CN105462693A - Swill-cooked dirty oil pre-esterification process - Google Patents
Swill-cooked dirty oil pre-esterification process Download PDFInfo
- Publication number
- CN105462693A CN105462693A CN201510844515.4A CN201510844515A CN105462693A CN 105462693 A CN105462693 A CN 105462693A CN 201510844515 A CN201510844515 A CN 201510844515A CN 105462693 A CN105462693 A CN 105462693A
- Authority
- CN
- China
- Prior art keywords
- sewer oil
- methyl alcohol
- reflux
- total mass
- add
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a swill-cooked dirty oil pre-esterification process including the following steps: 1) preheating and dehydrating swill-cooked dirty oil; 2) adding methanol and a catalyst into the dehydrated swill-cooked dirty oil, and carrying out heating reflux at the temperature of 110-120 DEG C; 3) then adding methanol, and carrying out heating reflux at the temperature of 85-95 DEG C; and 4) carrying out settlement layering, separating to obtain an upper material, heating the upper material to 90-100 DEG C, recycling methanol, then heating up to 100-110 DEG C, next dehydrating, and thus obtaining a pre-esterified product. The swill-cooked dirty oil pre-esterification process has safe, stable and easy-to-control reaction process, effectively improves the esterification rate of the swill-cooked dirty oil, and also effectively reduces the acid value; and furthermore, the catalyst can be recycled, and is green and environmentally friendly.
Description
Technical field
The present invention relates to oil and fat chemical field, particularly a kind of pre-esterifying process of sewer oil.
Background technology
Sewer oil makes a general reference people in life for the common name of all kinds of poor quality oil.Sewer oil can be divided into following a few class: one is the sewer oil of narrow sense, by the greasy floating matter in water drain or by the leftovers of hotel, restaurant, leftovers (common name swill) oil through simply processing, extracting; Two is pork inferior, haslet, pigskin processing and the oil of output after refining; Three is after exceeding specified requirement for the oily access times of fried food product, then is reused or toward the oil reused after wherein adding some fresh oils.
Sewer oil is quality extreme difference, extremely antihygienic inedible oil, peroxide value, acid number, moisture severe overweight.It contains toxin, flows to rivers and can cause water nutrition, once edible, then can destroy white cell and alimentary canal mucous membrane, cause food poisoning, even carcinogenic serious consequence.Such as, the fried Cargo Oil prolonged and repeated use at high operating temperatures of one of " excessively rape oil ", contact with the oxygen in air, be hydrolyzed, be oxidized, the complex reaction such as polymerization, cause oily viscosity to increase, color and luster is deepened, and peroxide value raises, and producing the material of the irritant smell such as some volatile matters and aldehyde, ketone, lactone, these materials have carcinogenesis.The toxicity of the main harm thing in " swill oil "---flavacin is then 100 times of arsenic.
Biofuel is oil, the substitute of diesel fuel of high-quality.At present, become ripe with the technology of chemical method production biofuel, but be that the biofuel that raw material manufactures is on the high side with Vegetable oil lipoprotein, limited popularization.Adopt that cheap waste oil comprises tankage, hogwash oil, waste cooking oil or sewer oil in the edible oil course of processing, oil expression waste residue, the ageing oil of grain reserves, useless lard, plant waste etc. are raw material, raw materials cost can be made greatly to reduce, and price is more competitive.And by this kind of raw material production biofuel, acid number is a factor being badly in need of controlling.
At present, biodiesel oil preparing process mainly contains direct mixing method, mini-emulsion process, high-temperature cracking method, supercritical methanol technology and ester-interchange method.First two method belongs to physical method, though simple, can reduce animals and plants oil viscosity, cetane value is not high, and in burning, the problem such as carbon deposit and lubricant pollution is difficult to solve.High-temperature cracking method process is simple, and do not have pollutent to produce, shortcoming is at high temperature carried out, and cracking apparatus is expensive, and level of response difficulty controls, and reaction product is complicated, and by product is many, and high-temperature cracking method main products is biogasoline, and yield of biodiesel is not high.Supercritical methanol technology be a kind of High Temperature High Pressure instead of catalyzer to carry out the method for transesterification reaction, but the shortcoming of supercritical methanol technology is High Temperature High Pressure, high alcohol oil rate (normally 42:1), causes production cost high.
Be that biofuel prepared by raw material with sewer oil, the free fatty acids that sewer oil contains, polymkeric substance, resolvent etc., prepared by methyl esters to transesterify very unfavorable, sewer oil acid number is up to 144 (KOH)/(mg/g), if directly and methyl alcohol carry out transesterification reaction can with basic catalyst saponification, have a strong impact on reaction effect.Therefore first by pre-esterification, sewer oil acid number to be reduced to certain value, carry out preparing biodiesel by ester exchange again, usual pre-esterification uses the vitriol oil to be catalyzer, but vitriol oil acidity is high, corrodibility is strong, totally unfavorable to conversion unit, and the waste water produced has serious pollution to environment.
Summary of the invention
For solving the problem, the invention discloses a kind of pre-esterifying process of sewer oil, this pre-esterifying process adopts catalyst compounded and two ground beetle alcohol reflux esterification process, improves the esterification yield of sewer oil, and significantly reduce acid number, reaction process safety and stability, be easy to control.
Technical scheme of the present invention is: a kind of pre-esterifying process of sewer oil, comprise the steps: 1) by sewer oil preheating, dehydration, 2) methyl alcohol and catalyzer is added in sewer oil after dewatering, reflux at 110-120 DEG C, 3) add methyl alcohol reflux at 85-95 DEG C again, 4) carry out sedimentation layering, isolate upper materials, be warming up to 90-100 DEG C and reclaimed methyl alcohol, be warming up to 100-110 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
, described step 2 preferred as one) methyl alcohol add-on is the 15-20% of sewer oil total mass.
, described step 2 preferred as one) catalyst charge is the 1-3% of sewer oil total mass.
, described step 2 preferred as one) catalyzer is sodium pyrosulfate.Sodium pyrosulfate has obvious catalytic activity to esterification, and is insoluble to reaction system, has reacted rear easy process, pollution-free, can be recycled.
, described step 2 preferred as one) catalyzer is the catalyst compounded of sodium pyrosulfate, ferric sulfate and Tai-Ace S 150.Wherein sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 all can pass through roasting pretreatment before composite.Roasting pretreatment can remove the crystal water in vitriol, vitriol can be made in addition to produce the acid site of a considerable amount of medium tenacity, and have higher selectivity to esterification, be conducive to the carrying out of esterification.
Preferred as one, the sodium pyrosulfate in described catalyzer, ferric sulfate and Tai-Ace S 150 mass ratio are (4-5): (1-3): 1.Sodium pyrosulfate has higher catalytic activity as the catalyzer of esterification, but it is active in order to improve it further, therefore itself and ferric sulfate and Tai-Ace S 150 are carried out composite, the active centre of these three kinds of vitriol can be made to play synergy, to strengthen the acidity of sodium pyrosulfate, when its mass ratio is 5:3:1, the catalytic activity of sodium pyrosulfate reaches maximum.
, described step 2 preferred as one) time of reflux is 1-2h.Because methyl alcohol volatility is high, boiling point only has 64.7 DEG C at ambient pressure, and when reacting by heating, methanol molecules is easily overflowed, so be employed herein technique of backflow, methyl alcohol be fully utilized, reduce the loss.And backflow can improve reaction mass transfer and rate of heat transfer, speed of reaction, mixing reactant can be accelerated, temperature of reaction can also be made simultaneously to keep constant, make reaction more stable.
, described step 3 preferred as one) methyl alcohol add-on is the 10-15% of sewer oil total mass.Because the reaction of the lipid acid in sewer oil and methyl alcohol is reversible reaction, and reaction is relatively violent, and in order to make esterification more thoroughly and more stable, therefore add methyl alcohol at twice, the methyl alcohol total amount added for twice is excessive.
, described step 3 preferred as one) time of reflux is 1-5h.After reflux completes, sampling carry out acid value detection, detected result carries out next step after reaching standard, the standard wherein detected be acid number lower than 3 (KOH)/(mg/g), if acid number does not meet this standard, then easily cause product saponification.
, described step 4 preferred as one) the lower floor's material also comprised sedimentation multi_layer extraction goes out processes, and reclaims methyl alcohol and catalyzer.The realization of this step can by filtering and clean and reuse catalyzer, and residue mixing waste is heated to 95 DEG C and reclaims residual methanol, and catalyzer and the methyl alcohol of recovery can be recycled.
Beneficial effect of the present invention: sewer oil pre-esterifying process of the present invention adopts catalyst compounded, by vacuum hydro-extraction and two ground beetle alcohol reflux esterification process, improve the esterification yield of sewer oil, and significantly reduce acid number, reaction process safety and stability, be easy to control, and catalyzer can be recycled, environmental protection.
Embodiment
Below in conjunction with embodiment, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
The pre-esterifying process of sewer oil of the present invention, comprise the steps: 1) by sewer oil preheating, dehydration, 2) methyl alcohol and catalyzer is added in sewer oil after dewatering, reflux at 110-120 DEG C, 3) add methyl alcohol reflux at 85-95 DEG C again, 4) carry out sedimentation layering, isolate upper materials, be warming up to 90-100 DEG C and reclaimed methyl alcohol, be warming up to 100-110 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
, step 2 preferred as one) methyl alcohol add-on is the 15-20% of sewer oil total mass.
, step 2 preferred as one) catalyst charge is the 1-3% of sewer oil total mass.
, step 2 preferred as one) catalyzer is sodium pyrosulfate.
, step 2 preferred as one) catalyzer is the catalyst compounded of sodium pyrosulfate, ferric sulfate and Tai-Ace S 150.
Preferred as one, the sodium pyrosulfate in described catalyzer, ferric sulfate and Tai-Ace S 150 mass ratio are (4-5): (1-3): 1.
, step 2 preferred as one) time of reflux is 1-2h.
, step 3 preferred as one) methyl alcohol add-on is the 10-15% of sewer oil total mass.
, step 3 preferred as one) time of reflux is 1-5h.
, step 4 preferred as one) the lower floor's material also comprised sedimentation multi_layer extraction goes out processes, and reclaims methyl alcohol and catalyzer.
Embodiment 1
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 102 DEG C, carries out vacuum hydro-extraction,
2) methyl alcohol and sodium bisulfate catalysis agent is added, reflux 1h at 110 DEG C in sewer oil after dewatering; Wherein methyl alcohol add-on is 15% of sewer oil total mass, and catalyst charge is 1% of sewer oil total mass,
3) add methyl alcohol reflux 1.5h at 85 DEG C again, methyl alcohol add-on is 10% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 90 DEG C and reclaim methyl alcohol, be warming up to 102 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
Embodiment 2
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 107 DEG C, carries out vacuum hydro-extraction,
2) add methyl alcohol and sodium bisulfate catalysis agent, reflux 1.1h at 112 DEG C in sewer oil after dewatering, wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass,
3) add methyl alcohol reflux 3h at 86 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 95 DEG C and reclaim methyl alcohol, be warming up to 107 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
Embodiment 3
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 105 DEG C, carries out vacuum hydro-extraction,
2) add methyl alcohol and sodium bisulfate catalysis agent, reflux 1.5h at 114 DEG C in sewer oil after dewatering, wherein methyl alcohol add-on is 16% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass,
3) add methyl alcohol reflux 4.5h at 93 DEG C again, methyl alcohol add-on is 14% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 100 DEG C and reclaim methyl alcohol, be warming up to 105 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
Embodiment 4
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 109 DEG C, carries out vacuum hydro-extraction,
2) add methyl alcohol and sodium bisulfate catalysis agent, reflux 1.9h at 116 DEG C in sewer oil after dewatering, wherein methyl alcohol add-on is 19% of sewer oil total mass, and catalyst charge is 3% of sewer oil total mass,
3) add methyl alcohol reflux 2h at 94 DEG C again, methyl alcohol add-on is 13% of sewer oil total mass;
4) carry out sedimentation layering, isolate upper materials, be warming up to 98 DEG C and reclaim methyl alcohol, be warming up to 109 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
Embodiment 5
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 105 DEG C, carries out vacuum hydro-extraction,
2) add methyl alcohol and sodium bisulfate catalysis agent, reflux 1.5h at 120 DEG C in sewer oil after dewatering, wherein methyl alcohol add-on is 18% of sewer oil total mass, and catalyst charge is 3% of sewer oil total mass,
3) add methyl alcohol reflux 5h at 95 DEG C again, methyl alcohol add-on is 11% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 92 DEG C and reclaim methyl alcohol, heat up again 105 DEG C after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
Embodiment 6
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 102 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of methyl alcohol and sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 is added in sewer oil after dewatering, reflux 1h at 114 DEG C; Wherein methyl alcohol add-on is 15% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass,
3) add methyl alcohol reflux 1.5h at 86 DEG C again, methyl alcohol add-on is 10% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 90 DEG C and reclaim methyl alcohol, be warming up to 102 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 7
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 107 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of methyl alcohol and sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 is added in sewer oil after dewatering, reflux 1.1h at 111 DEG C, wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass
3) add methyl alcohol reflux 3h at 88 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 94 DEG C and reclaim methyl alcohol, be warming up to 107 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 8
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 105 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of methyl alcohol and sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 is added in sewer oil after dewatering, reflux 1.5h at 115 DEG C, wherein methyl alcohol add-on is 16% of sewer oil total mass, and catalyst charge is 1% of sewer oil total mass
3) add methyl alcohol reflux 4.5h at 94 DEG C again, methyl alcohol add-on is 14% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 96 DEG C and reclaim methyl alcohol, be warming up to 105 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 9
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 109 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of methyl alcohol and sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 is added in sewer oil after dewatering, reflux 1.9h at 119 DEG C, wherein methyl alcohol add-on is 18% of sewer oil total mass, and catalyst charge is 1% of sewer oil total mass
3) add methyl alcohol reflux 2h at 94 DEG C again, methyl alcohol add-on is 13% of sewer oil total mass;
4) carry out sedimentation layering, isolate upper materials, be warming up to 99 DEG C and reclaim methyl alcohol, be warming up to 110 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 10
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 105 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of methyl alcohol and sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 is added in sewer oil after dewatering, reflux 1.5h at 120 DEG C, wherein methyl alcohol add-on is 18% of sewer oil total mass, and catalyst charge is 3% of sewer oil total mass
3) add methyl alcohol reflux 4.5h at 95 DEG C again, methyl alcohol add-on is 12% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 100 DEG C and reclaim methyl alcohol, be warming up to 105 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 11
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 100 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of sodium pyrosulfate, ferric sulfate and the Tai-Ace S 150 that methyl alcohol and mass ratio are 4:1:1 is added in sewer oil after dewatering, reflux 1h at 110 DEG C; Wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 3% (wherein sodium pyrosulfate, ferric sulfate and Tai-Ace S 150 are before composite by roasting pretreatment) of sewer oil total mass,
3) add methyl alcohol reflux 1h at 85 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 95 DEG C and reclaim methyl alcohol, be warming up to 100 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 12
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 102 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of sodium pyrosulfate, ferric sulfate and the Tai-Ace S 150 that methyl alcohol and mass ratio are 4:2:1 is added in sewer oil after dewatering, reflux 1.2h at 112 DEG C, wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 3% of sewer oil total mass
3) add methyl alcohol reflux 3h at 87 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 95 DEG C and reclaim methyl alcohol, be warming up to 102 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 13
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 105 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of sodium pyrosulfate, ferric sulfate and the Tai-Ace S 150 that methyl alcohol and mass ratio are 4:3:1 is added in sewer oil after dewatering, reflux 1.5h at 114 DEG C, wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass
3) add methyl alcohol reflux 4h at 89 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 95 DEG C and reclaim methyl alcohol, be warming up to 105 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 14
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 108 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of sodium pyrosulfate, ferric sulfate and the Tai-Ace S 150 that methyl alcohol and mass ratio are 5:1:1 is added in sewer oil after dewatering, reflux 1.7h at 116 DEG C, wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass
3) add methyl alcohol reflux 2h at 85 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass;
4) carry out sedimentation layering, isolate upper materials, be warming up to 95 DEG C and reclaim methyl alcohol, be warming up to 108 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Embodiment 15
The pre-esterifying process of the sewer oil of the present embodiment, step is as follows:
1) sewer oil is preheated to 110 DEG C, carries out vacuum hydro-extraction,
2) the catalyst compounded of sodium pyrosulfate, ferric sulfate and the Tai-Ace S 150 that methyl alcohol and mass ratio are 5:3:1 is added in sewer oil after dewatering, reflux 2h at 120 DEG C, wherein methyl alcohol add-on is 20% of sewer oil total mass, and catalyst charge is 2% of sewer oil total mass
3) add methyl alcohol reflux 5h at 95 DEG C again, methyl alcohol add-on is 15% of sewer oil total mass,
4) carry out sedimentation layering, isolate upper materials, be warming up to 95 DEG C and reclaim methyl alcohol, be warming up to 110 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product; Lower floor's material that sedimentation multi_layer extraction goes out is processed, reclaims methyl alcohol and catalyzer.
Comparative example
In sewer oil, add the vitriol oil dewater, the sewer oil after dehydration and methyl alcohol are joined in reactor, then adds the vitriol oil, be heated to 120 DEG C, react after 2 hours and stop heating, take out mixture, stratification, isolates upper materials, obtains pre-esterification product.
The pre-esterification product getting above each embodiment and comparative example carries out acid value detection, and calculates esterification yield, and wherein the data of embodiment 6-15 are listed in table 1.
Table 1
| Acid number [(KOH)/(mg/g)] | Esterification yield (%) | |
| Embodiment 1 | 0.80 | 97.5 |
| Embodiment 2 | 0.80 | 97.4 |
| Embodiment 3 | 0.78 | 97.4 |
| Embodiment 4 | 0.77 | 97.5 |
| Embodiment 5 | 0.79 | 97.9 |
| Embodiment 6 | 0.75 | 98.1 |
| Embodiment 7 | 0.68 | 98.0 |
| Embodiment 8 | 0.78 | 98.6 |
| Embodiment 9 | 0.53 | 98.5 |
| Embodiment 10 | 0.59 | 98.4 |
| Embodiment 11 | 0.33 | 98.4 |
| Embodiment 12 | 0.40 | 98.5 |
| Embodiment 13 | 0.36 | 98.9 |
| Embodiment 14 | 0.35 | 98.7 |
| Embodiment 15 | 0.25 | 99.4 |
| Comparative example | 1.68 | 88.9 |
In data measured by various embodiments of the present invention, acid number is all less than or equal to 0.80 (KOH)/(mg/g), and esterification yield is all more than or equal to 97.4%, therefore pre-esterifying process of the present invention has better technique effect compared with comparative example.
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize herein to illustrate, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment herein.
The technical scope mid point value non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned technique means, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. the pre-esterifying process of a sewer oil, it is characterized in that comprising the steps: 1) by sewer oil preheating, dehydration, 2) methyl alcohol and catalyzer is added in sewer oil after dewatering, reflux at 110-120 DEG C, 3) add methyl alcohol reflux at 85-95 DEG C again, 4) carry out sedimentation layering, isolate upper materials, be warming up to 90-100 DEG C and reclaimed methyl alcohol, be warming up to 100-110 DEG C again after recovery methyl alcohol completes and dewater, obtain pre-esterification product.
2. the pre-esterifying process of sewer oil according to claim 1, is characterized in that: described step 2) methyl alcohol add-on is the 15-20% of sewer oil total mass.
3. the pre-esterifying process of sewer oil according to claim 1, is characterized in that: described step 2) catalyst charge is the 1-3% of sewer oil total mass.
4. the pre-esterifying process of the sewer oil according to claim 1 or 3, is characterized in that: described step 2) catalyzer is sodium pyrosulfate.
5. the pre-esterifying process of the sewer oil according to claim 1 or 3, is characterized in that: described step 2) catalyzer is the catalyst compounded of sodium pyrosulfate, ferric sulfate and Tai-Ace S 150.
6. the pre-esterifying process of sewer oil according to claim 5, is characterized in that: the sodium pyrosulfate in described catalyzer, ferric sulfate and Tai-Ace S 150 mass ratio are (4-5): (1-3): 1.
7. the pre-esterifying process of sewer oil according to claim 1, is characterized in that: described step 2) time of reflux is 1-2h.
8. the pre-esterifying process of sewer oil according to claim 1, is characterized in that: described step 3) methyl alcohol add-on is the 10-15% of sewer oil total mass.
9. the pre-esterifying process of sewer oil according to claim 1, is characterized in that: described step 3) time of reflux is 1-5h.
10. the pre-esterifying process of sewer oil according to claim 1, is characterized in that: described step 4) the lower floor's material also comprised sedimentation multi_layer extraction goes out processes, and reclaims methyl alcohol and catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510844515.4A CN105462693A (en) | 2015-11-27 | 2015-11-27 | Swill-cooked dirty oil pre-esterification process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510844515.4A CN105462693A (en) | 2015-11-27 | 2015-11-27 | Swill-cooked dirty oil pre-esterification process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105462693A true CN105462693A (en) | 2016-04-06 |
Family
ID=55600861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510844515.4A Pending CN105462693A (en) | 2015-11-27 | 2015-11-27 | Swill-cooked dirty oil pre-esterification process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105462693A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085929A (en) * | 2007-02-12 | 2007-12-12 | 源华卓越能源科技（福建）有限公司 | Technique for producing biological diesel oil by Louis acid catalysis one-step method |
| CN101161784A (en) * | 2007-11-22 | 2008-04-16 | 中国农业科学院油料作物研究所 | Method for extracting conversion biodiesel from oil pressing cake |
| CN101445742A (en) * | 2008-12-30 | 2009-06-03 | 浙江工业大学 | Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil |
| CN102181324A (en) * | 2011-03-30 | 2011-09-14 | 杨大伟 | Method for producing biodiesel by using solid acid to catalyze waste animal and vegetable oils and fats |
| CN102876465A (en) * | 2012-09-07 | 2013-01-16 | 宝林 | Method for preparing biodiesel by using kitchen waste oil |
| CN103031216A (en) * | 2013-01-09 | 2013-04-10 | 杨玉峰 | Pre-esterification process for producing biodiesel from illegal cooking oil |
| CN103421615A (en) * | 2013-05-20 | 2013-12-04 | 西安市宝润实业发展有限公司 | Technology for producing biodiesel through illegal cooking oil or waste cooking oil |
| CN104004596A (en) * | 2014-06-18 | 2014-08-27 | 刘火成 | Method for producing biodiesel by means of animal and plant waste oil at high acid value |
-
2015
- 2015-11-27 CN CN201510844515.4A patent/CN105462693A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085929A (en) * | 2007-02-12 | 2007-12-12 | 源华卓越能源科技（福建）有限公司 | Technique for producing biological diesel oil by Louis acid catalysis one-step method |
| CN101161784A (en) * | 2007-11-22 | 2008-04-16 | 中国农业科学院油料作物研究所 | Method for extracting conversion biodiesel from oil pressing cake |
| CN101445742A (en) * | 2008-12-30 | 2009-06-03 | 浙江工业大学 | Method for preparing biodiesel by utilizing stratified and graded esterified deacidification of high acid value oil |
| CN102181324A (en) * | 2011-03-30 | 2011-09-14 | 杨大伟 | Method for producing biodiesel by using solid acid to catalyze waste animal and vegetable oils and fats |
| CN102876465A (en) * | 2012-09-07 | 2013-01-16 | 宝林 | Method for preparing biodiesel by using kitchen waste oil |
| CN103031216A (en) * | 2013-01-09 | 2013-04-10 | 杨玉峰 | Pre-esterification process for producing biodiesel from illegal cooking oil |
| CN103421615A (en) * | 2013-05-20 | 2013-12-04 | 西安市宝润实业发展有限公司 | Technology for producing biodiesel through illegal cooking oil or waste cooking oil |
| CN104004596A (en) * | 2014-06-18 | 2014-08-27 | 刘火成 | Method for producing biodiesel by means of animal and plant waste oil at high acid value |
Non-Patent Citations (1)
| Title |
|---|
| 俞凌云等: "两步化学法催化猪皮废油和潲水油制备生物柴油", 《西部皮革》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qian et al. | Preparation of biodiesel from Jatropha curcas L. oil produced by two-phase solvent extraction | |
| Rashid et al. | Production of sunflower oil methyl esters by optimized alkali-catalyzed methanolysis | |
| EP2636747B1 (en) | Process for preparing biodiesel with lipase and separate online dehydration | |
| Lianhua et al. | Esterification of high FFA tung oil with solid acid catalyst in fixed bed reactor | |
| He et al. | Continuous biodiesel production from acidic oil using a combination of cation-and anion-exchange resins | |
| CN104004596B (en) | A kind of method utilizing high acid value propagation waste oil production biofuel | |
| CN105273837A (en) | Comprehensive utilization method for swill-cooked dirty oil | |
| CN101338214B (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 | |
| CN104450207A (en) | Improved process for reducing acid value of illegal cooking oil or acidified oil by using glycerin esterification process | |
| CN1670128A (en) | Process for preparing biological diesel oil by using waste oil | |
| CN102618391B (en) | Method for synthesizing biodiesel by waste oil under catalysis of composite solid acid | |
| Go et al. | Biodiesel from rice bran lipids: resource assessment and technological review | |
| CN101148599B (en) | Method for preparing biological diesel oil from waste animals and plants grease with high acid value | |
| CN101104810A (en) | Preparation method for biological diesel oil | |
| CN105462693A (en) | Swill-cooked dirty oil pre-esterification process | |
| CN101649333B (en) | Method for producing biodiesel by utilizing leftovers from deep processing of litchi | |
| CN112251471A (en) | Enzymatic process for preparing biodiesel from acidified oil | |
| Costa et al. | Glycerolysis of two high free fatty acid waste materials for biodiesel production | |
| CN101993784A (en) | Method for preparing biodiesel from hogwash oil catalyzed by solid super acid | |
| CN102181324A (en) | Method for producing biodiesel by using solid acid to catalyze waste animal and vegetable oils and fats | |
| CN101113363A (en) | Method for producing biodiesel | |
| CN104726145B (en) | A kind of biodiesel and preparation method thereof | |
| CN101289629A (en) | Process for preparing biodiesel by one-step method using biomass based sulfonation charcoal as fatty acid esterification and triglyceride transform esterification catalysts | |
| CN107034243A (en) | The preparation technology of fatty acid short-chain ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160406 |