CN108929787A - Tubular type-alternating temperature continuity method preparation biodiesel method and system - Google Patents
Tubular type-alternating temperature continuity method preparation biodiesel method and system Download PDFInfo
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- CN108929787A CN108929787A CN201710393725.5A CN201710393725A CN108929787A CN 108929787 A CN108929787 A CN 108929787A CN 201710393725 A CN201710393725 A CN 201710393725A CN 108929787 A CN108929787 A CN 108929787A
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- tubular reactor
- vertical tubular
- temperature
- reactor
- alcohol
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Classifications
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The present invention relates to the preparation fields of biodiesel, disclose tubular type-alternating temperature continuity method preparation biodiesel method and system, and this method includes：Raw material containing grease and alcohol is directly introduced into vertical tubular reactor from the lower part of vertical tubular reactor and is reacted, is flowed out by the top of vertical tubular reactor to obtain first material；By first material be introduced to one or at least two be connected in series vertical tubular reactor in react, second material is obtained by the top of the last one vertical tubular reactor；Second material is successively carried out to the separating treatment of de- monohydric alcohol processing and ester phase and glycerol.The method of tubular type provided by the invention-alternating temperature continuity method preparation biodiesel can be avoided into deposit can be caused to accumulate in the heater of high pressure when being preheated in preheater and make device can not long-period stable operation defect.
Description
Technical field
The present invention relates to the preparation fields of biodiesel, and in particular to a kind of tubular type-alternating temperature continuity method preparation biodiesel
Method and a kind of tubular type-alternating temperature continuity method preparation biodiesel system.
Background technique
Biodiesel can carry out ester exchange reaction by grease and methanol and be made, ester exchange reaction refer to triglycerides with
Another alcohol (usually low-carbon alcohols, such as C1-C8Monohydric alcohol) carry out reaction.There is aliphatic ester in the product of ester exchange reaction
As biodiesel, monoglyceride, two sweet esters, glycerol, pure and mild triglycerides are raw material.The preparation method of biodiesel can be divided into
Acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
A kind of acid catalyzed process is disclosed in CN1412278A, with the method for preparing biological diesel oil from high acid value waste animal and plant oil,
It uses sulfuric acid as catalyst, and according to raw material dehydration, esterification and transesterification, split-phase, the process of decoloration are carried out, raw material first 60~
100 DEG C, dehydrated under vacuum, then carried out at 40~85 DEG C esterification and ester exchange reaction 6 hours, sulphuric acid be 2~
6%, fatty acid methyl ester phase is separated, biodiesel can be obtained by carrying out decoloration at 90~125 DEG C with atlapulgite.
The leftover bits and pieces and edible oil recovery that CN1473907A uses vegetable oil refining for raw material, catalyst by sulfuric acid, hydrochloric acid,
The inorganic acids such as p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acids and organic acid compound, acidified removal of impurities, continuous vacuum
The processes such as dehydration, esterification, layering, vacuum distillation are produced, and the vacuum degree of continuous vacuum dehydration is -0.08~-0.09Mpa,
Temperature is 60~95 DEG C, is dehydrated to water content 0.2% hereinafter, catalyst charge is 1~3% in esterif iotacation step, esterification is anti-
Answering temperature is 60~80 DEG C, and the reaction time is 6 hours.Product is first neutralized to remove catalyst after reaction, and then layering removes
Water is removed, product is gone after water to obtain biodiesel through vacuum distillation.
What above-mentioned two prior art was all made of is acid catalyzed process next life generation diesel oil, however, existing for acid catalyzed process
Problem is that reaction speed is more much slower than base catalysis method, in addition, having a large amount of spent acid and waste water generation.
In natural oil, free fatty acid is usually contained, in the case where free fatty acid is more, is urged if directlying adopt alkali
Change method is reacted using base metal catalysts, can generate fatty acid soaps, and such base metal catalysts have to excess, and
And the separation of fatty acid ester layer and glycerin layer becomes difficult.In order to avoid these problems, DE3444893 discloses a kind of new side
Method, including：Firstly, pre-esterification processing is carried out to oil plant, with acid catalyst, normal pressure, 50~120 DEG C, by free fatty acid and alcohol
Esterification is carried out, excessive base metal catalysts are then added and first neutralize the acid catalyst that pre-esterification is left, then carry out ester friendship
Reaction is changed, the requirement of base metal catalysts has a larger increase.It there are problem is that process flow is long, step using pre-esterifying process
Rapid more, equipment investment and energy consumption are substantially increased, in addition, acidic catalyst and basic catalyst are removed from reaction process and product
It goes, needs that a large amount of waste water can be generated in this way using a large amount of washing water.The concentration of by-product glycerin is low, and recycling is difficult.
US5713965A discloses a kind of method for preparing biodiesel, and in the presence of lipase, hexane makees solvent, oil
Rouge and alcohol are reacted to prepare fatty acid methyl ester, i.e. diesel fuel.Although being mitigated using enzyme catalyst reaction condition, deposit
Deficiency be that the reaction time is long, efficiency is lower, need solvent, moreover, the cost using enzyme is very high, first of the enzyme in high-purity
Also inactivation is easy in alcohol.
A kind of method that PCT/JP99/0543 discloses grease and monohydric alcohol reaction prepares aliphatic ester, 270~280
DEG C, under 11~12MPa, methanol is reacted with oil plant.However, the fatty acid methyl ester production rate in the prior art be only 55~
60%.
By above content it can be seen that：Most of biodiesel raw material be during waste grease or refining raw food oil under
Heel, the general acid value of this quasi-grease is higher, meanwhile, contain a large amount of organic and inorganic impurity.This kind of raw material carry out esterification or
While ester exchange reaction, it is often accompanied by other side reactions, it may appear that some depositions, these deposits can be in hyperbaric heatings
It is accumulated in device and reactor, makes device can not long-period stable operation.
Summary of the invention
An object of the present invention is to overcome the method for the prior art when being preheated the raw material for preparing biodiesel
Deposit can be caused to accumulate in the heater of high pressure and make device can not long-period stable operation defect.
The second object of the present invention is to high reaction conversion ratio and product yield are obtained when preparing biodiesel.
As described in the background section, the raw material for preparing biodiesel is generally during waste grease or refining raw food oil
Leftover bits and pieces, acid value is very high and organic and inorganic impurity content is very high.The present inventor has found under study for action, this type
If the raw material of type is processed using continuous reaction apparatus, the reaction process that grease reacts preparation biodiesel with alcohol is one
The process of a reaction and deposit sedimentation while progress.Deposition in high-pressure heater and reactor is to cause to prepare biological bavin
The continuous system of oil is unable to one of major influence factors of long-term operation.In order to overcome the problems, such as this, the present inventor
Biodiesel preferably is prepared with deposit collection tank and the different vertical tubular reactor of temperature by using at least two,
Aforementioned raw material carried out simultaneously in the first vertical tubular reactor preheating and a small amount of transesterification or and esterification, and
And one or more temperature is connected in series after the first vertical tubular reactor according to the in poor quality degree of raw material
The vertical tubular reactor different from the described first vertical tubular reactor is spent, so that carrying out in the first vertical tubular reactor
The material obtained after reaction is subsequently entered into one or more subsequent the second vertical tubular reactor and is carried out into one
The reaction of step wherein the 1st to n-th temperature of reactor can be different, such as can be gradually increased；Reaction mass is always in the temperature of variation
It is reacted under degree until the reaction is complete, such as carries out reaction under the temperature of charge that is gradually increased always of reaction mass until anti-
It should be complete.It was found by the inventors of the present invention that high reaction conversion ratio and production can be obtained when preparing biodiesel in this way
Object yield, and the continuous operation period of reaction system significantly extends.
To achieve the goals above, in a first aspect, the present invention provides a kind of tubular type-alternating temperature continuity method preparation biodiesel
Method, including：
(1) raw material containing grease and alcohol described first is directly introduced into from the lower part of the first vertical tubular reactor to erect
It is reacted in straight tubular reactor, is flowed out by the top of the described first vertical tubular reactor to obtain first material；
(2) by the first material be introduced to one or at least two be connected in series the second vertical tubular reactor in into
Row reaction, obtains second material by the top of the last one the second vertical tubular reactor；
(3) second material is successively carried out to the separating treatment of de- monohydric alcohol processing and ester phase and glycerol,
Wherein, the temperature of the second vertical tubular reactor in step (2) is than the first vertical tubular type in the step (1)
The temperature of reactor is high.
Second aspect, the present invention provide a kind of system of tubular type-alternating temperature continuity method preparation biodiesel, including：
First reaction member, for by the raw material containing grease and alcohol from the first vertical tubular reactor wherein contained
Lower part, which is introduced in the described first vertical tubular reactor, is reacted, with from the overhead stream of the described first vertical tubular reactor
Out to obtain first material；
Second reaction member, for the first material from first reaction member to be introduced to wherein contain one
Or at least two reacted in the second vertical tubular reactor for being connected in series, with from the last one the second vertical pipe reaction
The top of device obtains second material；
Separative unit, the separating and treating apparatus including sequentially connected de- monohydric alcohol processing unit and ester phase and glycerol come
Successively pass through separating for the monohydric alcohol processing unit and ester phase and glycerol from the second material of second reaction member
Processing unit, to carry out the separating treatment of de- monohydric alcohol processing and ester phase and glycerol respectively.
Tubular type provided by the invention-alternating temperature continuity method preparation biodiesel method passes through the raw material containing grease and alcohol
It is directly introduced into and is reacted in the first vertical tubular reactor and (eliminated without conventional feed preheater or heater
Conventional feed preheater or heater), it can be avoided into deposit can be caused when being preheated in preheater or heater
Accumulated in the preheater or heater of high pressure and make device can not long-period stable operation defect.
Meanwhile tubular type provided by the invention-alternating temperature continuity method preparation biodiesel method can also realize high reaction
Conversion ratio and product yield.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of tubular type of the invention-alternating temperature continuity method preparation biodiesel system.
Description of symbols
1, the first vertical tubular reactor 21, the second vertical tubular reactor I
22, the second vertical tubular reactor II 31, the first deposit collection tank
32, the second deposit collection tank 33, third deposit collection tank
4, first material 5, second material
6, grease 7, raw alcohol
8, alcohol 9, valve are supplemented
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The content of the first aspect of the present invention is described below：
In step (2), in an only second vertical tubular reactor, second material is by only described second
The material that the top of vertical tubular reactor obtains.
In step (1), " raw material containing grease and alcohol is directly introduced into the first vertical tubular reactor " is indicated,
Raw material containing grease and alcohol, which is directly introduced into the first vertical tubular reactor without the pre-heat treatment, to be reacted.
In step (1), the raw material containing grease and alcohol is directly introduced into institute from the lower part of the first vertical tubular reactor
It states and is reacted (including ester exchange reaction or and esterification) in the first vertical tubular reactor, that is to say, that reaction
Material main flow direction in the described first vertical tubular reactor is from bottom to top.
According to the first preferred embodiment, in step (2), the first material is introduced at least two
It is reacted in the second vertical tubular reactor being connected in series.In at least two second vertical tubular reactors of series connection
In, the neighbouring vertical tubular reactor of the latter second is entered by the material that the previous second vertical tubular reactor top obtains
In reacted；When the number of the concatenated second vertical tubular reactor is greater than two, and so on.
According to the first aforementioned preferred embodiment, according to the flow direction of liquid phase material in system, preferred downstream
The temperature of the second vertical tubular reactor is higher than the temperature of the described second vertical tubular reactor of upstream.
According to the first aforementioned preferred embodiment, according to the flow direction of liquid phase material in system, preferred downstream
The temperature of the second vertical tubular reactor is respectively more only than the temperature of the described second vertical tubular reactor of adjacent upstream
It is on the spot 20~100 DEG C high, it is more preferably 40~80 DEG C high.
According to second of preferred embodiment, the described first vertical tubular reactor in preferred steps (1)
Temperature is 20~130 DEG C lower than the temperature of first second vertical tubular reactor in step (2), more preferably low 40~
100℃。
In the present invention, indicate each anti-in relation to the temperature of the first vertical tubular reactor and the second vertical tubular reactor
The set temperature of device is answered, and is not reaction temperature, also, enters the temperature of the initial feed of the first vertical tubular reactor
Generally room temperature, or be environment temperature, material in the reactor while reaction and while heat up.In general, with material to
The lower downstream of process route, temperature of charge are gradually heated to reach the set temperature of reactor, and material is always in the temperature of variation
It is reacted in degree.To prevent material coking, reactor outer wall heating temperature or heating medium temperature are preferably shorter than 350 DEG C.
It was found by the inventors of the present invention that preferred specific using the first aforementioned preferred embodiment and second
Embodiment carries out having reaction conversion ratio and product yield high and reactant when the method for preparation biodiesel of the invention
It is the long advantage of continuous operation period.
Under preferable case, flow direction of the liquid phase material in each second vertical tubular reactor be from lower and
On.
Preferably, this method further comprises：Alcohol is supplemented into each second vertical tubular reactor respectively.It is preferred that
In the case of, the additional amount of the supplement alcohol in each reactor is each independently 10~90 weights of the dosage of the alcohol in step (1)
Measure %.
Under preferable case, before carrying out step (2), first the first material that step (1) obtains is carried out at standing
Reason is to remove sediment.
Preferably, in step (1) and step (2), the condition of each reactor includes each independently：Temperature is
100~260 DEG C；Pressure is 1~9MPa, more preferably 2.5~6MPa；Volume space velocity is 0.1~20h when liquid-1, more preferably
0.1~15h-1, particularly preferably 0.34~12h-1.Also, the temperature of the first vertical tubular reactor is vertical lower than each second
The temperature of tubular reactor.Under preferable case, the temperature of the described second vertical tubular reactor in downstream is than adjacent upstream
The temperature of the second vertical tubular reactor is high.That is, the temperature of step (1) and each reactor in step (2)
Preferably 100~260 DEG C, and the temperature of the vertical tubular reactor of temperature < second of the first vertical tubular reactor.This hair
It is bright inventors have found that control the temperature of each reactor between 100~260 DEG C, and the first vertical pipe reaction of control
The temperature of device is lower than the temperature of each second vertical tubular reactor, the temperature ratio of the described second vertical tubular reactor in downstream
It, can be under the premise of guaranteeing that reaction conversion ratio improves when the temperature of described second vertical tubular reactor of adjacent upstream is high
It prevents in product black because burnt matter is generated, and improves the yield of biodiesel.
In the present invention, preferred alcohols/grease weight ratio is (0.1~2.5)：1, more preferably (0.1~0.7)：1, herein
Pure and mild grease respectively indicates total dosage of pure and mild grease in reaction process.Present inventor has further discovered that control alcohol/grease weight
Amount is than being (0.1~2.5)：1, more preferably (0.1~0.7)：When 1, the conversion ratio and biology of grease of the invention are enabled to
The yield of diesel oil is significantly raised；Alcohol/oil ratio is improved, it is more heavy than that can reduce especially closely or under supercriticality to improve alcohol/oil in methanol
Product object.
In more preferred situation, in step (1), the temperature of the first vertical tubular reactor is 120~160 DEG C；And
Preferably, in step (2), the temperature of each second vertical tubular reactor is 170~260 DEG C.
Under preferable case, in step (1) and step (2), the condition of each reactor makes entire reaction system
In material be in a kind of subcritical state.
Under preferable case, the reaction of step (1) carries out in the presence of alkaline matter or acylate.
It is preferred that the alkaline matter or acylate be in periodic table group ia, group iia element, zinc, iron, manganese,
Zirconium, cerium, the hydroxide of lead, alcoholates, oxide, carbonate, bicarbonate, C1~C24At least one of fatty acid salt,
More preferably sodium, potassium, caesium, magnesium, calcium, barium, zinc, iron, manganese, zirconium, cerium, the hydroxide of lead, alcoholates, oxide, carbonate, carbon
At least one of sour hydrogen salt, fatty acid salt, at least one of particularly preferably following compound：Sodium, potassium, magnesium, zinc, iron,
Manganese, the hydroxide of zirconium, oxide, alcoholates or C1~C24Fatty acid salt.The preferred C of fatty acid salt carbon number2~C20Carboxylic acid, it is more excellent
Select C12~C20Carboxylic acid.
Preferably, the dosage weight ratio of the alkaline matter and the grease is (0.005~2)：100, more preferably
(0.005~0.05)：100.
Preferably, the dosage weight ratio of the acylate and the grease is (0.001~5)：100, more preferably
(0.5~4)：100, further preferably (0.5~2)：100.
Preferably, method of the invention further comprises：By the described first vertical tubular reactor and each described second
The deposit of the bottom of vertical tubular reactor is drawn.
Preferably, in step (1), the grease includes the triglyceride from animal oil and/or vegetable oil.
Method of the invention can handle the very high grease of acid value content, it is preferable that in step (1), the grease
Acid value is 0~200mg KOH/g.
Under preferable case, in step (1), the alcohol is C1~C6At least one of unitary fatty alcohol；More preferable institute
Stating alcohol is methanol and/or ethyl alcohol.
Method of the invention to the specific steps of the de- monohydric alcohol processing and ester phase and the separating treatment of glycerol not
Special limitation, those skilled in the art can carry out de- monohydric alcohol processing and ester using various methods commonly used in the art
The separating treatment of phase and glycerol.Under preferable case, monohydric alcohol is steamed using flash distillation (under the conditions of 150 DEG C of flash temperature <).And
It is preferred that use the method for fiber beam separator or standing to carry out the separating treatment of ester phase and glycerol, thus respectively obtain ester phase and
Glycerol.It is preferred that ester phase and glycerol are distilled respectively by vacuum rectification tower or thin film evaporator, to obtain product biodiesel and return
The glycerol of receipts.In particularly preferred situation, the condition for distilling ester phase and glycerol respectively by vacuum rectification tower or thin film evaporator is each
From independently being：Pressure is less than 0.1MPa, preferably smaller than 0.04MPa；Reflux ratio (0.1~10) in rectifying column：1, preferably (1
~6)：1, the temperature of tower reactor or thin film evaporator is 100~300 DEG C, preferably 120~280 DEG C.
According to another preferred embodiment, tubular type of the invention-alternating temperature continuity method preparation biodiesel side
Method, including：
(1) raw material containing grease and alcohol described first is directly introduced into from the lower part of the first vertical tubular reactor to erect
Ester exchange reaction is carried out in straight tubular reactor, is flowed out by the top of the described first vertical tubular reactor to obtain the first object
Material；
(2) first material is introduced in the second vertical tubular reactor of at least two series connections and is carried out instead
It answers, second material is obtained by the top of the last one the second vertical tubular reactor；
(3) second material is successively carried out to the separating treatment of de- monohydric alcohol processing and ester phase and glycerol,
Wherein, the temperature of the second vertical tubular reactor in step (2) is than the first vertical tubular type in the step (1)
The temperature of reactor is high, and in step (2), second of temperature than adjacent upstream of the vertical tubular reactor of the second of downstream
The temperature of vertical tubular reactor is high.
Under preferable case, each reactor (including the first vertical tubular reactor and each second vertical tubular type it is anti-
Answer device) deposit of lower part leads to except reactor for example, by deposit collection tank.
According to the method provided by the invention, reaction conversion ratio is close to 100%, and fatty-acid monoester yield can be realized >=
95%.
The content of the second aspect of the present invention is described below：
The second vertical pipe reaction under preferable case, containing at least two series connections in second reaction member
Device.It is connected between at least two the second vertical tubular reactors being connected in series by pipeline, so that be located at upstream second is perpendicular
Material in straight tubular reactor is drawn from the top of its second vertical tubular reactor, subsequently enters the second of adjacent downstream
It is further anti-that progress (is preferably introduced) in vertical tubular reactor by the lower part of the second vertical tubular reactor in adjacent downstream
It answers.
Preferably, it is respectively arranged with alcohol feeding device in each second vertical tubular reactor, for respectively to each
Alcohol is supplemented in a second vertical tubular reactor.
Preferably, in first reaction member and second reaction member, the first vertical tubular reactor
It is provided with deposit collection tank with the bottom of each second vertical tubular reactor, is respectively used to receive from described anti-
Answer the deposit of device bottom.
Preferably, valve is provided between the deposit collection tank and the reactor being directly connected to.
According to a kind of preferred embodiment, the tubular type of the invention-alternating temperature continuity method preparation biodiesel
The structural schematic diagram of system is as shown in fig. 1, specifically, including：
First reaction member, including the first vertical tubular reactor 1, the bottom setting of the first vertical tubular reactor 1
There is the first deposit collection tank 31, passes through valve 9 and pipe between the first deposit collection tank 31 and the first vertical tubular reactor 1
Line connection, the raw material containing grease 6 and raw alcohol 7 is reacted in the first vertical tubular reactor 1, from the first vertical tubular type
The top of reactor 1 obtains first material 4；
Second reaction member, the second vertical tubular reactor being connected in series including two, respectively the second of upstream are perpendicular
The second vertical tubular reactor II22 of straight tubular reactor I21 and downstream, the first material 4 in first unit first introduce
It is reacted into the second vertical tubular reactor I21, the deposit of the second lower part vertical tubular reactor I21 passes through valve 9
It is introduced to the second deposit collection tank 32 with pipeline, the material on the second top vertical tubular reactor I21 enters the second vertical pipe
It is reacted in formula reactor II22, and in the second vertical vertical tubular reactor II22 of tubular reactor I21 and second
It is provided with the feeding device of supplement alcohol 8；The deposit of second lower part vertical tubular reactor II22 is introduced by valve 9 and pipeline
To third deposit collection tank 33, second material 5 is obtained by the second top vertical tubular reactor II22；
Separative unit, the separating and treating apparatus including sequentially connected de- monohydric alcohol processing unit and ester phase and glycerol come
From in the separating and treating apparatus that the second material 5 of the second reaction member sequentially enters de- monohydric alcohol processing unit and ester phase and glycerol
The separating treatment of de- monohydric alcohol processing and ester phase and glycerol is carried out respectively.
In the present invention, it is preferred to which the first reaction member and the second reaction member carry out instead under of substantially equal constant-pressure conditions
It answers, in order to enable material can be flowed by upstream toward downstream, has very between more preferable first reaction member and the second reaction member
Low pressure difference.The present invention is not particularly limited the pressure difference, as long as can be conducive to the flowing of material.
The method and system of tubular type of the invention-alternating temperature continuity method preparation biodiesel also has following some specific
Advantage：
Remove preheater or heater, raw material be directly entered the first vertical tubular reactor at relatively low temperature into
Row transesterification or and esterification, the first vertical tubular reactor can play the role of preheater simultaneously, so as to
Avoid using when the prior art in order to make material reach preheater, heater required for reaction temperature, and these preheaters plus
Hot device is since temperature rise is big, so that sediment yield is big, the present invention overcomes in the prior art due to that must use preheater, heater
Caused by the device cycle of operation short defect.The bottom of each reactor of the invention is preferably provided with deposit collection tank,
It is provided with valve between reactor and deposit collection tank, valve is normally open valve in reaction, when reaction, in each reaction tube
Deposit can be flowed into deposit collection tank simultaneously to be discharged in time.Method of the invention can remove in time in the preferred case
Deposit in each reactor, so as to extend the continuous operating time of device.
Reaction mass is not preheated to reaction temperature first according in general technology process by the present invention, then under fixed temperature into
The conventional thinking of row reaction, material react until the reaction is complete under varying temperatures always.The present invention uses more reaction tubes,
The mode that reaction temperature gradually rises generates deposit and is dispersed, and will not excessively concentrate, also, the present invention is perpendicular second
Methanol is added in straight tubular reactor I, II and is more advantageous to fully reacting, and reduces sinking in second vertical tubular reactor I, II
Product object.
In addition, technique of the invention has universality to various refined oils and unrefined oil, even if very high non-with acid value
Refined oil is raw material, also can directly be processed, and many and diverse pretreatment of process is saved, and makes energy consumption, equipment investment decline.
Tubular type of the invention-alternating temperature continuity method preparation biodiesel method can also in the prior art must that need not be added
The catalyst such as the soda acid that must be used are reacted, and are reduced the pollution of spent acid, alkali, are reduced production cost.
Each temperature of reactor of the present invention can need easily to be adjusted according to reaction.
The present invention will be described in detail by way of examples below.Following embodiment is all made of as shown in Fig. 1 of the present invention
Structural schematic diagram system carry out.
The yield of following biodiesel=(products weight/oil plant weight) × 100%
Yield when initial yield expression reaction system incipient stability below.
Embodiment 1
Waste grease and methanol are continuously presented to the first vertical pipe respectively with the rate of 600 Grams Per Hours, 155 Grams Per Hours
In formula reactor, volume space velocity is 1h when liquid-1, the temperature of the first vertical tubular reactor is 120 DEG C, pressure 6Mpa, liquid phase
Material flows from bottom to top in the described first vertical tubular reactor, while the sedimentation in the first vertical tubular reactor
Object enters in the deposit collection tank of the described first vertical tubular type reactor bottom by gravity.By the described first vertical tubular type
The first material of reactor top evolution enters the lower part of the second vertical tubular reactor I, the temperature of the second vertical tubular reactor I
Degree is 190 DEG C, and the quantity of methyl alcohol added is 32 Grams Per Hours, and the material after reaction draws from the top of the second vertical tubular reactor I
Out, and into the lower part of the second vertical tubular reactor II, the temperature of the second vertical tubular reactor II is 260 DEG C, is added
Quantity of methyl alcohol is 70 Grams Per Hours, and the second material after reaction is drawn from the top of the second vertical tubular reactor II, meanwhile, material
It is flowed up in the described second vertical tubular reactor I and the second vertical tubular reactor II, volume space velocity is equal when liquid
For 1h-1, the sediment in the second vertical tubular reactor I and the second vertical tubular reactor II distinguishes by gravity
It enters in the deposit collection tank of corresponding reactor bottom.The second material enters flash column, removes methanol, and to first
Alcohol is recycled, is reused, and surplus material carries out sedimentation separation, separates ester phase and glycerol phase, and ester mutually enters thin film evaporator,
It is that 7mmHg steams biodiesel under conditions of temperature is 240 DEG C in pressure, the initial yield of the biodiesel is 95%.
Behind continuous service 20 days of the system of the present embodiment, biodiesel yield with it is initial when it is identical, open reactor after,
Each reactor lower part has no obvious deposition.
Comparative example 1
Waste grease and methanol same as Example 1 is continuous with the rate of 600 Grams Per Hours, 257 Grams Per Hours respectively
It provides in heater, sets heter temperature as 260 DEG C, the material after heating enters in the first vertical tubular reactor, instead
260 DEG C of temperature, pressure 6Mpa are answered, single vertical tubular reactor, the not set deposit collection in tubular reactor bottom are only set
Tank, material are fed from mouth under vertical tubular reactor, and from outflow reactor suitable for reading, pressure 6Mpa, material is in the first vertical pipe
Volume space velocity is 1h when liquid in formula reactor-1.Sudden strain of a muscle is entered by the reacting coarse product that the first vertical tubular reactor top obtains
Tower is steamed, removes methanol, and recycled, reused to methanol, surplus material carries out sedimentation separation, separates ester phase and glycerol
Phase, ester mutually enter thin film evaporator, are that 7mmHg steams biodiesel, the biology bavin under conditions of temperature is 240 DEG C in pressure
The initial yield of oil is 93.1%.
Behind continuous service 20 days of the system of this comparative example, in the state that heated condition is constant, heater outlet material
Temperature declines about 70 DEG C.Reactor lower part deposit height about 3cm is found after opening reactor.
Comparative example 2
It is carried out using method similar with comparative example 1, except that：
After being run 20 days using the systems stay of comparative example 1, discovery heater outlet temperature of charge declines about 70 DEG C,
In the case that heating and other conditions are constant, the additional amount of methanol is increased into 380 Grams Per Hours, as a result, find after 3 hours
Heater outlet temperature of charge gos up 44 DEG C, and heat transfer conditions are clearly better in reactor.
But the dosage of methanol is big in the comparative example, processing cost increases.
Embodiment 2
Waste grease and methanol are continuously presented to the first vertical pipe respectively with the rate of 600 Grams Per Hours, 181 Grams Per Hours
In formula reactor, volume space velocity is 1.2h when liquid-1, the temperature of the first vertical tubular reactor is 140 DEG C, pressure 5.7Mpa,
Main liquid phase material flows from bottom to top in the described first vertical tubular reactor, while the first vertical pipe reaction
Sediment in device enters in the deposit collection tank of the described first vertical tubular type reactor bottom by gravity.By described
The first material of one vertical tubular reactor top evolution enters the lower part of the second vertical tubular reactor I, the second vertical tubular type
The temperature of reactor I is 190 DEG C, and the quantity of methyl alcohol added is 46 Grams Per Hours, and material after reaction is from the second vertical tubular reactor
The top of I is drawn, and enters the lower part of the second vertical tubular reactor II, and the temperature of the second vertical tubular reactor II is 260
DEG C, the quantity of methyl alcohol added is 91 Grams Per Hours, and the second material after reaction is drawn from the top of the second vertical tubular reactor II,
Meanwhile material flows up in the described second vertical tubular reactor I and the second vertical tubular reactor II, body when liquid
Product air speed is 1.2h-1, sediment in the second vertical tubular reactor I and the second vertical tubular reactor II according to
In the deposit collection tank that gravity has respectively entered corresponding reactor bottom.The second material enters flash column, removes
Methanol, and methanol is recycled, is reused, surplus material carries out sedimentation separation, separates ester phase and glycerol phase, ester mutually enters
Thin film evaporator is that 15mmHg steams biodiesel, the initial receipts of the biodiesel under conditions of temperature is 250 DEG C in pressure
Rate is 95.1%.
Behind continuous service 20 days of the system of the present embodiment, biodiesel yield with it is initial when it is identical, open reactor after,
Each reactor lower part has no obvious deposition.
Embodiment 3
Acidification oil and methanol are continuously presented to the first vertical tubular type respectively with the rate of 600 Grams Per Hours, 167 Grams Per Hours
In reactor, volume space velocity is 0.7h when liquid-1, the temperature of the first vertical tubular reactor is 140 DEG C, pressure 4.9Mpa, main
The liquid phase material wanted flows from bottom to top in the described first vertical tubular reactor, while the first vertical tubular reactor
In sediment enter in the deposit collection tank of the described first vertical tubular type reactor bottom by gravity.By described first
The first material of vertical tubular reactor top evolution enters the lower part of the second vertical tubular reactor I, and the second vertical tubular type is anti-
The temperature for answering device I is 210 DEG C, and the quantity of methyl alcohol added is 40 Grams Per Hours, and material after reaction is from the second vertical tubular reactor I
Top draw, and enter the lower part of the second vertical tubular reactor II, the temperature of the second vertical tubular reactor II is 250
DEG C, the quantity of methyl alcohol added is 32 Grams Per Hours, and the second material after reaction is drawn from the top of the second vertical tubular reactor II,
Meanwhile material flows up in the described second vertical tubular reactor I and the second vertical tubular reactor II, body when liquid
Product air speed is 0.7h-1, sediment in the second vertical tubular reactor I and the second vertical tubular reactor II according to
In the deposit collection tank that gravity has respectively entered corresponding reactor bottom.The second material enters flash column, removes
Methanol, and methanol is recycled, is reused, surplus material carries out sedimentation separation, separates ester phase and glycerol phase, ester mutually enters
Thin film evaporator is that 18mmHg steams biodiesel, the initial receipts of the biodiesel under conditions of temperature is 260 DEG C in pressure
Rate is 92.2%.
Behind continuous service 20 days of the system of the present embodiment, biodiesel yield with it is initial when it is identical, open reactor after,
Each reactor lower part has no obvious deposition.
Embodiment 4
Two vertical tubular reactors are only set in the present embodiment.
Acidification oil and methanol are continuously presented to the first vertical tubular type respectively with the rate of 600 Grams Per Hours, 197 Grams Per Hours
In reactor, the temperature of the first vertical tubular reactor is 130 DEG C, pressure 4.9Mpa, and main liquid phase material is described the
It is flowed from bottom to top in one vertical tubular reactor, volume space velocity is 1h when liquid in the first vertical tubular reactor-1, while institute
State the deposition that the sediment in the first vertical tubular reactor enters the described first vertical tubular type reactor bottom by gravity
In object collecting tank.Second vertical tubular reactor I is entered by the first material of the described first vertical tubular reactor top evolution
Lower part, the temperature of the second vertical tubular reactor I is 245 DEG C, and the quantity of methyl alcohol added is 40 Grams Per Hours, second after reaction
Material is drawn from the top of the second vertical tubular reactor I, meanwhile, when liquid of the material in the described second vertical tubular reactor
Volume space velocity is 1h-1, and the sediment in the second vertical tubular reactor I has respectively entered corresponding reaction by gravity
In the deposit collection tank of device bottom.The second material enters flash column, removes methanol, and is recycled, repeated to methanol
It using, it is 20mmHg in pressure that surplus material, which carries out sedimentation separation, separates ester phase and glycerol phase, and ester mutually enters thin film evaporator,
Under conditions of temperature is 260 DEG C, biodiesel is steamed, the yield of the biodiesel is 90.2%.
Behind continuous service 20 days of the system of the present embodiment, biodiesel yield with it is initial when it is identical, open reactor after,
Each reactor lower part has no obvious deposition.
Tubular type provided by the invention-alternating temperature continuity method preparation biodiesel it can be seen from the result of above-described embodiment
Method and system enable to the high income of the biodiesel obtained by grease, and reaction conversion ratio is close to 100%, simultaneity factor
Continuous operation period it is long.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (14)
1. a kind of tubular type-alternating temperature continuity method preparation biodiesel method, including：
(1) raw material containing grease and alcohol is directly introduced into first vertical pipe from the lower part of the first vertical tubular reactor
It is reacted in formula reactor, is flowed out by the top of the described first vertical tubular reactor to obtain first material；
(2) first material is introduced in one or at least two the second vertical tubular reactors for being connected in series carry out it is anti-
It answers, second material is obtained by the top of the last one the second vertical tubular reactor；
(3) second material is successively carried out to the separating treatment of de- monohydric alcohol processing and ester phase and glycerol,
Wherein, the temperature of the second vertical tubular reactor in step (2) is than the first vertical pipe reaction in the step (1)
The temperature of device is high.
2. according to the method described in claim 1, wherein, in step (2), the first material is introduced at least two strings
Join and is reacted in the second vertical tubular reactor of connection.
3. according to the method described in claim 2, wherein, according to the flow direction of liquid phase material in system, described the second of downstream is perpendicular
The temperature of straight tubular reactor is higher than the temperature of the described second vertical tubular reactor of upstream；Preferably,
The the described second vertical tubular reactor of the temperature of the described second vertical tubular reactor in downstream than adjacent upstream
Temperature is 20~100 DEG C high each independently, preferably 40~80 DEG C high.
4. according to right to remove any one of 1-3 described in method, wherein the described first vertical tubular type in step (1) is anti-
Answer the temperature of device 20~130 DEG C lower than the temperature of first second vertical tubular reactor in step (2)；It is preferred that low 40
~100 DEG C.
5. method described in any one of -4 according to claim 1, wherein this method further comprises：Respectively to each institute
It states in the second vertical tubular reactor and supplements alcohol.
6. method described in any one of -4 according to claim 1, wherein each described in step (1) and step (2)
The condition of reactor includes each independently：Temperature is 100~260 DEG C；Pressure is 1~9MPa, preferably 2.5~6MPa；Liquid
When volume space velocity be 0.1~20h-1；Preferably,
In step (2), the temperature of each second vertical tubular reactor is 170~260 DEG C.
7. method described in any one of -4 according to claim 1, wherein the reaction of step (1) is in alkaline matter or organic
It is carried out in the presence of hydrochlorate；Preferably,
The dosage weight ratio of the alkaline matter and the grease is (0.005~2)：100, preferably (0.005~0.05)：
100；Preferably,
The dosage weight ratio of the acylate and the grease is (0.001~5)：100, preferably (0.5~4)：100, more
Preferably (0.5~2)：100.
8. method described in any one of -4 according to claim 1, wherein this method further comprises：Described first is erected
The deposit of the bottom of straight tubular reactor and each second vertical tubular reactor is drawn.
9. according to the method described in claim 1, wherein, the grease includes the glycerol from animal oil and/or vegetable oil
Three acid esters.
10. according to the method described in claim 1, wherein, in step (1), the alcohol is C1~C6Unitary fatty alcohol in
It is at least one；Preferably,
The alcohol is methanol and/or ethyl alcohol.
11. a kind of tubular type-alternating temperature continuity method preparation biodiesel system, including：
First reaction member, for by the raw material containing grease and alcohol from the lower part of the first vertical tubular reactor wherein contained
Be introduced in the described first vertical tubular reactor and reacted, with from the top of the described first vertical tubular reactor flow out with
Obtain first material；
Second reaction member, for the first material from first reaction member to be introduced to wherein contain one or extremely
It is reacted in second vertical tubular reactors of few two series connections, with from the last one the second vertical tubular reactor
Top obtains second material；
Separative unit, the separating and treating apparatus including sequentially connected de- monohydric alcohol processing unit and ester phase and glycerol come from institute
The second material for stating the second reaction member successively passes through the separating treatment of the monohydric alcohol processing unit and ester phase and glycerol
Device, to carry out the separating treatment of de- monohydric alcohol processing and ester phase and glycerol respectively.
12. system according to claim 11, wherein be connected in series in second reaction member containing at least two
Second vertical tubular reactor.
13. system according to claim 11 or 12, wherein be respectively set in each second vertical tubular reactor
There is alcohol feeding device, for supplementing alcohol into each second vertical tubular reactor respectively.
14. system described in any one of 1-13 according to claim 1, wherein in first reaction member and described
In two reaction members, the bottom of the first vertical tubular reactor and each second vertical tubular reactor is provided with
Deposit collection tank is respectively used to receive the deposit from the reactor bottom；Preferably,
Valve is provided between the deposit collection tank and the reactor being directly connected to.
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