g, methyl alcohol 20g, sodium hydroxide 1.2g (1.0g is used for transesterification reaction, and 0.2g is used for by-product recovery), 98% sulfuric acid 1.0g (being used for by-product recovery),
Output: biofuel 95.41g, raw glycerine 9.50g (glycerol content is 82.07%), sodium sulfate 1.5g, residue 2.93g (the fatty acid glycerine ester content is 59.50%) reclaims methyl alcohol 7.45g.
4. the main quality index of product
Adopt the main quality index of the peanut oil biofuel that Technology of the present invention prepares to see Table 2.
Embodiment 8 plam oil production biofuel
1. raw material basic condition: the palmitic basic condition of stock oil sees Table 1.
2. processing parameter
1. transesterify
Temperature of reaction: 70 ℃.
Transesterify number of times: once
Reaction times: 90 minutes
2. biofuel is refining
Temperature: biofuel still kettle liquid phase is 180～250 ℃, and gas phase is 120～200 ℃; Steam generator is 100 ± 5 ℃.Water vapor feeding amount: 5.5 liters/minute.
3. by-product recovery glycerine and sodium sulfate reclaim the glycerine recovery technology in the main reference sugar water.
3. produce and consume and output
In the biodiesel manufacture process, the result of the input of raw material and product output is as follows:
Drop into: plam oil 100g, methyl alcohol 20g, (1.0g is used for transesterification reaction to sodium hydroxide 1.3g, 0.3g be used for by-product recovery), 98% sulfuric acid 1.1g (being used for by-product recovery), output: biofuel 95.10g, raw glycerine 10.67g (glycerol content is 80.25%), sodium sulfate 1.7g, residue 4.5g (the fatty acid glycerine ester content is 76.62%) reclaims methyl alcohol 7.3g.
4. the main quality index of product
Adopt the main quality index of the plam oil biofuel that Technology of the present invention prepares to see Table 2.
The basic index of the various raw materials of table 1
| Raw material | Density (g/mL, 20 ℃) | Saponification value (mg KOH/g) | Acid number (mg KOH/g) | Unsaponifiables (%) | Fat glycerides (%) | Theoretical glycerol content (%) | Relative molecular weight |
| Swill oil | 0.89 | 194.3 | 163.0 | 2.82 | 15.24 | 1.89 | 323.5 |
| Jatropha curcas oil | 0.9093 | 183.6 | 19.0 | 1.20 | 89.98 | 9.08 | 759.5 |
| Rapeseed oil | 0.9115 | 192.7 | 0.4 | 2.51 | 97.29 | 10.05 | 869.8 |
| Soybean oil | 0.9178 | 198.8 | 1.6 | 1.28 | 97.91 | 10.47 | 833.2 |
| Oleum lini | 0.9149 | 189.2 | 0.7 | 2.52 | 97.13 | 10.03 | 883.0 |
| Peanut oil | 0.9172 | 192.7 | 0.3 | 1.25 | 98.60 | 10.14 | 870.7 |
| Plam oil | 0.92 | 197.4 | 0.7 | 2.31 | 97.34 | 10.55 | 846.6 |
The main quality index of table 2 biofuel
| Analysis project | Product index | ||||||
| The swill oil biofuel | Little tung oil biofuel | The rapeseed oil biofuel | The soybean oil biofuel | The oleum lini biofuel | The peanut oil biofuel | The plam oil biofuel | |
| Density (g/cm 3，20℃) | 0.8775 | 0.8742 | 0.8764 | 0.8800 | 0.8800 | 0.8783 | 0.8754 |
| Boiling range (95%), ℃ | 290 | 294 | 292 | 295 | 290 | 302 | 296 |
| Viscosity (mm 2/s，40℃) | 4.1 | 3.6 | 4.0 | 4.5 | 4.4 | 4.2 | 4.3 |
| Flash-point (℃) (open cup) | 152 | 153 | 156 | 156 | 158 | 160 | 152 |
| Burning-point (℃) (open cup) | 174 | 176 | 186 | 178 | 184 | 178 | 176 |
| Neutralization value (mgKOH/g oil) | 0.8 | 0.5 | 0.2 | 0.7 | 0.6 | 0.3 | 0.4 |
| Moisture (mg/kg) | 240 | 280 | 200 | 170 | 50 | 300 | 200 |
| Fatty acid methyl ester (%) | 99.38 | 98.82 | 98.55 | 98.94 | 96.50 | 98.41 | 97.30 |
| Total glycerol content (%) | 0.05 | 0.08 | 0.08 | 0.04 | 0.24 | 0.10 | 0.15 |
| Iodine number | 88.7 | 88.6 | 107.6 | 107.4 | 125.6 | 121.1 | 82.7 |
| Impurity (%) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Sulphur (%) | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 |
| Ash content (%) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Copper corrosion (50 ℃ of copper sheets, 3 hours) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Calorific value (KJ/g) | 38.15 | 39.12 | 38.76 | 40.83 | - | 40.22 | 39.90 |
Claims (6)
1, a kind of animal and vegetable oil prepares the technology of biofuel, is stock oil with lipid acid, high acid value or neutral animal-plant oil, comprises following production stage:
A. vapour phase esterification: 60～70 ℃ of methanol vapor that methanol gasifying device (1) produces are that the speed of 6～8 liters of/minute 100g stock oils enters into the esterifier (5) that stock oil and an acidic catalyst are housed through rectifying columns (2) back by the feeding amount, in temperature of reaction is to participate in esterification 30～120 minutes under 95～105 ℃ of conditions, the water vapor that reacted methanol vapor and reaction produce turns back in the methanol gasifying device (1) after condensation tower (3) condensation, and an acidic catalyst consumption is 0.2%～1.0% of a stock oil weight;
B. transesterify: the stock oil of handling through esterification enters transesterification reactor (10), 60～80 ℃ of transesterification reaction temperature; Methanol usage be in the stock oil glycerin fatty acid ester weight 20～25%, the basic catalyst consumption is 0.4～1.5% of a stock oil weight, reaction finishes the back and reclaims methyl alcohol earlier, separation of glycerin again, the coarse biodiesel that obtains enters biofuel rectifying reactor (15), and raw glycerine enters the by-product recovery art breading;
C. biofuel is refining: the water vapor that with temperature is 95～105 ℃ is the speed of 5～6 liters of/minute 100g stock oils by the feeding amount, enter from the bottom of rectifying reactor (15), carry out steam distillation, the liquid phase of biofuel rectifying reactor is 180～280 ℃, gas phase is 120～220 ℃, the biofuel that steams enters in the biofuel separator (18) after (17) condensation is leant in condensation with water vapor carries out separating of biofuel and water, biofuel is removed from separator (18), and the residual residue in the reactor (15) turns back in the biodiesel manufacture technology after the by-product recovery art breading.
2, preparation technology according to claim 1 is characterized in that: described an acidic catalyst is a sulfuric acid, and this catalyst preparation becomes 2% methanol solution use.
3, preparation technology according to claim 1 is characterized in that: described rectifying column reflux ratio is 2.0～2.5.
4, preparation technology according to claim 1 is characterized in that: described basic catalyst is potassium hydroxide or sodium hydroxide.
5, preparation technology according to claim 1 is characterized in that: described stock oil is oleic acid, catering trade waste oil, Jatropha curcas oil, rapeseed oil, soybean oil, oleum lini, peanut oil or plam oil.
6, preparation technology according to claim 1, it is characterized in that: it is that the raw glycerine that will produce from ester-exchange reaction is in neutralization reactor (20) that described by-product recovery is handled, in pH=3.5～4.5, refluxed 30 minutes under 65～75 ℃ of conditions of temperature, carry out acidification; Carry out separating of acidifying oil and glycerin layer then in acidifying oil separator (21), acidifying oil returns and carries out esterification treatment in the gaseous phase esterification reaction device, carries out the refining biofuel that obtains of steam distillation again; Glycerin layer is carried out basic treatment in alkaline purification reactor (22), hydro-oxidation potassium is to the pH=8, in evaporation concentration reactor (23), carry out concentration then, filter in strainer (24) and obtain raw glycerine and thick vitriolate of tartar, the methyl alcohol that is used for washing vitriolate of tartar reclaims at Methanol Recovery reactor (25).
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| CNB2005100757506A CN1328353C (en) | 2005-02-03 | 2005-06-01 | Technology of preparing biological diesel oil from animal and vegetable oil |
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| CNB2005100757506A CN1328353C (en) | 2005-02-03 | 2005-06-01 | Technology of preparing biological diesel oil from animal and vegetable oil |
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| CN101096602B (en) * | 2006-06-29 | 2011-02-16 | 周鼎力 | Method for continuous synthesis of biodiesel without catalyst |
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