CN105861162A - Preparation method of aliphatic ester by using solid catalyst - Google Patents
Preparation method of aliphatic ester by using solid catalyst Download PDFInfo
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Abstract
The present invention provides a preparation method of aliphatic ester. The method comprises the steps of: in the presence of a composite oxide catalyst, mixing grease with C1-C6 monohydric alcohol in a reactor, reacting at a temperature of 60-200 DEG C and under the pressure of 0.1-2 Mpa, and separating aliphatic esters from the reaction products. The catalyst has a general formula of CuMnaAlbOc; a, b, c respectively represents the atomicity of Mn, Al and O, and satisfy the relations of: a=0.01-1.5, b=0.2-2, and c=0.1-5; and X is the atomicity of oxygen meeting the requirements of electrically neutral compound. The method uses the solid catalyst, treats oil materials with high acid value and high oil impurities under the conditions of lower temperature and pressure, and conducts a one-step reaction to obtain high-yield biodiesel.
Description
Technical field
The method that the present invention relates to be prepared fatty acid ester (i.e. biodiesel) by oils and fats and monohydric alcohol reaction.
Background technology
Biodiesel can carry out ester exchange reaction by oils and fats and monohydric alcohol and prepare, and has fatty acid in product
Ester, also monoglyceride, two sweet esters, glycerol, and unreacted alcohol and oils and fats (i.e. triglyceride).Existing
In technology, the preparation method of biodiesel can be divided into acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
CN1473907A uses the leftover bits and pieces of vegetable oil refining and edible recovered oil to be raw material, catalyst by sulphuric acid,
Hydrochloric acid, p-methyl benzenesulfonic acid, DBSA, LOMAR PWA EINECS 246-676-2 etc. are inorganic and organic acid is compounding forms, acidified
Remove impurity, continuous dehydration, be esterified, be layered, the operations such as distillation that reduce pressure produce, the pressure of continuous vacuum dehydration
Being 0.08～0.09Mpa, temperature 60～95 DEG C, dehydration is to water content less than 0.2%, and esterif iotacation step catalyst adds
Enter amount 1～3%, esterification temperature 60～80 DEG C, 6 hours response time.Reaction afterproduct first neutralizes removing and urges
Agent, then, layering removes water, and the afterproduct that anhydrates obtains biodiesel through decompression distillation.
It is slow that acid catalysis there is problems of response speed compared with base catalysis, has a large amount of spent acid and produces, pollutes ring
Border.
JP9-235573 discloses a kind of discarded edible oil and methanol and prepares bavin in the presence of sodium hydroxide
Oil machine fuel, but in natural oil, usually contain free fatty, in the case of free fatty is more,
Using base metal catalysts, can produce fatty acid soaps, such base metal catalysts is wanted excess and makes fatty acid ester
Layer separates with glycerin layer and becomes difficulty,
DE3444893 discloses a kind of method, with acid catalyst, and normal pressure, 50～120 DEG C, by free-fat
Acid is esterified with alcohol, oil plant carries out pre-esterification process, then carries out ester exchange under base metal catalysts anti-
Should, but the acid catalyst left over to be neutralized by alkali, and the amount of base metal catalysts can increase.Use pre-esterification, make
Work flow is elongated, equipment investment, and energy consumption is substantially increased, it addition, base catalyst need to be removed from product,
A large amount of waste water is had to produce.Recovery glycerol difficulty.
US5713965A discloses a kind of method, and in the presence of lipase, hexane makees solvent, oils and fats and alcohol
Fatty acid methyl ester is prepared in reaction, i.e. diesel fuel.
CN1472280A discloses a kind of method, using fatty acid ester as acyl acceptor, in the existence of enzyme
Under, catalysis biological carries out transesterification reaction and produces biodiesel.The deficiency using enzyme catalyst to exist is: during reaction
Between long, inefficient, enzyme is more expensive, and easy in inactivation in high purity methanol.
A kind of method that CN1111591C discloses oils and fats and fatty acid ester is prepared in monohydric alcohol reaction, the method bag
Include and methanol is obtained fatty acid ester with oils and fats reaction, at 270～280 DEG C, under the conditions of 11～12Mpa, fat
Acid methyl ester production rate is 55～60%, and fatty acid methyl ester production rate is relatively low.
Summary of the invention
The present invention provides a kind of method preparing fatty acid ester, and the method uses solid catalyst, can be at relatively low temperature
Under degree, pressure condition, process high acid value, high impurity oil plant, i.e. be can get the life of high yield by single step reaction
Thing diesel oil.
The present invention provide the method preparing fatty acid ester include: with composite oxides as catalyst, by oils and fats with
C1～C6Monohydric alcohol mixes, and reaction temperature 60～200 DEG C, reacts, from instead under pressure 0.1～2Mpa
Fractionation of fatty acid esters in material after should.
The main component of described oils and fats is fatty acid triglycercide, including various animal and plant fats, the most also wraps
Include from the oil plant in the material such as microorganism, algae.Vegetable oil lipoprotein such as soybean oil, Oleum Brassicae campestris, Oleum Arachidis hypogaeae semen, to
Day seed oil of sunflower, Petiolus Trachycarpi oil, Oleum Cocois and come from other various crops and the fruit of wild plant, stem, leaf,
Branch and the material (including the tall oil produced in paper-making process) containing fat-based of root.Animal oil
Such as Adeps Sus domestica, Adeps Bovis seu Bubali, Adeps Caprae seu ovis, fish oil etc..Described oils and fats can Shi Wei polished fat, polished fat, acidification oil
Fat, frying oil and waste grease etc..
The inventive method be particularly suited for containing high impurity, the oils and fats of high acid value, such as acid number can be 0.1～
200mgKOH/g, preferably 10-150mgKOH/g.Use the inventive method raw oil can not carry out pretreatment.
Described monohydric alcohol refers to carbon number unitary fatty alcohol between 1～6, can be saturated alcohols or not
Saturated alcohols.As methanol, ethanol, propanol, isopropanol, 1-propenol-3, n-butyl alcohol and isomer thereof, amylalcohol and
Isomer etc..Single alcohol or their mixture can be used.Preferably methanol or ethanol.
Catalyst of the present invention has a below formula:
CuMnaAlbOc
Wherein, a, b, c represent the atomic number of Mn, Al, O respectively, and its span is: wherein a=0.01-1.5,
Preferably 0.04-1.0, b=0.2-2, preferably 0.2-1.5, c is for meeting the oxygen atomicity that compound electric neutrality requires.
The preparation method of catalyst of the present invention is coprecipitation, the method comprise the following steps: by Cu,
The water soluble salt (the preferably nitrate of Cu, Mn, Al) of Mn, Al is dissolved in deionizing by a certain percentage
In water, make mixed solution, at 10～80 DEG C, at preferably 20～50 DEG C, with alkali precipitation to PH=4～11,
Preferably PH=5～10, aging 0～5 hour, preferably 1～3 hour, then filter, wash, collect heavy
Form sediment, in 70～200 DEG C, preferably 100～150 DEG C, be dried 2～30 hours, then at 300～900 DEG C, excellent
Select 300～700 DEG C, roasting 2～30 hours, obtain the catalyst that the present invention uses.
Wherein soluble-salt can be the solution simultaneously containing tri-kinds of slaines of Cu, Mn, Al, it is also possible to be
Comprise only one of which or the solution of two kinds of slaines, if the latter, can first by several containing different metal salt
Solution respectively with alkali precipitation more aging after reacted solution is mixed.Described Cu, Mn, Al's can
The preferred respective nitrate of soluble.Described alkali can be ammonium carbonate, ammonium hydrogen carbonate, ammonia, sodium carbonate,
Sodium hydroxide and potassium hydroxide etc., preferably ammonium carbonate, ammonium hydrogen carbonate, ammonia.The concentration of alkali liquor is 5～40wt%,
Preferably 10～35wt%.
Use when prepared by catalyst ammonium carbonate, ammonium hydrogen carbonate, ammonia as precipitant, catalysis can be greatly reduced
The consumption of washings time prepared by agent, reduces washing times, improves the production efficiency of catalyst.
Specifically, the present invention can use autoclave or fixed bed (tubular reactor), if using autoclave,
Oils and fats, alcohol and catalyst are added in autoclave, react under conditions of stirring, if using tubular type anti-
Answering device, preferably oils and fats and monohydric alcohol are entered from tubular reactor bottom, product is from tubular reactor upper end
Flow out, obtain reacting coarse product, from reacting coarse product, steam monohydric alcohol, by mixed ester phase (containing fatty acid
Ester, monoglyceride, two sweet esters, unreacted triglyceride) separate with glycerol, by mixed ester phase and glycerol difference
High purity fatty acid ester and glycerol is obtained by distillation.
According to the inventive method, if use autoclave, the addition of catalyst be oils and fats weight 0.01%～
7%, preferably 0.1%～3%, more preferably 0.5%～2%.If employing tubular reactor, liquid hourly space velocity (LHSV) 0.1～
9h-1, preferably 0.1～3h-1, more preferably 0.1～1h-1。
Temperature of reactor is 100～200 DEG C, preferably 120～170 DEG C, pressure 0.1～2Mpa, preferably 0.3～
1.2Mpa, monohydric alcohol is 0.05～2:1 with the mass ratio of oils and fats, preferably 0.1～1.5:1.
Temperature raises, and reaction conversion ratio is the highest, because for aerodynamic point, temperature raises and is conducive to reaction
Carry out, but when temperature is higher than 300 DEG C, product is black, has burnt matter to produce, also results in meanwhile
Glycerol decomposes, and therefore, temperature of reactor answers ＜ 300 DEG C, best 100～200 DEG C.
Pressure is the highest the most favourable to reaction, but pressure is the highest, makes plant investment and operating cost improve more, institute
With, pressure 0.1～2Mpa, preferably 0.3～1.2Mpa.
In the inventive method, monohydric alcohol can in very large range change with the mass ratio of oils and fats, methanol and oily quality
Making Methanol Recovery amount be significantly increased than too high meeting, plant energy consumption and operating cost increase, and make under the utilization rate of equipment
Fall.So, monohydric alcohol is 0.05～2:1 with the mass ratio of oils and fats, preferably 0.1～1.5:1.
Widely, acid number can change the raw oil that the inventive method is suitable within a large range, and the present invention fits
For high acid value, high impurity oil plant.
The reactive mode of compound metal oxide solid catalyst with low pressure, low temperature is combined by the present invention, passes through
Single step reaction i.e. can get the biodiesel of high yield.During single step reaction, oil plant had both carried out esterification,
Carry out again ester exchange reaction.
Detailed description of the invention
Further illustrate the present invention below by example, but the present invention is not limited to this.
Embodiment 1～3 is the preparation of catalyst.
Embodiment 1
By 35.5g Cu (NO3)2.3H2O (Beijing Chemical Plant, chemical pure), 57g 50%Mn (NO3)2Water-soluble
Liquid (Beijing Chemical Plant, chemical pure), 79g Al (NO3)3.9H2O (Beijing Chemical Plant, chemical pure), is dissolved in 500ml
In deionized water, under agitation drip ammonia (23 weight %, Beijing Chemical Plant, chemical pure), to solution PH
When being 8 ± 0.4 aging 1 hour, then filtering, washing once, collects precipitation, and 200 DEG C to be dried 2 little
Time, 300 DEG C of roastings 2 hours, obtain catalyst A:CuMn0.9Al1.5O4.2。
Embodiment 2
By 52.2g Cu (NO3)2.3H2O (Beijing Chemical Plant, chemical pure), 47g 50%Mn (NO3)2Aqueous solution
(Beijing Chemical Plant, chemical pure), 17g Al (NO3)3.9H2O (Beijing Chemical Plant, chemical pure), is dissolved in 500ml
In deionized water, make solution A.By Na2CO3(20 weight %) (Beijing Chemical Plant, chemical pure) is made molten
Liquid B.200ml deionized water is loaded in 1000ml beaker,
Two kinds of solution of A.B are under agitation simultaneously introduced in beaker, control A, B and drip speed, make PH begin
It is maintained at 5.5 ± 0.5 eventually, after titration aging 1 hour, then filters, through repeatedly washing, collect precipitation,
120 DEG C are dried 3 hours, and 740 ± 40 DEG C of roastings 2 hours obtain catalyst B:CuMn0.46Al0.2O1.76。
Embodiment 3
By 52.2g Cu (NO3)2.3H2O (Beijing Chemical Plant, chemical pure), 17.1g 50%Mn (NO3)2Water
Solution (Beijing Chemical Plant, chemical pure), 74.9g Al (NO3)3.9H2O (Beijing Chemical Plant, chemical pure), molten
In 500ml deionized water, make solution A.Ammonia (23 weight %) is made solution B.At 1000ml
Beaker loads 200ml deionized water, two kinds of solution of A, B are under agitation simultaneously introduced in beaker, control
A, B processed drip speed, make PH remain at 9 ± 0.5, after titration aging 1 hour, then filter, through one
Secondary washing, collects precipitation, is dried 2 hours at 120 DEG C, and 450 ± 40 DEG C of roastings 2 hours obtain catalyst
C:CuMn0.21Al0.9O2.42。
Embodiment 4
The waste grease of acid number 40mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.17:1, adds the catalyst A of oils and fats weight 0.6%, in autoclave temp 130 DEG C, pressure 0.4Mpa, stirring
Under conditions of speed 200 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 93.3%.
Embodiment 5
The waste grease of acid number 40mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.19:1, adds the catalyst B of oils and fats weight 0.6%, in autoclave temp 140 DEG C, pressure 0.9Mpa, stirring
Under conditions of speed 200 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 90.5%.
Embodiment 6
The acidification oil of acid number 122mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.17:1, adds the catalyst C of oils and fats weight 0.9%, in autoclave temp 140 DEG C, pressure 0.9Mpa, stirring
Under conditions of speed 400 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 89%.
Embodiment 7
The waste grease of acid number 91mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.17:1, adds the catalyst C of oils and fats weight 0.4%, in autoclave temp 110 DEG C, pressure 0.2Mpa, stirring
Under conditions of speed 200 revs/min, react 2.5 hours, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 60%.
Embodiment 8
Take granularity 26-40 mesh catalyst B 5.2 grams and load internal diameter 8 millimeters, the rustless steel that length is 391 millimeters
In the tubular reactor made, with the waste grease of acid number 97mg KOH/g as raw material, at alcohol oil quality ratio
0.25, liquid hourly space velocity (LHSV) 0.4h-1Under conditions of, oil and methanol continuously enter into from tubular reactor bottom
In tubular reactor, reaction temperature 140 DEG C, pressure 0.9Mpa, product flows out from tubular reactor upper end,
Reacting coarse product through steaming unreacted methanol, standing separation glycerol phase, rectification under vacuum ester phase, obtain biodiesel
Yield 89%.
Embodiment 9
Take granularity 26-40 mesh catalyst A 5 grams and load internal diameter 8 millimeters, the stainless steel of length 391 millimeters
In the tubular reactor become, with the waste grease of acid number 52mg KOH/g as raw material, at alcohol oil quality ratio 0.2,
Liquid hourly space velocity (LHSV) 0.6h-1Under conditions of, it is anti-that oil and methanol continuously enter into tubular type from tubular reactor bottom
Answer in device, reaction temperature 130 DEG C, press 0.7Mpa, product flows out from tubular reactor upper end, and reaction is thick
Product through steaming unreacted methanol, standing separation glycerol phase, rectification under vacuum ester phase, obtain biodiesel yield
92%.
Claims (10)
1. the method preparing fatty acid ester, including: in the presence of composite oxide catalysts,
Oils and fats is mixed in the reactor with C1～C6 monohydric alcohol, in reaction temperature 60～
200 DEG C, react under pressure 0.1～2Mpa, fractionation of fatty from reacted material
Described in acid esters, catalyst has below formula: CuMnaAlbOc, wherein, a, b, c divide
Not representing the atomic number of Mn, Al, O, its span is: wherein a=0.01-1.5,
B=0.2-2, c are for meeting the oxygen atomicity that compound electric neutrality requires.
The most in accordance with the method for claim 1, wherein, the main component of described oils and fats is fat
Fat acid glycerol three ester, acid number is 0.1～200mgKOH/g.
The most in accordance with the method for claim 1, wherein, described monohydric alcohol refers to carbon number
Unitary fatty alcohol between 1～6.
The most in accordance with the method for claim 1, wherein, in described catalyst Formula, a=
0.04-1.0, b=0.2-1.5, c are for meeting the oxygen atomicity that compound electric neutrality requires.
The most in accordance with the method for claim 1, wherein, described reactor is autoclave or tubular type
Reactor.
The most in accordance with the method for claim 1, wherein, if using autoclave, catalyst
Addition is the 0.01%～7% of oils and fats weight.
The most in accordance with the method for claim 1, wherein, if using tubular reactor, during liquid
Air speed 0.1～9h-1。
The most in accordance with the method for claim 1, wherein, temperature of reactor is 120～170 DEG C.
The most in accordance with the method for claim 1, wherein, pressure 0.3～1.2Mpa.
The most in accordance with the method for claim 1, wherein, monohydric alcohol with the mass ratio of oils and fats is
0.05～2:1.
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| CN202410511428.6A CN118207045A (en) | 2015-01-22 | 2015-01-22 | Method for preparing fatty acid ester by adopting solid catalyst |
| CN201510031336.9A CN105861162A (en) | 2015-01-22 | 2015-01-22 | Preparation method of aliphatic ester by using solid catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107916126A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The method that aliphatic acid and/or fatty acid ester prepare hydrocarbons |
| CN111411129A (en) * | 2019-01-04 | 2020-07-14 | 清华大学 | Process for improving enzymatic grease preparation biodiesel by adding decomposable ammonium salt |
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| CN101096615A (en) * | 2006-06-29 | 2008-01-02 | 中国石油化工股份有限公司 | Technical method for preparing fatty acid ester |
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| CN111411129B (en) * | 2019-01-04 | 2021-10-01 | 清华大学 | Process for improving enzymatic grease preparation biodiesel by adding decomposable ammonium salt |
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