CN103877958B - For preparing the catalyst and preparation method of biodiesel and the preparation technology of biodiesel - Google Patents
For preparing the catalyst and preparation method of biodiesel and the preparation technology of biodiesel Download PDFInfo
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- CN103877958B CN103877958B CN201410090678.3A CN201410090678A CN103877958B CN 103877958 B CN103877958 B CN 103877958B CN 201410090678 A CN201410090678 A CN 201410090678A CN 103877958 B CN103877958 B CN 103877958B
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- 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
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- 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
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Abstract
The invention discloses a kind of catalyst for preparing biodiesel, 85.38~91.42% ZrO is respectively by weight content2, 6.75~9.72% Al2O3TiO with 2.68~4.16%2Constitute, and the catalyst preparation method and application in prepare biodiesel new technology.The catalysis of solid catalyst ester exchange reaction produces biodiesel, reaction time is short, high conversion rate, various raw materials can widely be used, and ester exchange reaction production biodiesel can be carried out under methyl alcohol subcritical state, reaction terminates rear catalyst and product is automatically separated, and water washing operations are not needed, it is achieved thereby that the clean manufacturing of biodiesel, significantly reduces the production cost of biodiesel.
Description
Technical field
Preparing technical field in terms of the present invention relates to chemical industry, especially a kind of catalyst for preparing biodiesel,
And the production technology and process units of biodiesel are prepared using the catalyst.
Background technology
With the continuous intensification of energy crisis, find new alternative clean energy resource and be increasingly becoming countries in the world research
Emphasis.Biodiesel is high due to Cetane number, and greasy property is good, and sulfur content is low, and without the virtue polluted to environment
The advantages of fragrant hydrocarbon and turn into the focus that environmentally friendly renewable alternative energy source is studied in countries in the world.The composition of biodiesel is mainly long-chain
Saturation or unsaturated oxygen-containing organic acid low carbon alcohol ester class material, carbon chain lengths are more in C18~C22Between, it is sufficiently close to diesel oil,
Also it is quite similar in nature, so, reproducible fatty acid methyl ester is defined as biodiesel by initial people.But, with life
Thing diesel raw material is more and more diversified and people for recyclability pursuit, the definition of biodiesel is expanded to be made with oil plant
The water plant such as thing, oilseed plant, engineering microalgae grease and animal fat, waste cooking oil etc. are raw material, using low-carbon alcohols
Glyceryl ester exchange reaction, the aliphatic acid of the different carbon chain lengths of acquisition on methoxy substitution grease main component triglycerides
Mixtures of methyl esters.
Biodiesel is generally reproducible biomass resource due to raw material, once has a very long time to be considered as taking
Raw material sources nexhaustible not to the utmost, however, this reproducible raw material sources are serious for various reasons govern
The large-scale promotion application of biodiesel.Data shows that its cost of material has accounted for the 70~85% of totle drilling cost, high original
Material cost seriously hinders large-scale promotion and the application of biodiesel, greatly reduces its market competitiveness, not only makes it
The protection product under policy and law protection are become, also be there occurs with the original intention of people and greatly deviate.In order to change this situation,
Countries in the world are all continually striving to how to reduce the production cost of biodiesel, on the one hand find cheap and wide material sources
Raw material, is on the other hand then constantly innovated and is improved to production technology and equipment.
Current countries in the world utilize chemical catalysis mostly, are sent out with glyceride stock in the presence of catalyst by short chain alcohol
Raw ester exchange reaction production biodiesel, the reaction unit of use is generally batch stirred tank reactor.This traditional technique
Although method technology maturation, product property stabilization, because low-carbon alcohols are poor with raw oil material intersolubility, traditional interval is stirred
Mix tank reactor often due to mixing effect it is undesirable and have to extend the reaction time, not only increase energy consumption and also reduce
The market competitiveness of biodiesel.Such as Germany Lurgi (Shandong is strange) technique, it is normal that technique use is most widely used in the world
Temperature, two sections of Production of Biodiesel Via Transesterification Method of normal pressure, 96% can be reached by the technique grease conversion ratio, and excessive methyl alcohol leads to
Cross after methanol recovery device is reclaimed and re-use.The biodiesel of the technique productions has accounted for Gross World Product according to statistics
More than 60%, but, using liquid alkali as catalyst, more harsh to ingredient requirement, course of reaction is more complicated for the technique,
The liquid catalyst for using can not be reused, and washing can produce substantial amounts of waste liquor contamination environment, grease in course of reaction
It is immiscible with methyl alcohol to cause whole technique mass transfer poor.In addition, tank reactor needs Exchange Ester Process is repeated several times and could reach
To conversion ratio higher, react end rear catalyst and be difficult to separate, product has to pass through washing and can be only achieved demand of industrial production,
Result causes a large amount of waste water containing spent acid, salkali waste to produce, and these waste water have to pass through treatment and could discharge, so as to increased life
Produce cost.And traditional handicraft is higher to ingredient requirement, it is necessary to refined could use, and the cost of pretreatment of raw material is increased again,
Meanwhile, the utilization rate of batch device is often relatively low, is difficult to realize Automated condtrol, limits the industrialized production of biodiesel.
With going deep into for research, it has been found that carry out ester exchange reaction using different reaction units, to low-carbon alcohols and instead
Answering the mass transport process of grease influences larger.Based on this discovery, some production technologies are by improving traditional reaction unit or opening
The reaction unit for sending out new, to reduce the resistance to mass tranfer between methyl alcohol and glyceride stock, improve production efficiency, reduces cost.Such as Germany
The homogeneous ester exchange process of HTHP of Henkel (Henkel) company exploitation, Henkel techniques have very in the requirement of raw oil material
Much progress, is had been able to use the grease not refined as raw material, and product was waited by except soap, neutralization, washing, drying
Journey obtains biodiesel.Compared with Lurgi techniques, Henkel techniques have a grease conversion ratio high, and almost 100%, it is high
Temperature and pressure makes methyl alcohol in a supercritical state, can preferably dissolve raw oil material, makes the mass transfer between methyl alcohol and grease
There is obvious improvement.Most importantly the technique can be using the grease that did not refined as raw material, and W-response process
Shortened dramatically compared with Lurgi techniques.But the homogeneous catalyst that the technique is used is mixed with product, it is necessary to substantial amounts of water enters
Row cleaning, be returned to traditional handicraft to the process of product postprocessing in the middle of, be unfavorable for catalyst recycling and protection give birth to
State environment.And HTHP causes its reaction condition more harsh, it is necessary to special device is reacted, subsequent treatment needs
Substantial amounts of energy is used for the recovery of glycerine, increased production cost.The still-process carried out to reclaim methyl alcohol is to product
Inoxidizability is very unfavorable, and the cloud point of product is also higher.
Then, University of Toronto proposes to expand the selection model of biodiesel raw material using soda acid two-step catalysis method
Enclose, to reduce the cost of material of biodiesel, and develop BIOX techniques, the technique introduces a kind of proprietary in reaction system
Inert co-solvent is reducing the resistance to mass tranfer between grease and methyl alcohol.The addition of inert co-solvent makes whole course of reaction turn into equal
Phase reaction, greatly improves reaction speed and transformation efficiency, and raw oil material just can be converted into biodiesel within a few minutes, turns
Rate is up to 99%.The acid catalyzed reaction of early stage can significantly reduce the free acid content in raw material, the selection to expanding raw material
Scope, reduces cost of material highly beneficial.Current BIOX techniques can process the raw oil material that free acid content is up to 30%,
So that waste oil and waste animal and vegetable oil are directly utilized and be possibly realized, but inert co-solvent is added and recovery can increase volume
Outer production cost, and two-step catalysis operation also makes the production process become complicated.Main technique for being only is focused on solving
The problem of pretreatment of raw material, expand raw material range of choice, and product separated with catalyst with the later stage process still without departing from
Traditional handicraft.
In order to expand the range of choice of raw material, the separation problem of product and catalyst is solved, reduce late-stage products and treat
Three wastes product withdraw in journey, environmental protection realizes clean manufacturing.People develop a variety of production Technologies in succession,
Wherein overcritical production technology is most noticeable, because in the supercritical state, the moisture in raw material is to yield without obvious
Influence, or even the formation for being conducive to methyl esters to a certain extent.Methyl alcohol and grease are homogeneously under this condition, interphase mass transfer resistance
Power disappears, and reaction rate extremely increases, and whole reaction only needs the several minutes just can to complete.Due to there is no catalyst to deposit in reaction system
, product need not be washed, purify it is also more easy.But the temperature and pressure that supercritical reaction needs is all very high,
There is particular/special requirement to consersion unit, meanwhile, maintain HTHP to need substantial amounts of energy supply, even energy input has been sometimes
Industrialization promotion is difficult to through more than energy output.And alcohol oil rate required for the technique very big (typically larger than 20:1),
Needing extra retracting device carries out Methanol Recovery, not only increases energy ezpenditure, also improves production cost.
Then people envision the temperature and pressure for introducing catalyst to reduce supercritical reaction, as IFP
(IFP) Esterfip-H solid base two-stage reaction techniques are developed, the technique uses two stage fixed-bed reactor, with spinelle knot
The ZnAl of structure2O4•xZnO•yAl2O3, used as Catalyst Production biodiesel, simultaneously sedimentation separation is sweet for flash distillation methyl alcohol for composite oxides
Oil, products obtained therefrom is biodiesel after vacuum distillation.The technique can realize that the grease close to 100% is converted, fat in product
Fatty acid methyl esters content is up to 99%, and can simultaneously obtain glycerin by-product product of the purity more than 98%.Although Esterfip-H energy
It is enough to obtain glycerin by-product product more much higher than homogeneous ester exchange purity (homogeneous ester exchange reaction by-product glycerin purity is only
80%）, but its reaction process is excessively complicated, and continuous two stage fixed-bed reactor is reacted using temperature higher, and energy disappears
Consumption is larger, is unfavorable for reducing production cost.
By comparison, the Mcgyan techniques of U.S. SarTec companies exploitation are then simple many.The technology utilization tubular type is anti-
Answering utensil has larger draw ratio (generally>50), material content constantly changes on its flow direction, and with flowing side
To material on perpendicular interface all parameters as content, pressure, flow velocity and temperature etc. all keep constant the characteristics of, using one
Level fixed-bed tube reactor production biodiesel, with the ZrO that is modified2、Al2O3、TiO2Oxidate microspheres as catalyst, 300
DEG C, ester exchange reaction is carried out under the conditions of 17MPa, reaction terminates rear supernatant liquid carries out distillation procedure to remove excessive methyl alcohol,
The methyl alcohol of recovery reenters reaction system through methanol tank.Lower floor's product obtains biodiesel and accessory substance by respective handling
Glycerine.Because methyl alcohol is in supercriticality in course of reaction, can be good at dissolving grease, so that whole be reacted to
Phase reaction, reaction is completed within the several seconds, and can continuously be produced, and the production efficiency of biodiesel is greatly improved, to reducing into
This, improves product competitiveness in the market highly beneficial.Meanwhile, the requirement of the raw materials technology is relatively low, and catalyst is to free acid in raw material
Content, moisture are insensitive.Reaction terminates rear product and is automatically separated with catalyst, reduces product and step is separated with catalyst
Suddenly, and product is not required to wash the biodiesel that just can obtain meeting ASTM standard, production cost is made further to reduce, together
When also reduce pollution to environment.But the reaction condition that the technique is used is more harsh, reaction pressure higher is to anti-
Answering device has special manufacture requirement, so as to increased the manufacture difficulty and cost of equipment, has accordingly increased the danger of operation
It is dangerous, in addition, extra device fabrication cost can undoubtedly increase the production cost of biodiesel, it is unfavorable for improving biodiesel
The market competitiveness.
Therefore, biodiesel near critical production technology and reaction unit are developed for reducing production of biodiesel cost,
Expand the range of choice and saving water resource of raw material, preserve the ecological environment, realize clean manufacturing, the synthesis for improving biodiesel is competing
Power tool is striven to be of great significance.
The content of the invention
The present invention in view of the shortcomings of the prior art, propose a kind of catalyst for preparing biodiesel, excellent catalytic effect,
Reaction speed is fast.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：It is a kind of for preparing urging for biodiesel
Agent, 85.38~91.42% ZrO is respectively by weight content2, 6.75~9.72% Al2O3With 2.68~4.16%
TiO2Constitute.
Further, the weight content of the catalyst component is respectively ZrO2 88.47%、Al2O3 8.22%、TiO2
3.31%。
Present invention also offers the preparation method of catalyst as described above, including procedure below：ZrO is weighed in proportion2、
Al2O3、TiO2Powder, after being put into 24~36h of ball mill ball milling, adds appropriate NaCl, NaHCO3Powder and Ludox, fully
After mixing, granulating and forming, 105~120 DEG C of 12~24h of drying are transferred to roasting in Muffle furnace, and 500~600 DEG C are incubated 1~2h,
1550~1800 DEG C are warmed up to, 2~4h is incubated, cooling obtains final product solid catalyst.
The invention allows for the technique that biodiesel is prepared using above-mentioned catalyst, comprise the following steps：
(1) glyceride stocks and low-carbon alcohols by volume 1:1~5:1 mixes, and is heated to 200~250 DEG C；
(2) the mixed material after preheatings enters in the tubular reactor for loading catalyst as claimed in claim 1, in 260
Ester exchange reaction is carried out under~285 DEG C and 8~12MPa；
(3) is flashed to reacted material in 2~3MPa at 80~120 DEG C；
(4) the material after flash distillations distills at normal pressure and 65~80 DEG C, reclaims methyl alcohol；
(5) after standing separations glycerine, upper strata product enters rectifying column, collects 200~350 DEG C of products, as biodiesel.
Further, the ester exchange reaction is completed in tubular reactor, wherein the catalyst to account for whole tubular type anti-
2/5~4/5 volume of device is answered, tubular reactor remainder space is filled by mineral wool, ceramic bead or/and glass marble.
Further, the draw ratio of the tubular reactor is more than 200.
Further, the preparation technology is completed in following device, and the device includes the sampling device being sequentially connected, changes
Thermal, reaction unit, flash vessel, condenser, distiller, rectifying column；The reaction unit is by preheater and tubular reactor
Connection is constituted.
Further, it is provided with heat exchanger between the sampling device and the reaction unit.
Further, the tubular reactor is made up of upper end end socket, straight tube body, heating furnace and lower end end socket, upper end seal
Head and lower end end socket are respectively fixedly connected with the two ends of straight tube body；Heating furnace is located at the periphery of straight tube body；It is upper in the straight tube body
Portion is provided with gas distributor, and bottom is provided with catalyst grid；Feed pipe is provided with the upper end end socket, is provided with out in the lower end end socket
Expects pipe.
Compared with prior art, the present invention has advantages below：The biological bavin of catalysis of solid catalyst ester exchange reaction production
Oil, the reaction time is short, high conversion rate, can widely use various raw materials, and ester friendship can be carried out under methyl alcohol subcritical state
Change reaction production biodiesel.Reaction terminates rear catalyst and product is automatically separated, and does not need water washing operations, it is achieved thereby that
The clean manufacturing of biodiesel, significantly reduces the production cost of biodiesel.
By the catalysis for preparing biodiesel oil of solid catalyst, reaction temperature and reaction pressure are obtained for a certain degree of
Reduce, especially reaction pressure decline is larger, has been able to be carried out under methyl alcohol undercritical conditions the production of biodiesel.Instead
Answer temperature and pressure to decline and on the one hand reduce device fabrication cost and operation difficulty, on the other hand save equipment component manufacture
Cost, improves the price advantage of biodiesel oil product.The catalyst is insensitive to the moisture and free acid in raw material, so as to increase
Add the range of choice of raw material, it is fast with reaction speed, the advantages of high conversion rate, while having the excellent of Mcgyan technologies concurrently
Point, and equipment is more intensive, it is three-dimensional compact, vehicle-mounted mobile production can be carried out, so as to break away from the production of conventional chemical plant
Pattern.
The present invention has advantages below compared with traditional biological diesel production technique：
1. due in course of reaction methyl alcohol it is in a supercritical state, there is good solvability to grease, add solid
ZrO2The catalytic action of polycrystalline foamed ceramics catalyst, reaction is completed within more than ten minutes, and can continuously be produced, and is greatly improved
The production efficiency of biodiesel, to reduces cost, improves product competitiveness in the market highly beneficial.
2. the requirement of the raw materials technology is relatively low, and catalyst is insensitive to free acid content, moisture in raw material.Reaction knot
Product is automatically separated with catalyst after beam, reduces product and catalyst separating step, and product is not required to washing and just can obtain
Meet the product of biodiesel B100 national standards, production cost is further reduced, while also reducing the pollution to environment.
3. solid ZrO2Polycrystalline foamed ceramics catalyst greatly reduces reaction temperature and pressure, so as to greatly reduce
The manufacture requirement of production equipment, reaction more than ten minutes just can realize 98% or so conversion ratio, with transformation efficiency higher.
4. the heat that will be reclaimed by heat exchanger is used for feeding preheating, while rectifying column waste heat is used for into Methanol Recovery
Heating, realizes the recycling of heat, reduce further energy consumption and cost.
5. 2~3 square metres of flat board is integrated in so that device is more compact efficiently conveniently to carry out vehicle-mounted mobile transport, right
Certain mitigation can be played in field operation energy recharge, while can also avoid the cost that raw material and product are transported back and forth.
It, by the internal structure of particular design, is a kind of variant of fixed bed reactors that tubular reactor of the present invention is, tool
There is programming rate fast, be heated evenly, moderate pressure is easily controlled in reaction, material is well mixed in inside reactor, mass transfer resistance
Power is small, the advantages of do not have back-mixing.By foamed ceramics catalyst catalytic stability high and service life long, it is not necessary to frequently
More catalyst changeout, successfully solve fixed-bed reactor due to frequently change decaying catalyst and bring it is extra into
This.
Brief description of the drawings
Fig. 1 is biodiesel pipe reaction apparatus structure schematic diagram；
Fig. 2 is pipe reaction apparatus structure schematic diagram；
In figure：A-sampling system；B-reaction system；C-methyl alcohol flash system；D-methyl alcohol Distallation systm；E-glycerine
Piece-rate system；F-fatty acid methyl ester distillation system；
1-raw oil material high-pressure metering pump；2-raw material low-carbon alcohols high-pressure metering pump；3-oil way check valve；Stop on 4-alcohol road
Return valve；5-spinner flowmeter；6-electromagnetic flowmeter；7-gas circuit check-valves；8-sample introduction check-valves；9-heat exchanger；10—
Check-valves；11-preheater；12-check-valves；13-safety valve；14-tubular reactor；15-counterbalance valve；16-pressure-reducing valve；
17-methyl alcohol flash tank；18-condenser；19-methyl alcohol destilling tower reboiler；20-methyl alcohol destilling tower；21-condenser；22—
Methyl alcohol overhead collecting tank；23-Methanol Recovery tank；24-on-condensible gas collecting tank；25-condenser；26-methyl alcohol is followed
Ring pump；27-raw material low-carbon alcohols storage tank；28-glycerin separator；29-crude glycerine storage tank；30-Liquid level adjusting valve；31-fat
Sour methyl esters rectifying column；32-rectifying column reboiler；33-grease circulating pump；34-raw oil material storage tank；35-condenser；36—
Rectifying column tower top product storage tank；37-biodiesel storage tank；38-feed pipe；39-internal temperature detects mouth；40-upper end seal
Head；41-upper end end socket fastening bolt；42-gas distributor；43-lower end end socket；44-lower end end socket fastening bolt；45—
Catalyst grille cover；46-catalyst grid；47-discharging opening；48-interior pressure sensor；49-interior temperature sensor；50-upper end
Temperature sensor；51-stage casing temperature sensor；52-lower temperature sensor；53-heating furnace.
Specific embodiment
The present invention will be described in detail below in conjunction with the accompanying drawings, and the description of this part is only exemplary and explanatory, should not
There is any restriction effect to protection scope of the present invention.
A kind of preparation facilities of biodiesel as shown in Figure 1, including sampling system A, reaction system B, methyl alcohol flash distillation system
System C, methanol recovery system D, glycerine piece-rate system E, fatty acid methyl ester distillation system F and correlation control system；
Sampling system A：Including gas sampling pipeline and Liquid sample introduction pipeline, wherein Liquid sample introduction pipeline is divided into grease original again
Material sample introduction pipeline and reaction low-carbon alcohols sample introduction pipeline.Liquid sample introduction pipeline is connected by pipeline with high-pressure metering pump 1 and 2, gas
Sample introduction pipeline then controls flow by spinner flowmeter 5 and electromagnetic flowmeter 6.And set between sampling system and reaction system
Heat exchanger 9, and be connected with the preheater 11 in reaction system B by pipeline, heat is carried out to reactor lower end thermal material
Reclaim, for heating response device upper end cold feed, to improve utilization ratio of the whole system to heat.
Reaction system B：It is made up of preheater 11 and tubular reactor 14, wherein preheater 11 includes regenerator section and material
Mixing portion, the material mixing portion is static mixer, and material is after entering static mixer and be well mixed after preheating
Into tubular reactor 14.Tubular reactor 14 be specially designed internal structure, as shown in Fig. 2 the device have it is larger
Draw ratio (>200), material content can be made constantly to change in the flowing direction, and on the boundary perpendicular with flow direction
All parameters all keep constant including content, pressure, flow velocity and temperature etc. on face；And gas distributor is provided with charging aperture
42, main purpose is to be uniformly distributed low carbon alcohol vapor, it is fully soaked catalyst surface and internal gutter, increases gas-liquid-solid three
It is in contact, improves reaction efficiency.Reacted product is separated with catalyst by the catalyst grid 46 of bottom of device, should
Catalyst grid 46 is that sieve aperture sinters the porous pressure-resistant material such as screen component or ventilative steel between 200~500 mesh multilayer stainless steels.
Methyl alcohol flash system C：It is made up of pressure-reducing valve 16 and flash tank 17, the system uses adiabatic flash with recovery section first
Alcohol, reduces the pressure of methanol recovery system D and saves part energy consumption and production cost.Respectively by condenser 18 to gas phase and liquid
Mutually condensed, flash gas is condensed and reclaimed by gas condenser, through the recycling of Methanol Recovery tank 23, liquid condenser will
Methyl alcohol destilling tower reboiler 19 is sent into after product condensation.
Methanol recovery system D：Unreacted low-carbon alcohols are recovered to Methanol Recovery tank 23 by distilling, by methanol loop
Pump 26 is recycled, and to improve methyl alcohol service efficiency, saves production cost, is removed the product after methyl alcohol and is entered glycerine piece-rate system
E separates glycerine.
Glycerine piece-rate system E：Using the difference between each component density, glycerine, sedimentation are reclaimed by gravity settling separation
Upper strata is methyl esters layer afterwards, and lower floor is glycerin layer, by the height and the thing into rectifying column 31 of Liquid level Valve controlling methyl esters layer
Stream amount.
Fatty acid methyl ester distillation system F：Biodiesel, unreacted are obtained by the purifies and separates of fatty acid methyl ester rectifying column 31
Raw oil material by the circular response of grease circulating pump 33, to improve the transformation efficiency of whole system, while using rectification under vacuum
Vavuum pump be also responsible for package unit provide vacuumize.
Control system：Be responsible for whole system startup and stopping, and popped one's head in by each temperature and pressure and instrument to reaction
The operation such as temperature, pressure, vapo(u)rizing temperature is controlled.
The concrete operation step of above-mentioned process units is as follows：
1. sample introduction operation
Methyl alcohol and raw oil material in raw material low-carbon alcohols storage tank 27 and raw oil material storage tank 34 by volume 1:1~5:1 by
High-pressure metering pump pumps into the preheater equipped with static mixer and is preheated, and static mixer is entered after being preheating to 200~250 DEG C
It is well mixed, it is connected with tubular reactor 14 by pipeline and check-valves.
2. operation
Filling solid catalyst in tubular reactor 14, carries out rational loadings and sets with experimental data according to actual needs
Put, catalyst is excessive in this technique, it is considered to reserved raw material blending space and actual heating pipe range, this technique filling 2/5~4/
5,260~285 DEG C of heating-up temperature and 8~12MPa pressure and inlet amount are controlled by computer program.
The solid catalyst is respectively 85.38~91.42% ZrO by weight content2, 6.75~9.72% Al2O3With
2.68~4.16% TiO2Constitute；Prepared using following process：ZrO is weighed in proportion2、Al2O3、TiO2Powder, is put into ball mill
After 24~36h of ball milling, appropriate NaCl, NaHCO is added3Powder and Ludox, after fully mixing, granulating and forming, 105~120
DEG C 12~24h of drying, is transferred to roasting in Muffle furnace, and 500~600 DEG C of 1~2h of insulation are warmed up to 1550~1800 DEG C, insulation 2
~4h, cooling, obtains final product.
3. lock out operation
The step includes methyl alcohol flashing operation and glycerine lock out operation, wherein in product excessive methyl alcohol in 2~3MPa, 80
By entering flash tank after pressure-reducing valve at~120 DEG C, so as to realize the recovery of most of methyl alcohol, it is condensed after enter Methanol Recovery
Tank 23.Glycerine is separated by glycerin separator 28, under gravity, glycerine and fatty acid methyl ester and unreacted oil
Fat AUTOMATIC ZONING, lower floor is located at because glycerol density is larger.
4. purification process
Enter methyl alcohol Distallation systm D, 65~80 DEG C of temperature near methyl alcohol boiling point from methyl alcohol flash system C products out
Under distilled to remove residual methanol in product, after condensed device 21 is condensed, collected from condenser 21 with Methanol Recovery tank 23
The methyl alcohol returned with condenser 25, pumps into raw material low-carbon alcohols storage tank 27 and is circulated and use by methanol loop pump 26.Glycerine
The product of piece-rate system E outflows controls flow by fluid level control valve, and biodiesel product is carried out into fatty acid methyl ester rectifying column
The purification operations of product, remove unreacted grease and the glycerin component being mixed into, and the condensed device 35 of 200~350 DEG C of products of tower top is cold
Rectifying column tower top product storage tank 36 is flowed into after solidifying, unreacted oil component and the glycerin components brought on a small quantity then stay in rectifying column
In reboiler 32, pump into raw oil material storage tank 34 through grease circulating pump 33 and be circulated and use, products obtained therefrom is transferred to biological bavin
The special storage tank 37 of oil, that is, obtain meeting the biodiesel oil product of BD100 standards.
Tubular reactor of the invention 14, in the presence of gas distributor, catalyst grid and porous particle catalyst,
Making full use of supercritical methanol is sufficiently mixed reaction mass the solvability of grease, while ester exchange reaction activation energy
A certain degree of reduction is obtained under the catalytic action of catalyst, so that reaction temperature and pressure are obtained for a certain degree
Reduction, reaction rate accelerated, and the transformation efficiency of biodiesel 98% is realized within more than ten minutes, is effectively reduced
Energy consumption and cost.
The present invention carries out heat recovery by setting heat exchanger 9 to the hot fluid of the discharge end of tubular reactor 14, for adding
The cold material that hot feed system A is pumped into, while realizing excessive methanol by condenser 21, condenser 25 and methanol loop pump 26
Recycling, energy ezpenditure and production cost in production process has been obtained a certain degree of reduction.
The present invention uses fixed-bed tube reactor, and with simple to operate, programming rate is fast, high degree of automation, catalysis
The features such as agent can be recycled, while package unit is integrated on 2~3 square metres of flat board, facilitates vehicle-mounted transport.The other work
Skill raw material is not required to be pre-processed, applied widely, and suitable raw material is produced nearby, saves raw material freight and processing cost,
And the biodiesel of production is stable in properties.
The present invention uses solid catalyst, and reaction temperature and pressure is not compared with the supercritical process of catalyst is used
It is low, so as to save substantial amounts of device fabrication cost, there is larger advantage in device fabrication cost and on requiring.With it is traditional
Biodiesel production method is compared, and eliminates pretreatment of raw material and later stage water washing operations, is not only eliminated pretreatment cost and is also subtracted
The pollution to environment is lacked, has saved pretreatment of raw material cost and sewage disposal expense, with larger production cost advantage.
Embodiment 1
Proceeded as follows using the preparation facilities and corresponding preparation method of above-mentioned biodiesel：
1. ZrO is pressed2 88.47%、Al2O3 8.22%、TiO23.31% weight proportion weighs ZrO2、Al2O3、TiO2Powder, puts
After entering ball mill ball milling 24h, appropriate NaCl, NaHCO is added3Powder and Ludox, after fully mixing, granulating and forming, 120 DEG C
Drying 12h, is transferred to roasting in Muffle furnace, and 500 DEG C of insulation 1h are warmed up to 1550 DEG C, are incubated 2h, and cooling obtains final product solid catalysis
Agent, and the solid catalyst that will be prepared loads tubular reactor.
2. high-pressure metering pump is passed through by low-carbon alcohols alcohol and vegetable oil according to volume ratio 1:During 1 pumps into preheater, 200 are preheating to
DEG C, the material after preheating is sufficiently mixed into static mixer, and the vegetable oil is wilson dogwood oil, and low-carbon alcohols are methyl alcohol.
3. mixed material enters in the tubular reactor of constant temperature and pressure, in 8MPa, ester exchange is carried out under the conditions of 285 DEG C
Reaction, reaction time 15min, grease conversion ratio is 96.5%.
4. product pressure after heat exchange drops to 3MPa by 8MPa, and temperature drops to 80 DEG C by 285 DEG C, by flash distillation about 98%
Methyl alcohol be recycled in methyl alcohol collecting tank, remaining methyl alcohol is reclaimed using methyl alcohol destilling tower（Distillation pressure is normal pressure, temperature
It is 80 DEG C）, the methyl alcohol of recovery pumps into low-carbon alcohols storage tank and recycles by methanol loop pump.
5. remove the product after methyl alcohol and enter glycerin separator, gravitational settling glycerine, by after standing, methyl esters layer in upper strata is logical
Fluid level control valve into methyl esters rectifying column is crossed, 200~350 DEG C of products of rectifying column tower top is collected and is wanted biodiesel, bottom of towe
Unreacted grease and residual glycerine component guide methyl alcohol destilling tower into by the road in reboiler, are heated for methyl alcohol destilling tower, then
Return to raw oil material storage tank cycling and reutilization.Lower floor's glycerine phase then flows into crude glycerine storage tank, crude glycerine by fluid level control valve control
Glycerol content is 94% in component.
Embodiment 2
Proceeded as follows using the preparation facilities and corresponding preparation method of above-mentioned biodiesel：
1. ZrO is pressed2 85.38%、Al2O3 9.72% and TiO2 2.68% weighs ZrO2、Al2O3、TiO2Powder, is put into ball mill
After ball milling 36h, appropriate NaCl, NaHCO is added3Powder and Ludox, after fully mixing, granulating and forming, 105 DEG C of drying 24h,
Roasting in Muffle furnace is transferred to, 500 DEG C of insulation 2h are warmed up to 1800 DEG C, is incubated 4h, cooling obtains final product solid catalyst, and will system
The solid catalyst got ready loads tubular reactor.
2. high-pressure metering pump is passed through by low-carbon alcohols and vegetable oil according to volume ratio 5:During 1 pumps into preheater, 230 are preheating to
DEG C, the material after preheating is sufficiently mixed into static mixer, and the vegetable oil is wilson dogwood oil, and low-carbon alcohols are methyl alcohol.
3. mixed material enters in the tubular reactor of constant temperature and pressure, in 8MPa, ester exchange is carried out under the conditions of 260 DEG C
Reaction, reaction time 15min, grease conversion ratio is 97.2%
4. product pressure after heat exchange drops to 3MPa by 8MPa, and temperature drops to 80 DEG C by 285 DEG C, by flash distillation about 98%
Methyl alcohol be recycled in methyl alcohol collecting tank, remaining methyl alcohol is reclaimed using methyl alcohol destilling tower（Distillation pressure is normal pressure, temperature
It is 80 DEG C）, the methyl alcohol of recovery pumps into low-carbon alcohols storage tank and recycles by methanol loop pump.
5. remove the product after methyl alcohol and enter glycerin separator, gravitational settling glycerine, by after standing, methyl esters layer in upper strata is logical
Fluid level control valve into methyl esters rectifying column is crossed, 200~350 DEG C of products of rectifying column tower top is collected and is wanted biodiesel, bottom of towe
Unreacted grease and residual glycerine component in reboiler guide methyl alcohol destilling tower into by the road, are heated for methyl alcohol destilling tower, so
After return to raw oil material storage tank cycling and reutilization.Lower floor's glycerine phase then flows into crude glycerine storage tank by fluid level control valve control, thick sweet
Glycerol content is 95.5% in oil ingredient.
Embodiment 3
Proceeded as follows using the preparation facilities and corresponding preparation method of above-mentioned biodiesel：
1. 91.42% ZrO is pressed2, 6.75% Al2O3TiO with 4.16%2Ratio weighs ZrO2、Al2O3、TiO2Powder,
After being put into ball mill ball milling 30h, appropriate NaCl, NaHCO is added3Powder and Ludox, after fully mixing, granulating and forming, 110
DEG C drying 18h, is transferred to roasting in Muffle furnace, and 550 DEG C of insulation 1.2h are warmed up to 1670 DEG C, are incubated 3h, and cooling obtains final product solid
Catalyst, and the solid catalyst that will be prepared loads tubular reactor.
2. high-pressure metering pump is passed through by low-carbon alcohols alcohol and vegetable oil according to volume ratio 3:During 1 pumps into preheater, 250 are preheating to
DEG C, the material after preheating is sufficiently mixed into static mixer, and the vegetable oil is wilson dogwood oil, and low-carbon alcohols are methyl alcohol.
3. mixed material enters in the tubular reactor of constant temperature and pressure, in 10MPa, ester friendship is carried out under the conditions of 275 DEG C
Reaction is changed, reaction time 11min, grease conversion ratio is 98.3%
4. product pressure after heat exchange drops to 2.5MPa by 10MPa, and temperature drops to 90 DEG C by 285 DEG C, by flash distillation about
98% methyl alcohol is recycled in methyl alcohol collecting tank, and remaining methyl alcohol is reclaimed using methyl alcohol destilling tower（Distillation pressure is normal pressure,
Temperature is 65~80 DEG C）, the methyl alcohol of recovery pumps into low-carbon alcohols storage tank and recycles by methanol loop pump.
Remove the product after methyl alcohol and enter glycerin separator, gravitational settling glycerine, by after standing, methyl esters layer in upper strata passes through
Fluid level control valve enters methyl esters rectifying column, collects 200~350 DEG C of products of rectifying column tower top and is wanted biodiesel, and bottom of towe is again
Unreacted grease and residual glycerine component in boiling device guide methyl alcohol destilling tower into by the road, are heated for methyl alcohol destilling tower, then
Return to raw oil material storage tank cycling and reutilization.Lower floor's glycerine phase then flows into crude glycerine storage tank, crude glycerine by fluid level control valve control
Glycerol content is 97.6% in component.
Claims (7)
1. a kind of preparation method for preparing the catalyst of biodiesel, including procedure below：ZrO is weighed in proportion2、
Al2O3、TiO2Powder, after being put into 24~36h of ball mill ball milling, adds appropriate NaCl, NaHCO3Powder and Ludox, fully
After mixing, granulating and forming, 105~120 DEG C of 12~24h of drying are transferred to roasting in Muffle furnace, and 500~600 DEG C are incubated 1~2h,
1550~1800 DEG C are warmed up to, 2~4h is incubated, cooling obtains final product solid catalyst；Catalyst for preparing biodiesel, by
Weight content is respectively 85.38~91.42% ZrO2, 6.75~9.72% Al2O3TiO with 2.68~4.16%2Structure
Into.
2. a kind of preparation technology of biodiesel, comprises the following steps：
(1) glyceride stocks and low-carbon alcohols by volume 1:1~5:1 mixes, and is heated to 200~250 DEG C；
(2) the mixed material after preheatings enters the tubular reactor for loading catalyst prepared by preparation method described in claim 1
It is interior, in carrying out ester exchange reaction under 260~285 DEG C and 8~12MPa；
(3) is flashed to reacted material in 2~3MPa at 80~120 DEG C；
(4) the material after flash distillations distills at normal pressure and 65~80 DEG C, reclaims methyl alcohol；
(5) after standing separations glycerine, upper strata product enters rectifying column, collects 200~350 DEG C of products, as biodiesel.
3. preparation technology as claimed in claim 2, it is characterised in that：The ester exchange reaction is completed in tubular reactor, its
Described in catalyst account for 2/5~4/5 volume of whole tubular reactor, tubular reactor remainder space is by mineral wool, ceramics
Pearl or/and glass marble are filled.
4. preparation technology as claimed in claim 3, it is characterised in that：The draw ratio of the tubular reactor is more than 200.
5. preparation technology as claimed in claim 2, it is characterised in that：The preparation technology is completed in following device, the device
Including the sampling device, heat-exchanger rig, reaction unit, flash vessel, condenser, distiller, the rectifying column that are sequentially connected；The reaction
Device is connected with tubular reactor by preheater and constituted.
6. preparation technology as claimed in claim 5, it is characterised in that：It is provided between the sampling device and the reaction unit and is changed
Hot device.
7. the preparation technology as described in Claims 2 or 3, it is characterised in that：The tubular reactor by upper end end socket, straight tube body,
Heating furnace and lower end end socket are constituted, and upper end end socket and lower end end socket are respectively fixedly connected with the two ends of straight tube body；Heating furnace is located at
The periphery of straight tube body；Top in the straight tube body is provided with gas distributor, and bottom is provided with catalyst grid；Set in the upper end end socket
There is feed pipe, discharge nozzle is provided with the lower end end socket.
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| CN108219982A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Novel cosolvent method biodiesel synthesis |
| CN107597087B (en) * | 2017-09-07 | 2020-05-19 | 南京大学昆山创新研究院 | ZrO2Polycrystalline ceramic foam catalyst, method for the production thereof and use thereof |
| CN107617441B (en) * | 2017-09-12 | 2020-02-14 | 南京大学昆山创新研究院 | TiO2Polycrystalline foamed ceramic catalyst, preparation method thereof and method for catalyzing waste plastic and biodiesel to produce hydrocarbon by using polycrystalline foamed ceramic catalyst |
| CN112574826A (en) * | 2020-11-21 | 2021-03-30 | 贵州锦江生物能源科技有限公司 | Device and method for preparing fatty acid methyl ester by continuous ester exchange |
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| EP1593732A1 (en) * | 2004-05-03 | 2005-11-09 | Institut Français du Pétrole | Process for the transesterification of plant or animal oil using a catalyst based on zinc or bismuth, titanium and aluminium |
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