CN102134528A - Method for continuously reducing acid number of oils with high acid value under fluidized state - Google Patents

Method for continuously reducing acid number of oils with high acid value under fluidized state Download PDF

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Publication number
CN102134528A
CN102134528A CN2011100432641A CN201110043264A CN102134528A CN 102134528 A CN102134528 A CN 102134528A CN 2011100432641 A CN2011100432641 A CN 2011100432641A CN 201110043264 A CN201110043264 A CN 201110043264A CN 102134528 A CN102134528 A CN 102134528A
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acid value
oil
fluidized
grease
oils
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聂小安
蒋剑春
张天健
陈洁
李科
常侠
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JIANGSU QIANGLI BIO-ENERGY Co Ltd
Institute of Chemical Industry of Forest Products of CAF
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JIANGSU QIANGLI BIO-ENERGY Co Ltd
Institute of Chemical Industry of Forest Products of CAF
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Abstract

The invention discloses a method for continuously reducing the acid number of oils with high acid value under the fluidized state. The method comprises the steps of: causing bottom-up gaseous methanol and cosolvent and top-down liquid oils with high acid value, the acid number of which ranges from 10 to 140 mg.g-1, to flow reversely at a fluidized second-stage solid acid catalyst segment so as to achieve liquid-gas esterification reaction, separating the gaseous methanol remained after reaction from the top of a reaction tower, and causing the remained gaseous methanol to enter a methanol fractionating tower; the oils with high acid value becomes the oils with low acid value, the acid number of which is lower than or equal to 3mg.g-1, after the liquid-gas esterification reaction, and then caused to enter the bottom of the reaction tower; when the determined quantity is reached, the oils with low acid value automatically flows into a storage tank for the oils with low acid value; the solid acid catalyst is a sulfonated coal catalyst; and the height of the fixed layer of each stage of the second-stage solid acid catalyst segment is 100 centimeters, and the piling height of the solid acid catalysts at each stage is from 70 to 80 centimeters. The method realizes the continuity of the entire process, avoids the safety loopholes of release, leakage and dropping in the process of production and shortens the time of esterification of the oils with high acid value.

Description

A kind of serialization fluidized reduces the method for high acid value acid value of oil and fat
Technical field
The invention belongs to the preparation field of biofuel, be specifically related to the method that a kind of serialization fluidized reduces high acid value acid value of oil and fat.
Background technology
High acid value grease is owing to contain the free fatty acids of various structures, and the acid value height is difficult to be finished by one step of general ester-interchange method, and its suitability for industrialized production rests on intermittent type or semicontinuous state all the time.The research of high acid value preparing biodiesel from lipid is more, and as Japanese Patent JP-A-7-197047 and JP-A-9235573, the raw material of preparation biofuel is exactly edible waste grease.Chinese patent CN1473907A has set forth the method for the high acid value preparing biodiesel from lipid of intermittent type, the present application people has discussed the homogeneous phase serialization at Chinese patent CN1916114A and has prepared method of bio-diesel oil, the raw material that relates to is the refining grease of low acid value, and its acid value is below 3.The intermittent type of high acid value stearic reaction, potential safety hazards such as " run, leak, drip " in the inevitable production process, also very serious by the equipment corrosion that liquid an acidic catalyst causes, also make facility investment repeatability too high simultaneously, cause the waste of manpower and materials.According to existing patented technology, also there are not effective ways to realize that the complete serialization of acid value falls in high acid value grease.
Summary of the invention
Fall the acid value technology and have equipment corrosion and environmental pollution important disadvantages in order to solve the traditional batch formula, and the production process that exists in the prior art can't serialization, easily produce the potential safety hazard of " run, leak, drip ", the invention provides the method that a kind of serialization fluidized reduces high acid value acid value of oil and fat, but catalytic efficiency height continuous production, the potential safety hazard of " run, leak, drip " in the effectively solution process.
The present invention takes following route to reduce greasy acid value:
Figure 2011100432641100002DEST_PATH_IMAGE001
Technical scheme of the present invention is: a kind of serialization fluidized reduces the method for high acid value acid value of oil and fat, under 80～100 ℃ of temperature, gasiform methyl alcohol and cosolvent from bottom to top with the acid number of from top to bottom liquid state at 10～140mg.g -1High acid value grease carry out liquid gas esterification in the secondary solid acid catalyst section adverse current that is fluidized, the intact gaseous methanol of unreacted leaves from the reaction tower top and enters the methyl alcohol separation column, and high acid value grease becomes acid number≤3 mg.g after through liquid gas esterification -1Low acid value grease enter reaction tower bottom, after the quantity that reaches setting, enter low acid value grease basin automatically;
Described solid acid catalyst is the sulphonated coal catalyzer; The fixedly floor height that described secondary solid acid catalyst section is every grade is 100 centimetres, and the heap height of every grade solid acid catalyst is 70～80 centimetres.
Described sulphonated coal catalyzer is a particulate state, and diameter is 0.2～0.5 centimetre.
Described sulphonated coal catalyzer can adopt following method preparation: the different grain size that bituminous coal is crushed to 0.2～0.5cm, the ratio that is 10:0.5～1 in sour coal mass ratio adds the sulphonating agent vitriol oil, be warming up to 100～160 ℃ of temperature of reaction, keep this thermotonus 8～10 h, cooling, filtration, washing, dry, granulation get diameter at 0.2～0.5 centimetre of particulate solid sulphonated coal catalyzer.
Described cosolvent is any one in tetrahydrofuran (THF), dioxane, the butanone.
Described cosolvent consumption is 20～30 % of methanol quality.
Described high acid value grease be in raw plant oil, sewer oil, swill oil or the acidifying oil any one.
Gaseous state reclaiming after making with extra care that unreacted is intact comes back to and continues in the reaction to use.
Described gasiform methyl alcohol and cosolvent enter reaction tower with 2.0mL/min speed, and methyl alcohol pressure remains 2.0kgf/cm in the reaction tower 2
Beneficial effect:
1. adopt reverse the feeding in raw material of high acid value grease and methyl alcohol that methyl alcohol is entered in the reaction tower in the mode of gas phase, enlarged the contact surface of reaction system, realize high acid value stearic reaction serialization;
2. in order to overcome the not high shortcoming of solid acid catalyst low-temperature catalytic activity below 70 ℃, adopt catalyst fluidization attitude reaction of high order tower, solid acid catalyst becomes fluidized under gaseous methanol impacts, increased the catalyzing esterification effect, make the esterification be able in the continuous reaction state, finish rapidly, avoided occurring in the process of reproduction " run, leak, drip " and potential safety hazard;
3. compare with sulfuric acid or organic acid, the present invention has reduced the corrosion of catalyzer to equipment to greatest extent, has reduced the pollution of waste water to environment.Catalyst system therefor has environmental protection, is easy to advantages such as recovery.
4. adopt co-solvent technology, grease and methyl alcohol become homogeneous phase by two-phase, have further accelerated speed of response, have shortened the reaction times.
5. after the reaction of methyl alcohol and fatty acid esterification, leave from the top, enter the methyl alcohol separation column, the regeneration of purified Methanol Recovery comes back to reaction tower and continues to use.
Description of drawings
The acid value process flow sheet falls in the high acid value grease of Fig. 1 serialization.
Wherein 1 is reaction tower, and 2 is one-level solid acid catalyst section, and 3 is secondary solid acid catalyst section, and 4 is high acid value grease preheater, 5 is high acid value grease pump, and 6 is the methyl alcohol knockout tower, and 7 is condenser, and 8 is the methyl alcohol receiver, 9 is methanol pump, and 10 is the methanol gasifying interchanger, and 11 are low acid value grease receiver.
Fig. 2 hangs down acid value Oleum Gossypii semen (acid number 0.25mg.g -1) infrared spectrogram
High acid value grease (the acid number 140mg.g of Fig. 3 -1) infrared spectrogram
Embodiment
Following examples are to further specify of the present invention, are not limitations of the present invention.
A kind of serialization fluidized reduces the method for high acid value acid value of oil and fat, gasiform methyl alcohol and cosolvent from bottom to top with the high acid value grease of liquid state under 100 ℃, adverse current is carried out liquid gas esterification in secondary solid acid catalyst section, solid acid catalyst wherein is under gaseous methanol impacts, be fluidized, increased the catalyzing esterification effect greatly, after methyl alcohol and the fatty acid esterification reaction, the intact gaseous methanol of unreacted leaves from the top, enter the methyl alcohol separation column, the regeneration of purified Methanol Recovery, come back to reaction tower and continue to use, high acid value grease becomes low acid value grease through the secondary solid acid catalysis, enters the reaction tower bottom, after reaching certain quantity, enter low acid value grease basin automatically.
Described solid acid catalyst is a particulate state sulphonated coal catalyzer, and diameter is at 0.2-0.5 centimetre.Adopt the preparation of following method: bituminous coal is crushed to different grain size, by sour coal than (mass ratio) for the 10:1 adding sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, and is extremely neutral with distilled water repetitive scrubbing suction filtration.To constant weight, granulation must diameter be a 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
In order to reach better effect, in the low greasy reaction of acid value of preparation, can use cosolvent.Described cosolvent can be in tetrahydrofuran (THF), dioxane, the butanone any.
Described cosolvent consumption is methanol quality fractional 20～30 %.
The low greasy acid number of acid value of the product that uses present method to produce≤3 mg.g -1
Described high acid value grease be in raw plant oil, sewer oil, swill oil or the acidifying oil any one, acid number is at 10～140mg.g -1
A kind of serialization fluidized reduces the method for high acid value acid value of oil and fat, and step is as follows more specifically:
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter in the methyl alcohol vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid acid catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 80～140mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses through refrigeration cycle.
Embodiment 1
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter methanol gasifying interchanger 10 through methanol pump 9, be heated to about 100 ℃, constantly enter in the reaction tower 1 by the bottom of reaction tower 1 with 2.0mL/min speed, gaseous form, diameter in the one-level solid acid catalyst section 2 at reaction tower 1 middle part and the secondary solid acid catalyst section 3 is that the particulate solid sulphonated coal catalyzer of 0.2～0.5cm is fluidization under the impact of methyl alcohol and cosolvent steam, keeps methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 20mg.g -1High acid value grease enter high acid value grease preheater 4 through high acid value grease pump 5 and be preheating to 100 ℃, enter in the reaction tower 1 with spray pattern, constantly be under the catalyst action of fluidized from top to bottom, carry out the adverse current esterification with gaseous methanol, the bottom that the low acid value grease that the process esterification obtains is fallen reaction tower 1, after arriving certain altitude, enter low acid value grease receiver 11 automatically, the low acid value oil and fat product acid number 1.2mg.g that obtains -1The unreacted methanol steam keeps 2.0kgf/cm 2Pressure constantly flows out from reaction tower 1 top, enters methyl alcohol knockout tower 6 and purifies, and enters in the methyl alcohol receiver 8 after condenser 7 coolings, reenters in the system with new methyl alcohol to recycle.The fixedly floor height that secondary solid acid catalyst section is every grade is 100 centimetres, and the heap height of every grade solid acid catalyst is 70～80 centimetres.Described cosolvent is any one in tetrahydrofuran (THF), dioxane, the butanone, and consumption is 20～30% of a methanol quality.
Embodiment 2
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter the vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid sulphonated coal catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 40mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses the low acid value oil and fat product acid number 1.5mg.g that obtains through refrigeration cycle -1
Embodiment 3
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter the vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid sulphonated coal catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 80mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses low acid value oil and fat product acid number 2.0 mg.g that obtain through refrigeration cycle -1
Embodiment 4
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter the vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid sulphonated coal catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 80 mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses low acid value oil and fat product acid number 2.1 mg.g that obtain through refrigeration cycle -1
Embodiment 4
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter the vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid sulphonated coal catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 100 mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses low acid value oil and fat product acid number 2.5 mg.g that obtain through refrigeration cycle -1
Embodiment 5
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter the vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid sulphonated coal catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 120 mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses low acid value oil and fat product acid number 2.8 mg.g that obtain through refrigeration cycle -1
Embodiment 6
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol, cosolvent enter the vaporization interchanger through methanol pump, are heated to about 100 ℃, constantly enter in 2.0mL/min speed gaseous state mode and contain in the secondary granule shape solid sulphonated coal catalyst reaction tower, keep methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 140 mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses low acid value oil and fat product acid number 3.0 mg.g that obtain through refrigeration cycle -1
Embodiment 6
Step 1 is crushed to different grain size with bituminous coal, by sour coal than (mass ratio) for 10:1 adds the sulphonating agent vitriol oil, be warming up to 160 ℃ of temperature of reaction, keep this thermotonus 10h, cooling filters remaining acid, with distilled water repetitive scrubbing suction filtration to neutrality.To constant weight, granulation gets diameter at 0.2-0.5 centimetre of particulate solid sulphonated coal catalyzer with 50 ℃ of following vacuum-dryings of sulphonated coal.
Step 2, methyl alcohol enters the vaporization interchanger through methanol pump, is heated to about 100 ℃, constantly enters in 2.0mL/min speed gaseous state mode and contains in the secondary granule shape solid sulphonated coal catalyst reaction tower, keeps methyl alcohol pressure 2.0kgf/cm in the tower 2; Acid value is 140 mg.g -1Grease enter the grease interchanger through grease pump, be heated to 100 ℃, enter in the reaction tower with spray pattern, from top to bottom constantly under the catalyst action of fluidized, carry out the adverse current esterification with gaseous methanol, through the bottom that the grease of second catalyst is fallen tower, behind the arrival certain altitude, enter low acid value grease basin automatically; Methyl alcohol keeps 2.0kgf/cm 2Pressure constantly flows out from the top, enters the methyl alcohol knockout tower and purifies, and uses low acid value oil and fat product acid number 5.8 mg.g that obtain through refrigeration cycle -1
Do not having under the situation of cosolvent, the low greasy acid number of acid value obviously increases.This explanation, the adding of cosolvent under the identical reaction times, helps improving speed of response, reduces the product acid number.
Embodiment 8
With acid number is 60mg.g -1Grease, with the catalytic treatment of secondary sulphonated coal, obtain acid number and be lower than 3 mg.g -1Low acid value grease the time, the catalytic activity reduction degree of catalyzer sees Table 1.
Table 1 sulphonated coal activity over time
Time (hr) 10 30 50 100 120 140
Acid number mg.g -1 1.3 1.6 2.2 2.5 3.0 3.3
As seen from the figure, acid number is 60mg.g -1Grease, as catalyzer, the catalysis time amounts up to 120 hours with sulphonated coal, sulphonated coal just must be changed, to keep the stability of esterification degree.
Sulphonated coal sees Table 2 to different acid number catalytic materials working lipe.
Table 2 sulphonated coal is to the catalytic material working lipe of different acid numbers
Effective catalysis time of catalyzer (hr) 180 150 120 100 90 80
Raw material acid number mg.g -1 20 40 60 80 100 140

Claims (8)

1. a serialization fluidized reduces the method for high acid value acid value of oil and fat, it is characterized in that, under 80～100 ℃ of temperature, gasiform methyl alcohol and cosolvent from bottom to top with the acid number of from top to bottom liquid state at 10～140mg.g -1High acid value grease carry out liquid gas esterification in the secondary solid acid catalyst section adverse current that is fluidized, the intact gaseous methanol of unreacted leaves from the reaction tower top and enters the methyl alcohol separation column, and high acid value grease becomes acid number≤3 mg.g after through liquid gas esterification -1Low acid value grease enter reaction tower bottom, after the quantity that reaches setting, enter low acid value grease basin automatically;
Described solid acid catalyst is the sulphonated coal catalyzer; The fixedly floor height that described secondary solid acid catalyst section is every grade is 100 centimetres, and the heap height of every grade solid acid catalyst is 70～80 centimetres.
2. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that, described sulphonated coal catalyzer is a particulate state, and diameter is 0.2～0.5 centimetre.
3. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that, described sulphonated coal catalyzer can adopt following method preparation: the different grain size that bituminous coal is crushed to 0.2～0.5cm, the ratio that is 10:0.5～1 in sour coal mass ratio adds the sulphonating agent vitriol oil, be warming up to 100～160 ℃ of temperature of reaction, keep this thermotonus 8～10 h, cooling, filtration, washing, dry, granulation get diameter at 0.2～0.5 centimetre of particulate solid sulphonated coal catalyzer.
4. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that, described cosolvent is any one in tetrahydrofuran (THF), dioxane, the butanone.
5. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that, described cosolvent consumption is 20～30 % of methanol quality.
6. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that described high acid value grease be in raw plant oil, sewer oil, swill oil or the acidifying oil any one.
7. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that gaseous state reclaiming after making with extra care that unreacted is intact comes back to and continues in the reaction to use.
8. serialization fluidized as claimed in claim 1 reduces the method for high acid value acid value of oil and fat, it is characterized in that, described gasiform methyl alcohol and cosolvent enter reaction tower with 2.0mL/min speed, and methyl alcohol pressure remains 2.0kgf/cm in the reaction tower 2
CN2011100432641A 2011-02-23 2011-02-23 Method for continuously reducing acid number of oils with high acid value under fluidized state Pending CN102134528A (en)

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CN104031747A (en) * 2014-06-13 2014-09-10 太原理工大学 Production device and method of biodiesel
CN105132190A (en) * 2015-08-21 2015-12-09 中国林业科学研究院林产化学工业研究所 Cyclic esterification method for preparing biodiesel from high-acid-value grease
CN105176697A (en) * 2015-08-17 2015-12-23 龙岩卓越新能源股份有限公司 Continuous esterification column apparatus for preparing biodiesel from waste fat and oil

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CN101353589A (en) * 2008-09-05 2009-01-28 中国林业科学研究院林产化学工业研究所 Method for preparing biodiesel by catalysis of nano magnetic sulphonated coal
CN101423770A (en) * 2008-12-08 2009-05-06 中国科学院广州能源研究所 Method for preparing biodiesel by using high acid number feed lipid

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CN104031747A (en) * 2014-06-13 2014-09-10 太原理工大学 Production device and method of biodiesel
CN104031747B (en) * 2014-06-13 2016-02-24 太原理工大学 A kind of production equipment of biofuel and production method
CN105176697A (en) * 2015-08-17 2015-12-23 龙岩卓越新能源股份有限公司 Continuous esterification column apparatus for preparing biodiesel from waste fat and oil
CN105132190A (en) * 2015-08-21 2015-12-09 中国林业科学研究院林产化学工业研究所 Cyclic esterification method for preparing biodiesel from high-acid-value grease

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Application publication date: 20110727