Background technology
Biodiesel is also known as biodiesel, is the cleaning produced as raw material using renewable biological sources such as animal and plant greases
Fuel, physics and chemical property are very close even better with petrifaction diesel.Biodiesel be a kind of Novel pollution-free can
The renewable sources of energy, have many advantages, such as to be easy to that degradation, burning pollutant discharge is low, greenhouse gas emission is few.In industrialized production, generally
It is produced using chemical method, i.e., is raw material with animal or plant grease, with the low-carbon alcohols such as methanol or ethyl alcohol in acid or base catalysis
Agent effect is lower to carry out ester exchange reaction, and biodiesel is prepared.The reactor of traditional mode of production biodiesel mostly uses machinery and stirs
Reactor is mixed, industrial common reactor is the intermittent autoclave stirred reactor with stirring facility, and this reactor lacks
Point is that back-mixing is uneven, and stirring efficiency is not high, and is unsuitable for operating continuously.To solve this problem, it is proposed that a kind of novel
Reactor-impact flow reactor increases material contact area since material mutually clashes in reactor, makes heat transfer, mass transfer
Rate accordingly increases, and promotes carrying out for the chemical reaction influenced by mass transport process.
CN201046396Y discloses a kind of irrotationality vertical circulation impact flow reactor, is set in reactor there are two water conservancy diversion
Cylinder is correspondingly provided with propeller in each guide shell, and the hand of spiral of the propeller is on the contrary, be respectively used to push fluid from charging
Mouth is flowed through guide shell to fluid impingement zone, and contact area is increased by high-speed impact, to reach the mesh for strengthening mass transfer
's.But since fluid is invariably prone to stream line motion, contacting with each other between divided fluid is difficult, therefore impingement region
Strengthening mixing has certain limit.And vibrations or the bearing sealing failure of propeller and arbor are easily caused, lead to mechanical breakdown.
CN1814344A discloses one kind and being used for liquid reactive impact flow reactor, and two are mounted among the reactor
One or two pumps are arranged outside in guide shell, reactor, and the outlet of pump is symmetrically arranged on the feed side of guide shell, and reaction mass is through pump
Conveying is hit in opposite directions through guide shell flow at high speed and at center, effectively promotes the mixing of reaction mass.The reactor makes
Structure design is simplified instead of the structure of propeller type with pumped type outer circulation percussion flow, cost is reduced, reduces simultaneously
Caused by propeller type structure the problems such as vibrations, bearing sealing failure.But above-mentioned reactor center regional fluid speed is larger, and all
Side fluid velocity is small, and mixing nor very uniformly, using pumped type Circulative impinging stream, external Mechanical Driven being needed largely to flow in addition
Body high speed clashes, and energy consumption is larger.
CN1952048A discloses a kind of production method of biodiesel, and for this method in impact flow reactor, material is logical
Cross guide shell to move to middle part, and hit in opposite directions at this, striking face and around formed impingement region.After shock, fluid passes through
Ring casing between guide shell and container inner wall returns to the left and right ends of container respectively, is then divided into and does not pass through left and right two by charging conveying
A guide shell flow direction middle part is simultaneously hit again, is recycled repeatedly, achieve the purpose that it is uniformly mixed, it is fast to improve mass transfer
Rate.But the above method also uses pumped type Circulative impinging stream, needs a large amount of fluid high-speeds head-on collision of external Mechanical Driven, energy consumption compared with
Greatly.
Invention content
In view of the deficienciess of the prior art, the present invention provides a kind of method and system producing biodiesel, this method
Under the premise of keeping a wide range of efficiently mixing mass-transfer performance, the stability of system is enhanced, and can long-term continuous operation.
The method of the production biodiesel of the present invention, including following content:
(1)Raw oil material and alcohols are added to certain proportion in premixing tank and premixed;
(2)Liquid phase material after premix is passed through air and liquid mixer with gas, carries out gas-liquid mixed;
(3)Gas-liquid mixed material is passed through in the horizontal blending tank of mixing reactor and carries out esterification;Wherein, horizontal blending tank
It does reciprocating linear motion in the horizontal direction under the action of reciprocator;
(4)Esterification reaction product flows through ejector and enters products pot, after the partial reaction product reflux to ejector in products pot,
Ejector is passed through to come back in products pot.
In the method for the present invention, step(1)The grease and alcohols is made a living the common raw material of generation diesel oil.Grease uses
Animal and plant grease, the grease with 10 ~ 18 carbon atoms in preferred fat acid group;Alcohols uses low with 1 ~ 8 carbon atom
Molecular weight monohydric alcohol, preferably methanol or ethyl alcohol.The molar ratio of the grease and alcohols is 3:1~10:1, preferably 4:1~8:1.In advance
The catalyst such as the KOH and/or NaOH that are generally added during mixed, catalyst charge are the 0.1% ~ 1% of raw material total amount, premix temperature
Degree is 20 ~ 130 DEG C, and it is 0.1 ~ 0.5 hour to do time in advance, and the premixing tank is the common blending tank of industry.
In the method for the present invention, step(2)The gas is one or more of helium, neon, argon gas or nitrogen;Gas
The ratio between the volume flow of body and the total volumetric flow rate of liquid phase material are 1:5~1:20, preferably 1:8~1:15.The gas-liquid mixed
The common blending tank of industry may be used in device, and gas is passed through from mixing pot bottom, and is arranged at gas feed in blending tank and is bubbled
Device, bubbler are immersed in grease with alcohols, and gas after the aperture effusion in bubbler by, by being bubbled agitated liquid, promoting gas
Liquid mixes;The air and liquid mixer can also use the air and liquid mixer based on venturi principle, such as ejector gas-liquid to mix
Clutch.
In the method for the present invention, step(3)The esterification condition is:Reaction temperature be 30 ~ 130 DEG C, preferably 50 ~
120 DEG C, the reaction time is 0.5 ~ 6 hour.Horizontal blending tank, which is carried out continuously, first to be accelerated to slow down afterwards, reversed again first accelerates to slow down afterwards
The reciprocal change speed linear motion of periodical high-frequency rate, the frequency of reciprocating motion are generally 5 ~ 1000 times/second, preferably 10-600 times/
Second.The fill factor of horizontal blending tank is 0.6 ~ 0.8, wherein the fill factor is liquid volume and blending tank in blending tank
The ratio between volume.
In the method for the present invention, step(4)In, effect of the liquid through pump to flow back in products pot enters ejector, and passes through
Ejector nozzle at high speeds sprays, and the kinetic energy formed using high-velocity fluid generates negative pressure in the throat of ejector, thus by reactor
The liquid of outflow sucks ejector, and phegma and the liquid of reactor outflow carry out mixing jetting in the diffuser pipe of ejector, then
Into in products pot, the gas in products pot is then flowed out from gas vent, and comes back to gas feed to recycle.Step
(4)Described in ejector can also use the other types of mixer based on venturi principle.
Mixing reactor described in the method for the present invention, including horizontal blending tank, feed hose, discharge tube and reciprocal fortune
Dynamic device;The both ends of horizontal blending tank are respectively set inlet port and outlet port, one end of feed hose connect horizontal blending tank into
Material mouth, other end connection charging, one end of discharge tube connect the discharge port of horizontal blending tank, other end connection discharging;Back and forth
Telecontrol equipment includes two parallel guide rails, spring, sliding block or wheel, pedestal II, fixed seat, driving device and sliding rack;Its
Middle sliding rack includes pedestal I and connecting plate;Two parallel guide rails are horizontal positioned, and fixed seat is symmetrically fixed on two guide rails or so
The inside at both ends(I.e. a fixed seat is fixed in every guide rail left and right ends), connected by spring between fixed seat and pedestal II
It connects;Sliding rack and 4 fixed seats are in same plane, for the vertical guide rail direction of the left and right sides 2 pedestal I and be parallel to guide rail
Two connecting plates constitute rectangular configuration;Wherein pedestal I is strip, and length is slightly less than the spacing of two closed slides, even
Installation sliding block or wheel below fishplate bar, sliding block or wheel are equipped with groove, and rail crown is equipped with longitudinal ridge along its length, guide rail
Longitudinal ridge is engaged with the groove of sliding block or wheel;Horizontal blending tank is fixed on the sliding rack of reciprocator, driving device
It is connected with pedestal I or pedestal II;Deflector can be set inside horizontal blending tank.
Wherein, feed hose and the material of discharge tube are determined according to material properties, and rubber hose, plastics generally can be used
Hose, corrugated flexible hose and metal hose etc..Hose has certain length, ensures that hose begins in blending tank reciprocatory movement
There is certain slackness eventually, in order to avoid hose is caused to damage or leaked with blending tank and material import and export junction.Wherein
Feed inlet is preferably placed at discharge port on same level axis.
In the mixing reactor of the present invention, horizontal blending tank end socket can be ellipse, butterfly, taper, spherical or flat
Cover head.
In the mixing reactor of the present invention, the volume of horizontal blending tank is depending on actual conditions.Liquid is equipped in blending tank
Level detecting apparatus controls charging or discharge velocity by level sensing, maintains the liquid level in blending tank.
In the mixing reactor of the present invention, sliding block or the contact surface of wheel and guide rail are equipped with groove, and rail crown is along length
Direction is equipped with longitudinal ridge, and the longitudinal ridge of guide rail is engaged with the groove of sliding block or wheel, ensures sliding block or wheel in driving device
It moves along a straight line along rail length direction under effect.
In the mixing reactor of the present invention, sliding block or wheel are arranged symmetrically, and number is at least 2 pairs, preferably 2-4 pairs.Sliding block
Can be welded between connecting plate can also be threadedly coupled;Each pair of wheel is fixedly connected with a horizontal axis, between axis and connecting plate
It is connected through bearing.
In the mixing reactor of the present invention, guide rail will have certain guiding accuracy, movement to answer light steady;There is foot
Enough rigidity, to bear outer load.Guide rail should also have good wearability, guide rail in use, wear extent should be made smaller,
And can compensate or be conveniently adjusted automatically after wearing, the contact surface for sliding or rolling between guide rail and sliding block or wheel answers enough light
It is sliding, reduce frictional resistance.
In the mixing reactor of the present invention, the spring between connect base and fixed seat has enough rigidity and stiffness system
Number, depending on diameter, spring diameter, spring pitch and the spring material of spring steel wire are according to specific actual conditions.
In the mixing reactor of the present invention, the spacing of the longitudinal ridge of two closed slides is the 1.1-1.5 of blending tank diameter
Times, preferably 1.2-1.4 times, the both ends of guide rail are concordant with fixed seat outer end or slightly above fixed seat outer end.
In the mixing reactor of the present invention, horizontal blending tank is fixedly connected with two pieces of connecting plates of sliding rack.It can will connect
Fishplate bar is welded with blending tank;Or protrusion is set on connecting plate, blending tank is blocked;Can also on blending tank weld pad plate, then
Backing plate and connecting plate are bolted.
In the mixing reactor of the present invention, the reciprocating motion of the ranging from sliding rack between the fixed seat of guide rail left and right ends is empty
Between;Horizontal blending tank on sliding rack is linear reciprocating motion, pedestal I and pedestal II along guide rail between the fixed seat of left and right ends
It periodically collides and contacts in reciprocatory movement.
In the mixing reactor of the present invention, connecting plate length preferably mixes canister length slightly larger than mixing canister length
1.1-1.2 again.
In the mixing reactor of the present invention, the distance between fixed seat of same root guide rail left and right ends is not less than and fixation
1.1 times, preferably 1.1-1.3 times of the corresponding pedestal I spacing of seat.
In the mixing reactor of the present invention, driving device can use electronic, pneumatic, hydraulic-driven or magnetic drive etc.;
When using electronic, pneumatic and hydraulic-driven, driving device is connect with pedestal I 4-3, pedestal I4-3 is acted on, when using magnetic force
When driving, driving device is preferably connected with pedestal II 4-6, by continuous reverse drive or transformation pole orientation, make blending tank into
The reciprocal change speed linear motion of row.
Under driving device effect, blending tank carries out the reciprocal change speed linear motion in left and right.It is horizontal under driving device effect
Blending tank carries out reciprocal change speed linear motion;First, horizontal blending tank moves under driving force effect to the even acceleration in side, the side
Pedestal I contacted with the pedestal II on guide rail after, spring between pedestal II and fixed seat constantly generates flexible deformation by compression,
The kinetic energy of horizontal blending tank is converted into the elastic potential energy of spring;As spring is gradually compressed, horizontal blending tank is in spring force
Under effect, the speed of horizontal blending tank movement constantly reduces, until the speed of horizontal blending tank reduces to zero;Then, horizontal mixing
Tank accelerates under the side driving force and by the elastic force effect of compressed spring to the other side, as the pedestal I and guide rail of the other side
On pedestal II when just contacting, horizontal blending tank reaches maximum speed, with the constantly quilt of the spring between pedestal II and fixed seat
Compression, under the action of spring power, horizontal blending tank reduces speed now movement, and the speed of horizontal blending tank reduces to zero again;
Blending tank changes the direction of motion again under the action of driving force and spring force, and the horizontal such cyclic movement of blending tank makes
Constantly all directions are mutually hit at various locations between material and reactor wall, mixed material in tank, promote material mixed
It closes, strengthens material mass transfer, improve the reaction efficiency between material.
The mixing reactor of the present invention drives horizontal blending tank progress high-frequent reciprocating speed change straight by reciprocator
Line moves, and in movement section, blending tank is first accelerated under the action of driving device, and in the work of spring power
Blending tank is set to be gradually decrease to zero, then the reversed periodical high-frequency rate for accelerating, slowing down by compression process medium velocity in spring under
Reciprocal change speed linear motion.In blending tank motion process, the speed of blending tank or increase or reduce, the speed of any time
It is all changing, also blending tank plays progress variable motion to the gas-liquid mixture in blending tank therewith.Due to material itself in tank
Inertia force effect, mixed material with mix between top tank structure and continuous all directions phase at various locations between mixed material
It mutually hits, avoids the presence in dead zone.Material into horizontal blending tank is in preliminary gas-liquid mixture phase, by horizontal blending tank
High-frequency reciprocating change speed linear motion after, further promote gas-liquid mixed, so that whole materials is formd uniformly mixed gas-liquid mixed
Object is closed, the contact area of grease and alcohols is increased, enhances the microcosmic back-mixing effect of reactor, grease can reach with alcohols
The other mixed effect of molecular level is strengthened mass transfer and is reacted, material is made to mix on a large scale to realize between grease and alcohols
Each position all directions are all able to be sufficiently mixed and react in tank, accelerate reaction rate, substantially reduce the reaction time, carry
High mass transfer and production efficiency.Simultaneously because spring also acts the effect of buffering so that blending tank and reciprocator
Impact force is smaller, is conducive to the even running of device.Using intermittent operation and continous way operation can stable operation, it is preferential to select
It is operated with continous way.Overcome that the only main impingement region mixing situation of common impact flow reactor at present is good, the mixing of other regions is weaker
The shortcomings that and impact flow reactor be unsuitable for continuous operation the shortcomings that, can efficiently be run with long-term smooth.
The present invention production biodiesel system, include mainly:Premixing tank, air and liquid mixer, mixing reactor, jet stream
Device, pump and products pot;Grease feed inlet, alcohols feed inlet and premix material outlet is arranged in premixing tank;Air and liquid mixer is equipped with liquid
Phase import, gas phase import and the outlet of gas-liquid mixed material;Mixing reactor includes horizontal blending tank, feed hose, discharge tube
And reciprocator;Material inlet, refluxing opening, outlet for product and gas vent is arranged in products pot;The pre-composition of premixing tank
Material outlet is connected through the fluid inlet of pipeline and air and liquid mixer, the gas-liquid mixed material outlet of air and liquid mixer and hybrid reaction
The feed hose of device connects, and the discharge tube of mixing reactor connect with ejector feed entrance, ejector export through pipeline and
Products pot import connects, and product pot bottom is exported equipped with phegma, and phegma outlet is connect through pipeline with ejector reflux inlet,
Gas is returned again to gas phase import and is recycled after the outflow of the gas vent of products pot.
Reactor of the present invention using above-mentioned mixing reactor as production biodiesel, is passed through into reactor through gas-liquid
The gas-liquid mixed material tentatively mixed after mixer effect is being reacted by the high-frequency reciprocating change speed linear motion of reactor
Large-scale impingement region is formed in device so that the gas-liquid mixed material tentatively mixed further mixes, and then makes whole material shapes
At uniformly mixed gas-liquid mixture, the contact area of raw oil material and alcohols is increased, makes the grease in reactor and alcohols
It is sufficiently mixed, reaches the other mixed effect of molecular level, greatly enhance microcosmic mixing and microcosmic mass transfer, what is relatively mitigated
Under reaction condition, reaction rate is accelerated, shortens the reaction time, improves mass transfer and production efficiency.Present system structure
Simply, it is easily installed and safeguards, and simplify technological process, reduce production cost and capital cost of reactor, nothing in production process
Discharging of waste liquid is an environmentally protective process.