CN104818125A - Method for using waste oil and grease as raw material to prepare fatty acid methyl ester - Google Patents
Method for using waste oil and grease as raw material to prepare fatty acid methyl ester Download PDFInfo
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- CN104818125A CN104818125A CN201510217955.7A CN201510217955A CN104818125A CN 104818125 A CN104818125 A CN 104818125A CN 201510217955 A CN201510217955 A CN 201510217955A CN 104818125 A CN104818125 A CN 104818125A
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
- C11C3/10—Ester interchange
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0484—Vegetable or animal oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
Abstract
The invention discloses a method for using waste oil and grease as raw material to prepare fatty acid methyl ester. The method mainly comprises the steps of raw material oil preprocessing, esterification workshop section, ester exchange, coarse methyl ester rectification, washing and glycerinum purification and recovery. The utilization rate of raw material oil is high, and the water and sediment content of raw material oil is not limited. The coarse alkyl ester rectification efficiency of a rectification system is improved by adding boric acid. On the premise that the raw material requirement is net and by the adoption of process treatment, the conversion rate of drainage oil and swill oil is 86-87%, the conversion rate of fatty acid is 92-93%, and the processing cost is low (700-800 yuan/ton). The method is suitable for industrial fatty acid methyl ester preparation.
Description
Technical field
The invention belongs to the preparation field of fatty acid methyl ester (or biofuel), is the preparation method of the fatty acid methyl ester taking waste grease as raw material.
Background technology
Fatty acid methyl ester, prepares except fatty alcohol or environment-friendly plasticizer except can be used as chemical intermediate, at present mainly as procetane by people are familiar with.Each quasi-grease that its raw material is normally discarded, mainly from the waste oil of catering trade.Because the complicacy of raw material and the uncertainty of composition make the suitability for industrialized production preparation of fatty acid methyl ester there are some problems.Such as, prepare methyl esters normally adopt discontinuous preparation method, methyl alcohol batch feed at use abendoned oil, moisture cannot be discharged in time, easily causes saponification phenomenon, thus can not get alkyl ester or occur the phenomenons such as the productive rate that causes due to saponification is low, energy consumption is high.In addition, rectification efficiency is lower.
In prior art, name is called " production method of biofuel ", publication number: CN 103468413A, and biodiesel oil preparing process is prepared in a kind of acid of proposition, alkali two-step catalysis.The feature of its technique is mainly reflected in it and does not use common sulfuric acid as catalyzer in esterification operation.But its catalyzer used is the product of German BASF, its price is approximately four times of common sulfuric acid.
Name is called " a kind of preparation method of biofuel ", publication number: CN103320233A, the biofuel fabricating technology of a kind of serialization that the method proposes.This technique does not relate to transesterification reaction, is directly after the lipid acid on upper strata being carried out esterification by a kind of tubular reactor after stock oil acidication, to prepare fatty acid alkyl ester.But originally can not process as the glycerine of high added value product, therefore, discarded oil resource is not utilized fully.
Name is called " robust multienzyme preparation for fatty acid alkyl Lipase absobed ", publication number: CN101932717A.This patent application proposes to use prepares fatty acid methyl ester through immobilized lipase.But the preparation cost of fixed lipase catalyzed dose cannot be competed with the sulphonic acids catalyzer of common sulfuric acid or BASF AG.And this patent application just refer to and generates fatty acid methyl ester with grease under fixed lipase catalyzed dose of effect, obtains refining fatty acid methyl ester finished product also have a segment distance from reality.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of take waste grease as the preparation method of the fatty acid methyl ester of raw material.
Scheme is as follows: a kind of take waste grease as the preparation method of the fatty acid methyl ester of raw material, and step is as follows:
1) pre-treatment
Waste grease send into chemical oil pool by be heated to 60 ?about 80 DEG C, send into knockout tower after grease fusing to be solidified, in knockout tower, temperature remains on 40 DEG C, the water of bottom of draining after leaving standstill and impurity;
2) esterification:
By step 1) pretreated oil plant sends in pre-esterification reaction still by fresh feed pump, when temperature rises to 95 DEG C, pass into methyl alcohol, control the bubbles volume produced in reactor, logical methyl alcohol added sulfuric acid after 5 minutes, temperature was risen to 105 ± 4 DEG C, react 2 ?3 hours, when acid value is lower than 2mgKOH/g, stop logical alcohol, turn and expect separating tank;
3) acid discharge slag:
After static 1 hour, separating tank lower floor acid sludge is discharged;
4) transesterify:
By step 3) be separated the oil plant that obtains and pump into transesterification reaction still, add anhydrous methanol simultaneously, then appropriate NaOH is added, ester interchange vessel is added after dissolving with anhydrous first class alcohol, be warmed up to 55 DEG C, abundant stirring reaction is after 30 minutes, by step 3) acid sludge of discharging regulates mixture pH value to neutrality;
5) dealcoholysis, dehydration:
Start the dealcoholysis of vacuum pump intensification drying and dehydrating, negative pressure after first normal pressure, constant pressure and dry starts negative pressure drying to during visor wireless streams sample, until during visor wireless streams sample, is considered as thoroughly dry;
6) glycerine and smart alkyl ester separation, extraction:
Discharge bottom raw glycerine after crude fatty acid methyl ester stratification and enter raw glycerine storage tank,
Then enter vacuum rectifying tower by after the preheating of thick for upper strata methyl esters phase, through distillation oil plant by condenser after enter smart methyl esters holding tank, finally send into store tank field.
Step 2) described esterification be by reactor bottom gas distributor the alcohol gas being in boiling state is passed through reaction kettle of the esterification, and uniformly dispersing is in the middle of reaction interface, the water-band that reaction generates is gone out reacting phase, the gas overflowed obtains moisture crude carbinol after condensation, can reuse after processed.Described gas distributor is coil pipe type, helically type, coiled pipe is distributed with radius 0.5 ?the circular hole of 1cm.
Step 2) described sulfuric acid dripping quantity be oil plant heavy 0.8%.
Step 1) described in the acid value height of waste grease on reaction not impact, main raw material is sewer oil, swill oil, acidification oil.
Step 4) described in ester-exchange reaction in should first NaOH be dissolved in anhydrous methanol, then evenly instill in reactor.The consumption of sodium hydroxide is obtained by following formulae discovery:
W＝[0.0713×AV+0.4]×M/100
W ?alkali consumption,
The initial acid value of AV ?waste grease,
M ?waste grease quality.
Step 6) in, in thick methyl esters rectifying by add boric acid improve methyl esters rectification efficiency, by mass percentage 0.1% ?0.5% addition add boric acid reduce fuel-displaced time rectifying tower temperature.
Step 6) in, the purification of glycerine adopts the technique of rectification under vacuum to carry out, concrete operations are: use vacuum system by the vacuum cavitations of rectifying tower 0.7 ?open thermal oil after 0.8MPa, keep bottom temperature to be no more than 203 DEG C and to be advisable, the glycerine that rectifying is obtained and powdered active carbon by mass percentage 1.5% ratio mix and blend centrifugal glycerol product obtaining refining after 3 hours.
Determining whether step 6 according to the application target of fatty acid methyl ester further) the smart methyl esters that obtains washes, if the fatty acid methyl ester of preparation is used as vehicle fuel, wash, otherwise then do not need, the concrete steps of washing are: open water wash product pump using squeeze into as the distilling material of automobile oil washing pool pass into the aqueous solution being added with de-acidying agent again after static 1 hour, upper oil phase is required product.
Described washing adopts de-acidying agent to wash, de-acidying agent is made up of ammonium chloride, sodium-chlor, sodium hydroxide, with fresh water be mixed with mass percent 0.2 ?0.5% solution after in smart methyl esters weight 1 ?5% ratio add, upper oil phase can be used as vehicle fuel and uses, and lower floor's aqueous phase is reusable.
Beneficial effect of the present invention:
1, the grease mainly discarded of raw material, as swill oil, sewer oil, all low price of acidifying wet goods, discard and the mixture of the glyceryl ester can mixed containing water and free fatty acids, therefore there is the features such as source range is wide, cost is low, impurity is many, common process produces the phenomenon easily occurring saponification;
2, esterification technique is except using sulfuric acid, and use the reactor with gas distributor to carry out, the water that this esterification technique cost is low, use ratio of methanol is high, esterification produces takes reactor out of, on follow-up transesterification reaction of carrying out without impact under the effect of gas-phase methanol and heat;
3, transesterify system alkaline catalysts consumption according to formulae discovery accurately and adopt the mode that equal uniform flow adds, can prevent unnecessary saponification;
4, in distillation system, use boric acid, reduce rectifying and go out temperature required for product, thus reduce the energy consumption of rectifying;
Due to adding of dewatering agent, the water yield required for the washing process of smart methyl esters is significantly reduced, washing churning time and number of times reduce, and glycerine decreasing ratio is higher and do not need to heat water washing tank.Under general operating mode, can remove acid and glycerine preferably at about 20 DEG C, production process is environmental protection more.
Accompanying drawing explanation
Fig. 1 is the method flow diagram of the embodiment of the present invention;
Fig. 2 be the embodiment of the present invention a kind of reactor bottom the structural representation of gas distributor, comprise the site plan of left half gas distributor, the vertical view of upper right portion gas distributor, the upward view of lower right-most portion gas distributor;
Fig. 3 is the survey report figure of a finished product of the embodiment of the present invention.
Embodiment
The present patent application selects sulfuric acid as catalyzer, and carries out acid discharge technique.The esterification that the acid catalyst of discharging can be used as next batch produce and in and the product of transesterify workshop section.That discards on a small quantity can enter Sewage treatment systems.Cost is lower than using the sulphonic acids catalyzer of BASF AG in general.In addition, when all using gas phase methyl esters to carry out esterification, we install aerating system additional in the reactor bottom of esterification technique, improve the result of use of methyl alcohol.Finally, we improve the rectification efficiency of thick methyl esters in rectification under vacuum system by adding boric acid, by adding a small amount of boric acid, significantly reduce the temperature required for rectifying.
Waste cooking oil is vegetables oil, animal oil mainly, and easily congeal into Tofu pudding shape grease or lump, for guaranteeing sewer oil mobility, heating installation must be adopted grease melt processed.After sewer oil is marched into the arena, be first unloaded in reception tank, reduced by viscosity after steam heating in pond, mobility increases, with whizzer by grease≤the solid material of 0.5mm removes.Oil-water mixture enters follow-up fatty acid methyl ester and prepares workshop.The crude product obtained distills out residual methyl alcohol, and by raw glycerine and thick methyl esters standing separation.Finally enter rectification cell respectively.
Acid-base catalysis unit will add methyl alcohol, and the useless methyl alcohol after catalyzed reaction enters standing tank, flashes off methyl alcohol reuse through methyl alcohol distillation tower.In addition, spent acid, alkali decontaminated water treatment plant.
Take waste grease as a preparation method for the fatty acid methyl ester of raw material, as shown in Figure 1,
Step is as follows:
1) pre-treatment
Waste grease send into chemical oil pool by be heated to 60 ?about 80 DEG C, grease melt after send into knockout tower, in knockout tower, temperature remains on 40 DEG C, leave standstill after drain bottom water and impurity;
2) esterification:
By step 1) pretreated oil plant sends in pre-esterification reaction still by fresh feed pump, when temperature rises to 95 DEG C, pass into methyl alcohol, control the bubbles volume produced in reactor, logical methyl alcohol added sulfuric acid after 5 minutes, temperature was risen to 105 ± 4 DEG C, react 2 ?3 hours, when acid value is lower than 2mgKOH/g, stop logical methyl alcohol, turn and expect separating tank;
3) acid discharge slag:
After static 1 hour, separating tank lower floor acid sludge is discharged;
4) transesterify:
By step 3) be separated the oil plant that obtains and pump into transesterification reaction still, add anhydrous methanol simultaneously, then appropriate NaOH is added, ester interchange vessel is added after dissolving with anhydrous methanol, be warmed up to 55 DEG C, abundant stirring reaction is after 30 minutes, by step 3) acid sludge of discharging regulates mixture pH value to neutrality;
5) dealcoholysis, dehydration:
Start vacuum pump, and the oil plant in ester interchange vessel is warmed up to 80 DEG C, until stop after bubble-free, dealcoholysis turns completely afterwards expects thick alkyl ester tundish, the alcohol distilled through the laggard thick alcohol tank of flash distillation process for step 2) esterification;
6) glycerine is separated with smart methyl esters, extracts:
Discharge bottom raw glycerine after thick methyl esters stratification and enter raw glycerine storage tank,
Then enter vacuum rectifying tower by after thick methyl esters preheating, through distillation oil plant by condenser after enter smart methyl esters holding tank, finally send into store tank field.
Step 2) described esterification be by reactor bottom gas distributor the alcohol gas being in boiling state is passed through reaction kettle of the esterification, and uniformly dispersing is in the middle of reaction interface, the water-band that reaction generates is gone out reacting phase, the gas overflowed obtains moisture crude carbinol after condensation, can reuse after flash distillation process; Described gas distributor is coil pipe type, helically type, coiled pipe is distributed with radius 0.5 ?the circular hole of 1cm, as shown in Figure 2.
Step 2) described sulfuric acid dripping quantity be oil plant heavy 0.8%, time for adding control 20 ?30 minutes.
Step 1) described in the acid value height of waste grease on reaction not impact, main raw material is sewer oil, swill oil, acidification oil.
Step 4) described in ester-exchange reaction in the consumption of NaOH obtained by following formulae discovery:
W＝[0.0713×AV+0.4]×M/100
W ?alkali consumption,
The initial acid value of AV ?waste grease,
M ?waste grease quality.
Step 6) the present invention in thick methyl esters rectifying by add boric acid improve methyl esters rectification efficiency.By 0.1% ?0.5% addition add the temperature of rectifying tower when boric acid can reduce fuel-displaced.
Step 6) in, the purification of glycerine adopts the technique of rectification under vacuum to carry out.Concrete operations are: use vacuum system by the vacuum cavitations of rectifying tower 0.7 ?open thermal oil (keeping bottom temperature to be no more than 203 DEG C to be advisable) after 0.8MPa.The centrifugal glycerol product obtaining refining after when the glycerine of yellowish rectifying obtained is little in the ratio mix and blend 3 of quality hundred parts of ratios 1.5% with powdered active carbon.
Determining whether step 6 according to the application target of alkyl ester further) the smart methyl esters that obtains washes, if the fatty acid methyl ester of preparation is used as vehicle fuel, wash, otherwise then do not need, the concrete steps of washing are: open water wash product pump using squeeze into as the distilling material of automobile oil washing pool pass into the aqueous solution being added with de-acidying agent again after static 1 hour.Upper oil phase is required product.In order to the usage quantity that reduces water and the glycerine removed more efficiently in smart fatty acid methyl ester.The present invention uses de-acidying agent to wash.De-acidying agent is made up of ammonium chloride, sodium-chlor, sodium hydroxide, with fresh water be mixed with 0.2 ?0.5% solution after in smart methyl esters weight 1 ?5% ratio add.Upper oil phase can be used as vehicle fuel and uses, and lower floor's aqueous phase is reusable.
Embodiment 1
1, raw materials pretreatment: by acid value be the stock oil of 102mgKOH/g send into steam that chemical oil pool sent here by boiler systems by carburetion room temperature to 60 ?80 DEG C of constant temperature 1 hour, water of draining after intensification material is staticized 8 hours by take away pump feeding knockout tower is mixed, water is assorted drops to less than 3%, staticizes temperature 40 DEG C insulation.
2, pre-esterification: the oil plant after being staticized by 4500L is sent in pre-esterification reaction still by pre-esterified fresh feed pump, opens stirring, heats up in dnockout limit, limit.During dnockout, when liquid level floods the first stirring wing, open and stir, and open pre-esterification still steam valve, heat up in charging limit, limit, Steam pressure control, at 0.4MPa, has been broken material and continued to heat up, when temperature rises to 95 DEG C, pass into crude carbinol gas, flow is not less than 450L/h.Logical methyl alcohol, after 5 minutes, drips the vitriol oil, dripping quantity be oil heavy 0.8%, time for adding control 20 ?30 minutes.After adding sulfuric acid, stop stirring, when temperature rises to 105 ± 5 DEG C, adjustment steam valve.Censorship is sampled after 2 hours, when acid value is at below 8mgKOH/g, steam off valve, enter low-temp reaction, and switch to pass into and reclaim refined methanol gas, flow from 450L/h progressively bring up to 550 ?600 L/h, and note observing liquid level, with erosion control material, when there being punching material sign, present flow rate being turned down 50L/h, the low liquid level of pre-esterification still must not be occurred and pass into methyl alcohol low flow condition.Low-temp reaction is after 1.5 hours, and sample presentation, when acid value is lower than 2mgKOH/g, stops logical methyl alcohol, turns and expect separating tank.
3, depickling: the oil plant after pre-esterified operation enters and is separated irrigated area Hou Pai separating tank lower floor acid in static 1 hour, and acid is noted observing with oil viscosity is different, arranges once row altogether for 10 minutes and sees that acid discharge valve turned off by oil for 3 times.Aged oil plant is squeezed into transesterification reaction still through transesterify fresh feed pump by the oil plant after separation, does transesterification reaction cooling and prepares.
4, transesterify: add 250L refined methanol, then get after 13kg sodium hydroxide 50L crude carbinol dissolves and evenly instill in reactor, after the water coolant of reactor outer wall coil pipe of draining, slowly open steam valve and start to heat up, within 20 minutes, be warmed up to 60 DEG C, react 30 minutes.After main reaction terminates, then regulate pH value to 6 ?7.Transesterify main reaction terminate rear logical steam oil plant is warmed up to 120 DEG C start dealcoholysis when after bubble-free in still, start vacuum pump control vacuum cavitations 0.7 ?0.8MPA start negative pressure dealcoholysis until stop after bubble-free.Dealcoholysis is opened completely afterwards and is turned oil plant pump and turn and expect thick methyl esters tundish.After tundish are filled, discharge bottom glycerine to raw glycerine storage tank.
5, the rectifying of thick methyl esters: get 500 kilograms of crude fatty acid methyl ester respectively, add boric acid by the addition of 0.1%, 0.2%, 0.5%.Effect is as shown in table 1 below:
Table 1
| Boric acid addition | Temperature of lower time fuel-displaced | Upper temp time fuel-displaced |
| 0.50％ | 186 | 170 |
| 0.2％ | 188 | 170 |
| 0.10％ | 200 | 188 |
| End is added | 212 | 192 |
| End is added | 218 | 180 |
Result shows: interpolation boric acid can reduce the temperature needed for rectifying.
6, glycerine is refining
Raw glycerine in raw glycerine tank is pumped into interchanger preheating, use vacuum system by the vacuum cavitations of rectifying tower 0.7 ?open thermal oil after 0.8MPa.Bottom temperature is kept to be no more than 200 DEG C.The glycerine of the yellowish that rectifying is obtained and powdered active carbon in 1.5% ratio mix and blend centrifugal glycerol product obtaining refining after 3 hours.
7, wash
The rectifying alkyl ester material of 500kg as automobile oil is squeezed into water washing tank with pump.Take the solution that the ammonium chloride of equivalent, sodium-chlor, sodium hydroxide and fresh water are mixed with 0.2,25L solution stirs stratification after 10 minutes after pouring water washing tank into altogether, with the glycerol content that sodium periodate oxidation is surveyed in upper oil phase be 0.047%, acid value is 0.59, meet " diesel-fuel blending biofuel (BD100) " national standard, survey report as shown in Figure 3.
Claims (9)
1. be a preparation method for the fatty acid methyl ester of raw material with waste grease, it is characterized in that,
Step is as follows:
1) pre-treatment
Waste grease send into chemical oil pool by be heated to 60 ?about 80 DEG C, send into knockout tower after grease fusing to be solidified, in knockout tower, temperature remains on 40 DEG C, the water of bottom of draining after leaving standstill and impurity;
2) esterification:
By step 1) pretreated oil plant sends in pre-esterification reaction still by fresh feed pump, when temperature rises to 95 DEG C, pass into methyl alcohol, control the bubbles volume produced in reactor, logical methyl alcohol added sulfuric acid after 5 minutes, temperature was risen to 105 ± 4 DEG C, react 2 ?3 hours, when acid value is lower than 2mgKOH/g, stop logical alcohol, turn and expect separating tank;
3) acid discharge slag:
After static 1 hour, separating tank lower floor acid sludge is discharged;
4) transesterify:
By step 3) be separated the oil plant that obtains and pump into transesterification reaction still, add anhydrous methanol simultaneously, then appropriate NaOH is added, ester interchange vessel is added after dissolving with anhydrous first class alcohol, be warmed up to 55 DEG C, abundant stirring reaction is after 30 minutes, by step 3) acid sludge of discharging regulates mixture pH value to neutrality;
5) dealcoholysis, dehydration:
Start the dealcoholysis of vacuum pump intensification drying and dehydrating, negative pressure after first normal pressure, constant pressure and dry starts negative pressure drying to during visor wireless streams sample, until during visor wireless streams sample, is considered as thoroughly dry;
6) glycerine and smart alkyl ester separation, extraction:
Discharge bottom raw glycerine after crude fatty acid methyl ester stratification and enter raw glycerine storage tank,
Then enter vacuum rectifying tower by after the preheating of thick for upper strata methyl esters phase, through distillation oil plant by condenser after enter smart methyl esters holding tank, finally send into store tank field.
2. method according to claim 1, it is characterized in that: step 2) described esterification be by reactor bottom gas distributor the alcohol gas being in boiling state is passed through reaction kettle of the esterification, and uniformly dispersing is in the middle of reaction interface, the water-band that reaction generates is gone out reacting phase, the gas overflowed obtains moisture crude carbinol after condensation, can reuse after processed; Described gas distributor is coil pipe type, helically type, coiled pipe is distributed with radius 0.5 ?the circular hole of 1cm.
3. method according to claim 1, is characterized in that: step 2) described sulfuric acid dripping quantity be oil plant heavy 0.8%.
4. method according to claim 1, is characterized in that: step 1) described in the acid value height of waste grease on reaction not impact, main raw material is sewer oil, swill oil, acidification oil.
5. method according to claim 1, is characterized in that: step 4) described in ester-exchange reaction in the consumption of NaOH obtained by following formulae discovery:
W＝[0.0713×AV+0.4]×M/100
W ?alkali consumption,
The initial acid value of AV ?waste grease,
M ?waste grease quality.
6. method according to claim 1, is characterized in that: step 6) in, in thick methyl esters rectifying, improve methyl esters rectification efficiency by adding boric acid, by mass percentage 0.1% ?0.5% addition add the temperature of rectifying tower when boric acid reduces fuel-displaced.
7. method according to claim 1, it is characterized in that: step 6) in, the purification of glycerine adopts the technique of rectification under vacuum to carry out, concrete operations are: use vacuum system by the vacuum cavitations of rectifying tower 0.7 ?open thermal oil after 0.8MPa, keep bottom temperature to be no more than 203 DEG C and to be advisable, the glycerine that rectifying is obtained and powdered active carbon by mass percentage 1.5% ratio mix and blend centrifugal glycerol product obtaining refining after 3 hours.
8. method according to claim 1, it is characterized in that: determine whether step 6 according to the application target of fatty acid methyl ester further) the smart methyl esters that obtains washes, if the fatty acid methyl ester of preparation is used as vehicle fuel, wash, otherwise then do not need, the concrete steps of washing are: open water wash product pump using squeeze into as the distilling material of automobile oil washing pool pass into the aqueous solution being added with de-acidying agent again after static 1 hour, upper oil phase is required product.
9. method according to claim 8, it is characterized in that: described washing adopts de-acidying agent to wash, de-acidying agent is made up of ammonium chloride, sodium-chlor, sodium hydroxide, with fresh water be mixed with mass percent 0.2 ?0.5% solution after in smart methyl esters weight 1 ?5% ratio add, upper oil phase can be used as vehicle fuel and uses, and lower floor's aqueous phase is reusable.
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| CN111019720A (en) * | 2019-12-31 | 2020-04-17 | 浙江卓尚环保能源有限公司 | Green production process of biodiesel |
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