CN108949365A - Alternating temperature-transformation continuity method preparation biodiesel method and system - Google Patents
Alternating temperature-transformation continuity method preparation biodiesel method and system Download PDFInfo
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- CN108949365A CN108949365A CN201710392564.8A CN201710392564A CN108949365A CN 108949365 A CN108949365 A CN 108949365A CN 201710392564 A CN201710392564 A CN 201710392564A CN 108949365 A CN108949365 A CN 108949365A
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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 alternating temperature-transformation continuity method preparation biodiesel method and system, it is reacted this method comprises: the raw material containing grease and alcohol is directly introduced into first reactor, first material is obtained by the top of the first reactor；The first material is introduced in the second reactor of at least two series connections and is reacted, second material is obtained by the top of the last one second reactor.The method of alternating temperature provided by the invention-transformation continuity method preparation biodiesel pass through the raw material containing grease and alcohol is directly introduced into reacted in first reactor without the pre- thermal reactor of routine 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 alternating temperature-transformation continuity method preparation biodiesel
Method and a kind of alternating temperature-transformation 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, comprising: 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 and acquisition biodiesel
The relatively high defect for being difficult to be up to state standards of acid value.
The second object of the present invention is to improve the feed stock conversion and product yield of the method for preparation biodiesel, simultaneously
The acid value of product is reduced to a greater degree.
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, grease with
The reaction process of alcohol reaction preparation biodiesel is a reaction and the process that deposit is settled while being carried out.This above-mentioned seed type
Accumulation of the raw material in high-pressure heater and reactor be the master for causing the system for preparing biodiesel to be unable to long-term operation
Want one of influence factor.The present inventor passes through creatively using selected from tank reactor or tubular reactor conduct
First reactor make aforementioned raw material in the first reactor and meanwhile carry out preheating and a small amount of ester exchange reaction or and
Esterification, and at least two temperature are connected in series than according to the in poor quality degree of raw material and after the first reactor
The high second reactor of one reactor, and the pressure for limiting the pressure ratio first reactor of the last one second reactor is low,
So that carry out in the first reactor ester exchange reaction or and esterification after obtained material subsequently enter to subsequent
It is further reacted at least two second reactors.It was found by the inventors of the present invention that preparing biology in this way
It enables to feed stock conversion and product yield to be significantly increased when diesel oil, while significantly reducing the acid value of product, and react
The continuous operation period of system significantly extends.
To achieve the goals above, in a first aspect, the present invention provides a kind of alternating temperature-transformation continuity method preparation biodiesel
Method, comprising:
(1) raw material containing grease and alcohol is directly introduced into first reactor and is reacted, reacted by described first
The top of device obtains first material；
(2) first material is introduced in the second reactor of at least two series connections and is reacted, by last
The top of one second reactor obtains second material, wherein in the lower part that material is introduced to the last one second reactor
Before, material is first carried out to the separating treatment of ester phase and glycerol；
Wherein, temperature height and step of the temperature of the second reactor in step (2) than the first reactor in step (1)
(2) pressure of the first reactor in the pressure ratio step (1) of the last one second reactor in is low and described first anti-
Device and the second reactor is answered to be each independently tank reactor or vertical tubular reactor.
Second aspect, the present invention provide a kind of system of alternating temperature-transformation continuity method preparation biodiesel, comprising:
First reaction member is carried out for the raw material containing grease and alcohol to be introduced in the first reactor wherein contained
Reaction, to obtain first material from the top of the first reactor；
Second reaction member wherein contains at least for the first material from first reaction member to be introduced to
It is reacted in the second reactor of two series connections, to obtain second material from the top of the last one second reactor,
Also contain separator in second reaction member, for before the lower part that material is introduced to the last one second reactor
Material is first carried out to the separating treatment of ester phase and glycerol phase,
The first reactor and the second reactor are each independently tank reactor or vertical tubular reactor.
Alternating temperature provided by the invention-transformation continuity method preparation biodiesel method passes through the raw material containing grease and alcohol
Be directly introduced into reacted in first reactor (tank reactor or vertical tubular reactor) and without conventional preheating
Reactor, which can be avoided into that deposit can be caused to accumulate in the heater of high pressure when being preheated in preheater, makes device
Can not long-period stable operation defect.
Meanwhile alternating temperature provided by the invention-transformation continuity method preparation biodiesel method can also realize high raw material
Conversion ratio and product yield, while can be realized the acid value for significantly reducing product.
Detailed description of the invention
Fig. 1 is a kind of knot of alternating temperature-transformation continuity method preparation biodiesel system of preferred embodiment of the invention
Structure schematic diagram.
Fig. 2 is alternating temperature-transformation continuity method preparation biodiesel system of another preferred embodiment of the invention
Structural schematic diagram.
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
A1, the first collection device a2, the second collection device
10, first reactor 11a, the first agitating device
11b, the second agitating device 11c, third agitating device
12a, first stand tank 12b, the second standing tank
13a, the second tank reactor I 13b, the second tank reactor II
14, separator is added
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 (1), " raw material containing grease and alcohol is directly introduced into first reactor " is indicated, contains grease
It is directly introduced into first reactor and is reacted without the pre-heat treatment with the raw material of alcohol.
In step (1), when the first reactor is vertical tubular reactor, the raw material containing grease and alcohol is from the
The lower part of one reactor, which is directly introduced into the first reactor, is reacted, that is to say, that reaction product material is described
Overall flow direction is from bottom to top in first reactor.
In step (1), when the first reactor is tank reactor, has and stir in the preferably described first reactor
Device is mixed, so that the reaction in step (1) carries out in the presence of stirring.
In at least two second reactors of series connection, entered by the material that previous second reactor top obtains
It is reacted in neighbouring the latter second reactor；When the number of concatenated second reactor is greater than two, and so on.
In the method for the invention, the temperature of each second reactor can be mutually the same or different, also, on
The temperature of the second reactor of trip can be more high or low than the temperature of the second reactor in adjacent downstream or both temperature phase
Together.
Preferably, the temperature of the first reactor in preferred steps (1) is than first described second in step (2)
The temperature of reactor is 40~140 DEG C low, and more preferably low 70~120 DEG C.
In the present invention, the temperature in relation to first reactor and second reactor indicates the set temperature of each reactor,
And the temperature for being not reaction temperature, also, entering the initial feed of first reactor is generally room temperature, or is environment temperature
Degree, material in the reactor while reaction and while heat up.In general, with the lower downstream to process route of material, material
Temperature is gradually heated to reach the set temperature of reactor, and material is reacted in the temperature of variation always.To prevent material
Coking, reactor outer wall heating temperature or heating medium temperature are preferably shorter than 350 DEG C.
In the present invention, reaction mass first carries out the separation of ester phase and glycerol before entering the last one second reactor,
Wherein ester mutually enters in the last one second reactor, and glycerol mutually isolates system；Preferably, reaction mass is entering finally
Before one second reactor, when carrying out the separation of ester phase and glycerol, while it being also able to achieve the separation of deposit.
In the method for the invention, the pressure of remaining second reactor other than the last one second reactor can
With equal with the pressure of the first reactor or lower than the pressure of the first reactor.
Preferably, the pressure of the first reactor in the pressure ratio step (1) of the last one second reactor in step (2)
Power low 2~7MPa, preferably low 3~6MPa.It was found by the inventors of the present invention that it is raw to carry out preparation of the invention under the optimum condition
Have the advantages that feed stock conversion and product yield high and reaction system continuous operation period are long when the method for object diesel oil.
Under preferable case, in step (2), according to the flow direction of liquid phase material in system, described second from upstream is anti-
Stewing process is first carried out before answering the material on the top of device to be reacted in the second reactor for entering adjacent downstream
To remove sediment.Preferably, the stewing process carries out in sedimentary deposit tank, and average stop of the material in the sedimentary deposit tank
Time are as follows: 0.1~1h.
Preferably, the second reactor is vertical tubular reactor, and liquid phase material is in each second reactor
In flow direction be from bottom to top.
Preferably, method of the invention further comprises: supplementing alcohol into each second reactor respectively.It is preferred that feelings
Under condition, the additional amount of the supplement alcohol in each second reactor is each independently the 10~90 of the dosage of the alcohol in step (1)
Weight %.
Under preferable case, minimal amount of alkaline matter is added into the last one second reactor.The present inventor
It was found that process of the invention is when being added without alkaline matter, the method for the acid value of the biodiesel of acquisition than the prior art
The restricted reduction of the acid value of the biodiesel of acquisition.But if pole is added in the last one second reactor (relatively low pressure)
When a small amount of alkaline matter, the biodiesel that the acid value of biodiesel obtains technique through the invention can be substantially reduced
Without remaining post-processing, acid value can meet national standard.
Preferably, the second reactor is tank reactor, and the reaction in each second reactor exists respectively
Stirring is lower to be carried out.
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: that temperature is each independently
100~260 DEG C；Pressure is 0.1~10MPa；Volume space velocity is 0.1~20h when liquid-1, more preferably 0.4~2h-1.Also, the
The temperature of one reactor is lower than the temperature of each second reactor.That is, each reaction in step (1) and step (2)
The temperature of device is preferably 100~260 DEG C, and pressure is preferably 0.1~10MPa, and the temperature < second of first reactor reacts
The temperature of device, the pressure of the last one second reactor of the pressure > of first reactor.It was found by the inventors of the present invention that control is each
The temperature of a reactor is between 100~260 DEG C, and pressure is between 0.1~10MPa, and the temperature of control first reactor
It can when the pressure of first reactor is higher than the pressure of the last one second reactor lower than the temperature of each second reactor
It is prevented in product under the premise of guaranteeing that feed stock conversion improves black because burnt matter is generated, and improves biodiesel
Yield.
Under preferable case, volume space velocity is greater than the liquid of other reactors when the liquid of the last one second reactor of the invention
When volume space velocity.
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, enabling to the conversion ratio and biology of grease of the invention
The yield of diesel oil is significantly raised, improves alcohol/oil ratio, and 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 first reactor is 120~170 DEG C；And preferably, exist
In step (2), the temperature of each second reactor is 200~260 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 first reactor and each second reactor
The deposit of bottom is drawn.
Preferably, method of the invention further comprises: by the second material carry out de- monohydric alcohol processing or and
The separating treatment of ester phase and glycerol.
Preferably, in step (1), the grease includes the triglyceride from animal oil and/or vegetable oil.
There is no limit raw material acid value is high and low, it is preferable that in step (1) for the acid value of method of the invention to raw material
In, the acid value of the grease is 0-170mg 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 does not limit the method for the separating treatment of the ester phase and glycerol in step (2) particularly
It is fixed, such as can be separated using the method for stratification.The present invention limits the pressure ratio of the last one second reactor
The pressure of first reactor is low, and ester is carried out under lower pressure so that being entered by the material that penultimate second reactor comes out
The separation of phase and glycerol phase and deposit.
Obtaining second material from the last one second reactor top can be depressurized into vacuum distillation or rectification cell
Distillation or rectifying obtain biodiesel.
Method of the invention is not particularly limited the specific steps of the de- monohydric alcohol processing, those skilled in the art
Member can carry out de- monohydric alcohol processing using various methods commonly used in the art.Under preferable case, using flash distillation (flash distillation temperature
Under the conditions of 150 DEG C of < of degree) steam monohydric alcohol.
Resulting material can be carried out vacuum distillation or rectification process after the de- monohydric alcohol processing by method of the invention
And obtain biodiesel.
It is further the method for the present invention includes being carried out after the de- monohydric alcohol processing to the product of acquisition under preferable case
Ester phase and glycerol separation, and ester phase and glycerol are preferably distilled by vacuum rectification tower or thin film evaporator respectively, thus
Obtain the glycerol of product biodiesel and recycling.
In particularly preferred situation, after taking off monohydric alcohol processing, ester phase is distilled by vacuum rectification tower or thin film evaporator respectively
Each independently with the condition of glycerol are as follows: pressure is less than 0.1MPa, preferably smaller than 0.04MPa；Reflux ratio in rectifying column (0.1~
10): 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 a kind of preferred embodiment, first reactor and second reactor are vertical tubular reactor,
Alternating temperature of the invention-transformation continuity method preparation biodiesel method, comprising:
(1) by the raw material containing grease and alcohol from the lower part of first reactor be directly introduced into the first reactor into
Row reaction, obtains first material by the top of the first reactor；
(2) first material is introduced in the second reactor of at least two series connections and is reacted, by last
The top of one second reactor obtains second material, wherein in the lower part that material is introduced to the last one second reactor
Before, material is first carried out to the separating treatment of ester phase and glycerol phase and deposit；
Wherein, temperature height and step of the temperature of the second reactor in step (2) than the first reactor in step (1)
(2) pressure of the first reactor in the pressure ratio step (1) of the last one second reactor in is low.
According to there are also a kind of preferred embodiment, first reactor is tank reactor or tubular reactor, and
Second reactor is tank reactor, alternating temperature of the invention-transformation continuity method preparation biodiesel method, comprising:
(1) raw material containing grease and alcohol is directly introduced into first reactor, is reacted under stiring, by described
The top of first reactor obtains first material；
(2) first material is stood, and the material after standing is introduced to the of at least two series connections
It is reacted in two reactors, second material is obtained by the top of the last one second reactor, also, will be from upstream
The material on the top of second reactor is first stood before being introduced to the second reactor in adjacent downstream, and will be after standing
Material be introduced in the second reactor in adjacent downstream and reacted (material drawn in penultimate second reactor into
The separation of ester phase and glycerol and deposit is carried out under entering to lower pressure).
Wherein, temperature height and step of the temperature of the second reactor in step (2) than the first reactor in step (1)
(2) pressure of the first reactor in the pressure ratio step (1) of the last one second reactor in is low.
Under preferable case, the deposit of each reactor lower part is for example, by deposit in step (1) and step (2)
Collecting tank is led to except reactor.
According to the method provided by the invention, feed stock conversion can close to 100%, fatty-acid monoester yield can be realized >=
95%.
The content of the second aspect of the present invention is described below:
Second reactor under preferable case, containing at least two series connections in second reaction member.At least two
Connected between the second reactor of a series connection by pipeline so that the material being located in the second reactor of upstream from its
The top of two reactors is drawn, and is subsequently entered and is further reacted in the second reactor in adjacent downstream.
According to a kind of preferred embodiment, in second reaction member, the second reactor is autoclave
Reactor, and the downstream of each second reactor in addition to the last one second reactor are respectively arranged with standing dress
Set, for will the material from the top of the second reactor of upstream enter adjacent downstream the second reactor
In reacted before first carry out stewing process to remove sediment.That is, under preferable case, will except the last one second
The material that the top of second reactor except reactor obtains in the second reactor for being introduced to adjacent downstream into
Stewing process is carried out before row reaction first to remove sediment.Here in connection with method of the invention it should be noted that reciprocal the
The material drawn in two second reactors enters in the standing device of low pressure, can be realized solids in the standing device
The settle and separate of matter, while carrying out the separation of glycerol and ester phase.
According to a kind of preferred embodiment, in first reaction member, the first reactor is autoclave
Reactor, the downstream of the first reactor are provided with standing device, for the first material to be entered described second instead
It answers and carries out stewing process before unit first to remove sediment.
Under preferable case, valve is provided between standing device of the invention and the reactor being directly connected to.It is described
The setting of valve advantageously ensures that the pressure of reaction system is stablized.
Preferably, it is respectively arranged with alcohol feeding device in each second reactor, for respectively to each described the
Alcohol is supplemented in two reactors.
Preferably, in first reaction member and second reaction member, the first reactor and each institute
The bottom for stating second reactor is provided with deposit collection tank, is respectively used to receive the deposition from the reactor bottom
Object.
Preferably, valve is provided between the deposit collection tank and the reactor being directly connected to.
Preferably, system of the invention further include:
Separative unit, including take off monohydric alcohol processing unit or and ester phase and glycerol phase separating and treating apparatus, come from
The second material of second reaction member carries out de- monohydric alcohol by the monohydric alcohol processing unit and handles, or with
And de- monohydric alcohol treated product carries out the separation of ester phase and glycerol further across the separating and treating apparatus of ester phase and glycerol
Processing.
According to a kind of preferred embodiment, the alternating temperature of the invention-transformation continuity method preparation biodiesel
The structural schematic diagram of system is as shown in fig. 1, and the first reactor and the second reactor are vertical tubular reactor,
Specifically, comprising:
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, and in the second vertical tubular reactor I21 under
The additional separator for separating ester phase Yu glycerol and deposit is provided between second vertical tubular reactor II22 of trip
14, the first material 4 in first unit, which is first introduced in the second vertical tubular reactor I21, is reacted, and second is vertical
The deposit of the lower part tubular reactor I21 is introduced to the second deposit collection tank 32, the second vertical tubular type by valve 9 and pipeline
The material on the top reactor I21 is introduced into the separating treatment that ester phase and glycerol phase and deposit are carried out in additional separator 14,
Isolated ester, which mutually enters, is reacted (isolated glycerol extraction reactant in the second vertical tubular reactor II22
System, is not shown in the figure), and benefit is provided in the second vertical vertical tubular reactor II22 of tubular reactor I21 and second
Fill the feeding device of alcohol 8；The deposit of second lower part vertical tubular reactor II22 is introduced to third by valve 9 and pipeline and sinks
Product object collecting tank 33 obtains second material 5 by the second top vertical tubular reactor II22；
Separative unit, including take off monohydric alcohol processing unit or and ester phase and glycerol separating and treating apparatus, from the
The second material 5 of two reaction members, which enters in de- monohydric alcohol processing unit, carries out de- monohydric alcohol processing, or and carries out taking off one
Treated product enters back into ester phase and the separation that ester phase and glycerol are carried out in the separating and treating apparatus of glycerol of first alcohol.
According to another preferred embodiment, the alternating temperature of the invention-transformation continuity method prepares biodiesel
System structural schematic diagram it is as shown in Figure 2, the first reactor and the second reactor are tank reactor, tool
Body, comprising:
First reaction member, including first reactor 10 have the first agitating device 11a in the first reactor 10, and
The lower part of first reactor 10 is provided with the first deposit collection tank 31, the first deposit collection tank 31 and first reactor 10 it
Between connected with pipeline by valve 9, the raw material containing grease 6 and raw alcohol 7 is reacted in first reactor 10, from first
The top of reactor 10 obtains first material 4, which, which is first entered in the first standing tank 12a by lower part, carries out standing
To remove sediment, the sediment in the first standing tank 12a leads to the such as first collection by the pipeline containing valve 9 and fills reason
It sets in a1, it is of the invention by enabling to the first standing tank 12a and the first collection device a1 connection with valvular pipeline
Device realizes the online purpose for removing sediment；Also, it is preferred that introducing the raw material of grease 6 and raw alcohol 7 to the first reaction member
The outlet end of pipe is in the lower part of first reactor 10；
Second reaction member, the second tank reactor being connected in series including two, the second autoclave of respectively upstream are anti-
The second tank reactor II13b in device I13a and downstream is answered, the first material 4 in first unit is after eliminating sediment
It is introduced in the second tank reactor I13a with the second agitating device 11b and is reacted by lower part, the second tank reactor
The deposit of the lower part I13a is introduced to the second deposit collection tank 32 by valve 9 and pipeline, on the second tank reactor I13a
The material in portion by lower part enter second standing tank 12b in is stood to remove sediment, while can be realized herein glycerol and
The separation of ester phase, the second sediment stood in tank 12b lead to such as the second collection device a2 by the pipeline containing valve 9
In, by the way that the second standing tank 12b and the second collection device a2 connection are enabled to the device of the invention with valvular pipeline
It realizes the online purpose for removing sediment, is entered by the material that stewing process eliminates sediment by lower part and stirred with third
It is reacted in the second tank reactor II13b of device 11c, and the second tank reactor I13a and the second tank reactor
The feeding device of supplement alcohol 8 is provided in II13b；The deposit of second lower part tank reactor II13b passes through valve 9 and pipe
Line is introduced to third deposit collection tank 33, obtains second material 5 by the second top tank reactor II13b；
Separative unit, including take off monohydric alcohol processing unit or and ester phase and glycerol separating and treating apparatus, from the
The second material 5 of two reaction members, which enters in de- monohydric alcohol processing unit, carries out de- monohydric alcohol processing, or and carries out taking off one
Treated product enters back into ester phase and the separation that ester phase and glycerol are carried out in the separating and treating apparatus of glycerol of first alcohol.
The method and system of alternating temperature of the invention-transformation continuity method preparation biodiesel also has following some specific
Advantage:
First reactor of the invention carry out at relatively low temperature transesterification or and esterification, while energy
Play the role of preheater, enough so as to avoid further overcoming using the preheater that must be used in the prior art
The defect due to the device cycle of operation caused by must using preheater short in the prior art.Method of the invention can and
When removing system in deposit, extend the device continuous operation period.
Liquid phase material in method of the invention goes to flow from higher-pressure region to low pressure, spontaneous can carry out, and saves energy consumption, can
So that the acid value of product significantly reduces.
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 multiple reactors,
The mode that reaction temperature gradually rises generates deposit and is dispersed, and will not excessively concentrate at one.
Technique of the invention has universality to various refined oils and unrefined oil, even if with the very high unrefined oil of acid value
It for raw material, also can directly be processed, save many and diverse pretreatment of process, make energy consumption, equipment investment decline.
The present invention will be described in detail by way of examples below.
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 first with stirring respectively with the rate of 120 Grams Per Hours, 31 Grams Per Hours
In tank reactor, volume space velocity is 1h when liquid-1, the temperature of the first tank reactor is 170 DEG C, pressure 5Mpa, after reaction
First material escape into stand in tank from the top of the first tank reactor and stood, from standing removing of obtaining of tank top
The material of sediment has been gone to enter in the second tank reactor I with stirring, the temperature of the second tank reactor I is 250 DEG C, pressure
Power is 5Mpa, and volume space velocity is 1h when liquid-1, adding quantity of methyl alcohol is 10 Grams Per Hours, and material after reaction is from the second tank reactor
The top of I is drawn, and is stood into tank is stood, from the ester for eliminating deposit and glycerol phase for standing that tank top obtains mutually into
Enter in the second tank reactor II with stirring, the temperature of the second tank reactor II is 250 DEG C, pressure 1.2Mpa, when liquid
Volume space velocity is 1.1h-1, the quantity of methyl alcohol added is 14 Grams Per Hours (wherein containing the 0.017 weight %'s relative to grease weight
KOH), the second material after reaction is drawn from the top of the second tank reactor II, and second material enters flash column, removes first
Alcohol, 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 19mmHg steams biodiesel, the initial yield of the biodiesel under conditions of temperature is 240 DEG C in pressure
It is 94%, acid value 0.7mg KOH/g.First tank reactor, the second tank reactor I, the second tank reactor II and standing
The deposit or sediment of pot bottom respectively enter the deposit collection tank being connected with them.
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 are continuously mentioned with the rate of 120 Grams Per Hours, 55 Grams Per Hours respectively
It is supplied in heater, sets heter temperature as 250 DEG C, be heated to 250 DEG C of material and enter in tank reactor, reaction temperature
250 DEG C, pressure 5Mpa, volume space velocity is 1h when liquid-1, single tank reactor is only set, and tank reactor bottom is not set
Deposit collection tank, material mouth under tank reactor feed, flow up, from outflow reactor suitable for reading.By tank reactor
The reacting coarse product that top obtains enters flash column, removes methanol, and recycled, reused to methanol, surplus material into
Row sedimentation separation separates ester phase and glycerol phase, and ester mutually enters thin film evaporator, is 19mmHg, the item that temperature is 250 DEG C in pressure
Under part, biodiesel is steamed, the initial yield of the biodiesel is 92.8%, acid value 5.3mg KOH/g.
Behind continuous service 20 days of the system of this comparative example, reactor lower part deposit height is found about after opening reactor
1cm。
Embodiment 2
Waste grease and methanol are continuously presented to the first vertical pipe respectively with the rate of 600 Grams Per Hours, 160 Grams Per Hours
In formula reactor, volume space velocity is 1h when liquid-1, the temperature of the first vertical tubular reactor is 160 DEG C, pressure 6Mpa, described
Sediment in first vertical tubular reactor enters the deposit of the described first vertical tubular type reactor bottom by gravity
In collecting tank.Entered in the second vertical tubular reactor I by the first material of the described first vertical tubular reactor top evolution,
The temperature of second vertical tubular reactor I is 260 DEG C, pressure 6Mpa, and volume space velocity is 1h when liquid-1, the quantity of methyl alcohol added is
25 Grams Per Hours, the material after reaction are drawn from the top of the second vertical tubular reactor I to enter in additional separator and carry out
The settle and separate of ester phase and glycerol phase, wherein the ester after separation mutually enters in the second vertical tubular reactor II, the second vertical pipe
The temperature of formula reactor II is 260 DEG C, pressure 1.5Mpa, and volume space velocity is 1.1h when liquid-1, the quantity of methyl alcohol added is 72 grams/
Hour (KOH wherein containing the 0.027 weight % relative to grease weight), second material after reaction is from the second vertical tubular type
The top of reactor II is drawn, and heavy in the second vertical tubular reactor I and the second vertical tubular reactor II
Drop object has respectively entered in the deposit collection tank of corresponding reactor bottom by gravity.The second material enters flash distillation
Tower removes methanol, and is recycled, reused to methanol, and surplus material carries out sedimentation separation, separates ester phase and glycerol phase,
Ester mutually enters thin film evaporator, is that 9mmHg steams biodiesel, the biodiesel under conditions of temperature is 250 DEG C in pressure
Initial yield be 95%, acid value 0.4mgKOH/g.
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 2
Waste grease and methanol same as Example 2 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, only
Single vertical tubular reactor, 260 DEG C of reaction temperature, pressure 6Mpa, the not set deposit collection in tubular reactor bottom are set
Tank, material feeds from mouth under vertical tubular reactor, flows up, and from outflow reactor suitable for reading, material is in the first vertical tubular type
Volume space velocity is 1h when liquid in reactor-1.Flash column is entered by the reacting coarse product that the first vertical tubular reactor top obtains,
Methanol is removed, and methanol is recycled, is reused, surplus material carries out sedimentation separation, separates ester phase and glycerol phase, ester phase
It is that 7mmHg steams biodiesel under conditions of temperature is 240 DEG C in pressure, at the beginning of the biodiesel into thin film evaporator
Beginning yield is 93.1%, acid value 5.9mg KOH/g.
Behind continuous service 20 days of the system of this comparative example, in the state that reactor heated condition is constant, heater goes out
Mouth material reaction temperature declines about 70 DEG C.Reactor lower part deposit height about 3cm is found after opening reactor.
Embodiment 3
Waste grease and methanol are continuously presented to first with stirring respectively with the rate of 120 Grams Per Hours, 33 Grams Per Hours
In tank reactor, volume space velocity is 0.7h when liquid-1, the temperature of the first tank reactor is 160 DEG C, pressure 5.5Mpa, instead
First material after answering, which escapes into stand in tank from the top of the first tank reactor, to be stood, and is obtained from tank top is stood
The material for eliminating sediment enter in the second tank reactor I with stirring, the temperature of the second tank reactor I is 245
DEG C, pressure 5Mpa, volume space velocity 0.7h-1, the quantity of methyl alcohol added is 14 Grams Per Hours, and the material after reaction is from the second autoclave
The top of reactor I is drawn, and is stood into tank is stood, and eliminates deposit and glycerol phase from stand that tank top obtains
Ester mutually enters in the second tank reactor II with stirring, and the temperature of the second tank reactor II is 250 DEG C, and pressure is
0.7Mpa, volume space velocity 1h-1, the quantity of methyl alcohol added is 22 Grams Per Hours (wherein containing 0.019 weight relative to grease weight
Measure the KOH of %), the second material after reaction is drawn from the top of the second tank reactor II, and second material enters flash column, removes
Remove methanol, and methanol recycled, is reused, surplus material carries out sedimentation separation, separate ester phase and glycerol phase, ester mutually into
Enter thin film evaporator, pressure be 7mmHg, temperature be 240 DEG C under conditions of, steam biodiesel, the biodiesel it is initial
Yield is 92%, and product acid value is 0.74mg KOH/g.First tank reactor, the second tank reactor I, the second still reaction
The deposit or sediment of device II and standing pot bottom respectively enter the deposit collection tank being connected with them.
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
Waste grease and methanol are continuously presented to the first vertical tubular type respectively with the rate of 600 Grams Per Hours, 160 Grams Per Hours
In reactor, volume space velocity is 0.6h when liquid-1, the temperature of the first vertical tubular reactor is 170 DEG C, pressure 6Mpa, reaction
First material afterwards escapes into the second vertical tubular reactor I from the top of the first vertical tubular reactor, and second is vertical
The temperature of tubular reactor I is 260 DEG C, pressure 6Mpa, volume space velocity 0.6h-1, the quantity of methyl alcohol added is 95 Grams Per Hours,
Material after reaction is drawn from the top of the second vertical tubular reactor I to enter in additional separator and carry out ester phase and glycerol
Mutually separate, wherein the ester after separation mutually enters in the second vertical tubular reactor II, the temperature of the second vertical tubular reactor II
It is 250 DEG C, pressure 1Mpa, volume space velocity 1h-1, the quantity of methyl alcohol added is 115 Grams Per Hours (wherein containing relative to grease
The KOH of 0.014 weight % of weight), the second material after reaction is drawn from the top of the second vertical tubular reactor II, and second
Material is introduced into flash column, removes methanol, and recycled, reused to methanol, and surplus material carries out sedimentation separation, separates
Ester phase and glycerol phase, ester mutually enter thin film evaporator, are that 7mmHg steams biological bavin under conditions of temperature is 250 DEG C in pressure
Oil, the initial yield of the biodiesel are 95.1%, and product acid value is 0.5mg KOH/g.First vertical tubular reactor, second
Vertical tubular reactor I, the second bottom vertical tubular reactor II deposit respectively enter the deposit receipts being connected with them
Collect tank.
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.
Alternating temperature provided by the invention-transformation 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 feed stock conversion is close to 100%, simultaneity factor
Continuous operation period is long and the acid value of product is low.
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 (18)
1. a kind of alternating temperature-transformation continuity method preparation biodiesel method, comprising:
(1) raw material containing grease and alcohol is directly introduced into first reactor and is reacted, by the first reactor
Top obtains first material；
(2) first material is introduced in the second reactor of at least two series connections and is reacted, by the last one
The top of second reactor obtains second material, wherein before the lower part that material is introduced to the last one second reactor,
Material is first carried out to the separating treatment of ester phase and glycerol phase；
Wherein, temperature height and step (2) of the temperature of the second reactor in step (2) than the first reactor in step (1)
In the last one second reactor pressure ratio step (1) in first reactor pressure it is low and it is described first reaction
Device and the second reactor are each independently tank reactor or vertical tubular reactor.
2. according to right to go 1 described in method, wherein the temperature of the first reactor in step (1) is than in step (2)
First second reactor temperature it is 40~140 DEG C low；It is preferred that low 70~120 DEG C.
3. according to the method described in claim 1, wherein, the pressure ratio step of the last one second reactor in step (2)
(1) pressure of the first reactor in low 2~7MPa, preferably low 3~6MPa.
4. method described in any one of -3 according to claim 1, wherein in step (2), according to liquid phase material in system
Flow direction, the material on the top of the second reactor from upstream is in the second reactor for entering adjacent downstream
Stewing process is carried out before being reacted first to remove sediment.
5. method described in any one of -4 according to claim 1, wherein this method further comprises: respectively to each institute
It states and supplements alcohol in second reactor；Preferably,
The second reactor is tank reactor, and the reaction in each second reactor carries out under stiring respectively.
6. method described in any one of -4 according to claim 1, wherein before carrying out step (2), first by step (1)
The obtained first material carries out stewing process to remove sediment.
7. 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: that temperature is 100~260 DEG C each independently；Pressure is 0.1~10MPa；Volume space velocity is when liquid
0.1~20h-1；Preferably,
In step (2), the temperature of each second reactor is 200~260 DEG C.
8. 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.
9. method described in any one of -4 according to claim 1, wherein this method further comprises: anti-by described first
The deposit of the bottom of device and each second reactor is answered to draw.
10. method described in any one of -4 according to claim 1, wherein this method further comprises: by second object
Material carry out de- monohydric alcohol processing or and ester phase and glycerol separating treatment.
11. according to the method described in claim 1, wherein, the grease includes the glycerol from animal oil and/or vegetable oil
Three acid esters.
12. 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.
13. a kind of alternating temperature-transformation continuity method preparation biodiesel system, comprising:
First reaction member carries out instead for the raw material containing grease and alcohol to be introduced in the first reactor wherein contained
It answers, to obtain first material from the top of the first reactor；
Second reaction member, for the first material from first reaction member to be introduced to wherein contain at least two
It is reacted in the second reactor of series connection, to obtain second material from the top of the last one second reactor, this
Also contain separator in two reaction members, for first will before the lower part that material is introduced to the last one second reactor
The separating treatment of material progress ester phase and glycerol；
The first reactor and the second reactor are each independently tank reactor or vertical tubular reactor.
14. system according to claim 13, wherein in second reaction member, except the last one the second reaction
The downstream of each second reactor other than device is respectively arranged with standing device, for will be described second from upstream anti-
Stewing process is first carried out before answering the material on the top of device to be reacted in the second reactor for entering adjacent downstream
To remove sediment；Preferably,
In first reaction member, the downstream of the first reactor is provided with standing device, is used for first object
Material carries out stewing process first before entering second reaction member to remove sediment.
15. system according to claim 14, wherein set between standing device and the reactor being directly connected to
It is equipped with valve.
16. system described in any one of 3-15 according to claim 1, wherein set respectively in each second reactor
It is equipped with alcohol feeding device, for supplementing alcohol into each second reactor respectively；Preferably,
The second reactor is the tank reactor with agitating device.
17. system described in any one of 3-16 according to claim 1, wherein in first reaction member and described
In two reaction members, the bottom of the first reactor and each second reactor is provided with deposit collection tank, point
The deposit from the reactor bottom Yong Yu not received；Preferably,
Valve is provided between the deposit collection tank and the reactor being directly connected to.
18. system according to claim 13, wherein the system further include:
Separative unit, including take off monohydric alcohol processing unit or and ester phase and glycerol separating and treating apparatus, from described the
The second material of two reaction members carries out de- monohydric alcohol processing, or and de- one by the monohydric alcohol processing unit
First alcohol treated product carries out the separating treatment of ester phase and glycerol further across the separating and treating apparatus of ester phase and glycerol.
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