CN103877958A - Catalyst for preparing biodiesel and preparation method thereof as well as preparation process of biodiesel - Google Patents
Catalyst for preparing biodiesel and preparation method thereof as well as preparation process of biodiesel Download PDFInfo
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- CN103877958A CN103877958A CN201410090678.3A CN201410090678A CN103877958A CN 103877958 A CN103877958 A CN 103877958A CN 201410090678 A CN201410090678 A CN 201410090678A CN 103877958 A CN103877958 A CN 103877958A
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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
Abstract
The invention discloses a catalyst for preparing biodiesel and a preparation method of the catalyst as well as a novel process applied to preparation of the biodiesel. The catalyst comprises the following components by weight percent: 85.38%-91.42% of ZrO2, 6.75%-9.72% of Al2O3 and 2.68%-4.16% of TiO2. The solid catalyst is used for catalyzing an ester exchange reaction to produce the biodiesel, the reaction time is short, the conversion rate is high, various raw materials can be widely used, the ester exchange reaction can be carried out in a methanol subcritical state to produce the biodiesel, the catalyst is automatically separated from a product after the reaction is finished, and the rinsing operation is not required, thus the clean production of the biodiesel is realized and the production cost of the biodiesel is remarkably reduced.
Description
Technical field
The present invention relates to the preparing technical field of chemical industry aspect, especially a kind of catalyst for the preparation of biodiesel, and prepare production technology and the process units of biodiesel with this catalyst.
Background technology
Along with the continuous intensification of energy crisis, finding novel alternative clean energy resource becomes the emphasis of countries in the world research just gradually.Biodiesel is because Cetane number is high, and greasy property is good, and sulfur content is low, and does not become the focus of the renewable alternative energy source of countries in the world research environmental protection containing advantages such as the aromatic hydrocarbon to environment.It is saturated or unsaturated containing oxygen organic acid low-carbon alcohols Ester that the composition of biodiesel is mainly long-chain, and carbon chain lengths is many at C
18～C
22between, very approaching with diesel oil, also quite similar in nature, so reproducible fatty acid methyl ester is defined as biodiesel by initial people.But, along with biodiesel raw material is more and more diversified and people for the pursuit of recyclability, the definition of biodiesel expands to take the water plant greases such as oil crops, oilseed plant, engineering microalgae and animal fat, waste cooking oil etc. as raw material, utilize glyceryl ester exchange reaction on the methoxy substitution grease main component triglycerides of low-carbon alcohols, the fatty acid methyl ester admixture of the different carbon chain lengths of acquisition.
Biodiesel is because raw material mostly is reproducible biomass resource, once there is a very long time to be considered to inexhaustible raw material sources, but, the serious large-scale promotion application that is restricting biodiesel of this reproducible raw material sources for various reasons.Data shows that its cost of material has accounted for 70～85% of totle drilling cost; high cost of material has seriously hindered large-scale promotion and the application of biodiesel; greatly reduce its market competitiveness; not only make it become the protection product under policy and law protection, also occurred greatly to depart from people's original intention.In order to change this situation, the raw material of cheapness and wide material sources, all in constantly effort of the production cost for how reducing biodiesel, is found on the one hand in countries in the world, production technology and equipment is constantly innovated and is improved on the other hand.
At present countries in the world utilize chemical catalysis mostly, by short chain alcohol under the effect of catalyst with glyceride stock generation ester exchange reaction production biodiesel, the reaction unit of employing mostly is batch stirred tank reactor.Although this traditional process technology maturation, product property is stable, but due to low-carbon alcohols and raw oil material intersolubility poor, traditional batch stirred tank reactor often has to extend the reaction time because mixing effect is undesirable, has not only increased energy consumption and also reduced the market competitiveness of biodiesel.As German Lurgi (Shandong is strange) technique, two sections of Production of Biodiesel Via Transesterification Methods of normal temperature, normal pressure that this process using is most widely used in the world, can reach 96% by this technique grease conversion ratio, excessive methyl alcohol re-uses after reclaiming by methanol recovery device.The biodiesel of this explained hereafter has accounted for the more than 60% of Gross World Product according to statistics, but, the liquid alkali of this process using is as catalyst, comparatively harsh to ingredient requirement, course of reaction more complicated, the liquid catalyst using can not reuse, and a large amount of waste liquor contamination environment of washing meeting generation, and in course of reaction, grease and methyl alcohol do not dissolve each other and causes whole technique mass transfer poor.In addition, tank reactor need to repeatedly repeat Exchange Ester Process just can reach higher conversion ratio, reaction finishes rear catalyst and is difficult to separate, product must just can reach demand of industrial production through washing, result causes the waste water that contains in a large number spent acid, salkali waste to produce, these waste water must could discharge through processing, thereby have increased production cost.And traditional handicraft is higher to ingredient requirement, need refining could use, increase again the cost of pretreatment of raw material, meanwhile, intermittently the utilization rate of equipment is often lower, is difficult to realize automation control, has limited the suitability for industrialized production of biodiesel.
Along with going deep into of research, it is found that and adopt different reaction units to carry out ester exchange reaction, larger on the mass transport process impact of low-carbon alcohols and reaction grease.Based on this discovery, some production technologies, by improving traditional reaction unit or developing new reaction unit, to reduce the resistance to mass tranfer between methyl alcohol and glyceride stock, are enhanced productivity, and reduce costs.As the HTHP homogeneous phase ester exchange process of German Henkel (Henkel) company exploitation, Henkel technique has very much progress in the requirement of raw oil material, can use the grease of not refining as raw material, product is through obtaining biodiesel except soap, neutralization, washing, the process such as dry.Compared with Lurgi technique, Henkel technique has high grease conversion ratio, almost reaches 100%, and high temperature and pressure makes methyl alcohol in supercriticality, can dissolve preferably raw oil material, makes the mass transfer between methyl alcohol and grease have obvious improvement.Most importantly this technique can be using the grease of not refining as raw material, and W-response process shortens dramatically compared with Lurgi technique.But the homogeneous catalyst of this process using and product mix, need a large amount of water to clean, get back to again traditional handicraft in the middle of the process of product postprocessing, be unfavorable for catalyst recovery recycling and preserve the ecological environment.And HTHP causes its reaction condition comparatively harsh, need special device to react, subsequent treatment needs the recovery of a large amount of energy for glycerine, has increased production cost.The still-process carrying out in order to reclaim methyl alcohol is very unfavorable to the non-oxidizability of product, and the cloud point of product is also higher.
So, University of Toronto proposes to adopt soda acid two-step catalysis method to expand the range of choice of biodiesel raw material, to reduce the cost of material of biodiesel, and develop BIOX technique, this technique is introduced a kind of proprietary inert co-solvent to reduce the resistance to mass tranfer between grease and methyl alcohol in reaction system.Adding of inert co-solvent makes whole course of reaction become homogeneous reaction, improved greatly reaction speed and transformation efficiency, and raw oil material just can be converted into biodiesel within a few minutes, and conversion ratio is up to 99%.The acid catalyzed reaction in early stage can reduce the free acid content in raw material significantly, to expanding the range of choice of raw material, reduces cost of material very favourable.At present BIOX technique can have been processed free acid content up to 30% raw oil material, thereby make waste oil and waste animal and vegetable oil directly utilize and become possibility, but inert co-solvent adds and recovery can increase extra production cost, and two-step catalysis operation also makes production process become complicated.Main this technique that is only focuses on solving the problem of pretreatment of raw material, expand the range of choice of raw material, and product and catalyst separation and post-processed does not still depart from traditional handicraft.
In order to expand the range of choice of raw material, solve the separation problem of product and catalyst, reduce three waste product discharges in later stage product processing process, protection of the environment, realizes cleaner production.People develop various production Technology in succession, and wherein overcritical production technology is the most noticeable, because under supercriticality, the moisture in raw material, on not significantly impact of productive rate, is conducive to the formation of methyl esters even to a certain extent.Under this condition, methyl alcohol and grease are homogeneous phase, and interphase mass transfer resistance disappears, and reaction rate extremely increases, and whole reaction only needs just can complete for several minutes.Owing to there is no catalyst in reaction system, product does not need to wash, and purifies more easy yet.But the temperature and pressure that supercritical reaction needs is all very high, and consersion unit is had to specific (special) requirements, meanwhile, maintaining HTHP needs a large amount of energy supplies, and even energy input has been greater than Energy output and has been difficult to carry out industrialization promotion sometimes.And the required alcohol oil rate of this technique is large (being greater than 20:1) conventionally very, need extra retracting device to carry out Methanol Recovery, not only increase energy consumption, also improve production cost.
So imagining, people introduce catalyst to reduce the temperature and pressure of supercritical reaction, picture IFP (IFP) has developed Esterfip-H solid base two-stage reaction technique, this process using two stage fixed-bed reactor, with the ZnAl of spinel structure
2o
4xZnOyAl
2o
3composite oxides are as Catalyst Production biodiesel, flash distillation methyl alcohol sedimentation separation glycerine, and products obtained therefrom is biodiesel after decompression distillation.This technique can realize and approach 100% grease and transform, and in product, fatty acid methyl ester up to 99%, and can obtain the glycerine byproduct of purity more than 98% simultaneously.Although Esterfip-H can obtain than the high a lot of glycerine byproduct (homogeneous phase ester exchange reaction by-product glycerin purity is only 80%) of homogeneous phase ester exchange purity, but its reaction process is too complicated, two stage fixed-bed reactor all adopts higher temperature to react continuously, energy consumption is larger, is unfavorable for reducing production costs.
By comparison, the Mcgyan technique of U.S. SarTec company exploitation is simply many.This technology utilization tubular reactor has larger draw ratio (>50 conventionally), material content constantly changes on its flow direction, and with the perpendicular interface of flow direction on the feature that all remains unchanged as content, pressure, flow velocity and temperature etc. of all parameters of material, adopt one-level fixed-bed tube reactor production biodiesel, with modification ZrO
2, Al
2o
3, TiO
2oxidate microspheres is as catalyst, under 300 ℃, 17MPa condition, carries out ester exchange reaction, and reaction finishes rear supernatant liquid and carries out distillation procedure to remove excessive methyl alcohol, and the methyl alcohol of recovery reenters reaction system through methyl alcohol storage tank.Lower floor's product obtains biodiesel and by-product glycerin through respective handling.Because methyl alcohol in course of reaction is in supercriticality, can be good at dissolving grease, thereby make whole reaction become homogeneous reaction, reaction completes within the several seconds, and can produce continuously, has improved greatly the production efficiency of biodiesel, to reducing costs, improve product competitiveness in the market very favourable.Meanwhile, the requirement of this raw materials technology is lower, and catalyst is insensitive to raw material Free Acid content, moisture.Reaction finishes afterproduct and separates with catalyst is automatic, has reduced product and catalyst separation step, and product do not need washing just can obtain meeting the biodiesel of ASTM standard, and production cost is further reduced, and the while has also been reduced the pollution to environment.But the reaction condition that this technique is used is comparatively harsh, higher reaction pressure has special manufacture requirement to reaction unit, thereby manufacture difficulty and the cost of equipment are increased, increase accordingly the danger of operation, in addition, extra device fabrication cost can increase the production cost of biodiesel undoubtedly, is unfavorable for improving the market competitiveness of biodiesel.
Therefore; develop the nearly critical production technology of biodiesel and reaction unit for reducing production of biodiesel cost, expand range of choice and the saving water resource of raw material, preserve the ecological environment; realize cleaner production, the synthesized competitiveness tool that improves biodiesel is of great significance.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose a kind of catalyst for the preparation of biodiesel, excellent catalytic effect, reaction speed is fast.
In order to realize foregoing invention object, the invention provides following technical scheme: a kind of catalyst for the preparation of biodiesel, is respectively 85.38～91.42% ZrO by weight content
2, 6.75～9.72% Al
2o
3with 2.68～4.16% TiO
2form.
Further, the weight content of this catalyst component is respectively ZrO
288.47%, Al
2o
38.22%, TiO
23.31%.
The present invention also provides the preparation method of catalyst described above, comprises following process: take in proportion ZrO
2, Al
2o
3, TiO
2powder, puts into after ball mill ball milling 24～36h, adds appropriate NaCl, NaHCO
3powder and Ludox, after fully mixing, granulating and forming, dries 12～24h for 105～120 ℃, is transferred to roasting in Muffle furnace, and 500～600 ℃ of insulation 1～2h, are warmed up to 1550～1800 ℃, and insulation 2～4h is cooling, obtains solid catalyst.
The invention allows for the technique that adopts above-mentioned catalyst to prepare biodiesel, comprise the following steps:
(1). glyceride stock and low-carbon alcohols by volume 1:1～5:1 mix, and are heated to 200～250 ℃;
(2). the mixed material after preheating enters in the tubular reactor of loading catalyst as claimed in claim 1, under 260～285 ℃ and 8～12MPa, carries out ester exchange reaction;
(3). reacted material, at 2～3MPa, is carried out to flash distillation at 80～120 ℃;
(4). the material after flash distillation is distillation at normal pressure and 65～80 ℃, reclaims methyl alcohol;
(5). after standing separation glycerine, upper strata product enters rectifying column, collects 200～350 ℃ of products, is biodiesel.
Further, described ester exchange reaction completes in tubular reactor, and wherein said catalyst accounts for 2/5～4/5 volume of whole tubular reactor, the remaining space of this tubular reactor by mineral wool, ceramic bead or/and glass marble fill.
Further, the draw ratio of described tubular reactor is greater than 200.
Further, this preparation technology completes in as lower device, and this device comprises the sampling device, heat-exchanger rig, reaction unit, flash vessel, condenser, distiller, the rectifying column that connect successively; Described reaction unit is communicated with and is formed by preheater and tubular reactor.
Further, between described sampling device and described reaction unit, be provided with heat exchanger.
Further, described tubular reactor is made up of upper end end socket, straight tube body, heating furnace and lower end end socket, and upper end end socket and lower end end socket are fixedly connected on respectively the two ends of straight tube body; Heating furnace is located at the periphery of straight tube body; Top in this straight tube body is provided with gas distributor, and bottom is provided with catalyst grid; In this upper end end socket, be provided with feed pipe, in this lower end end socket, be provided with discharge nozzle.
Compared with prior art, the present invention has the following advantages: catalysis of solid catalyst ester exchange reaction production biodiesel, reaction time is short, conversion ratio is high, can use widely various raw materials, and can under methyl alcohol subcritical state, carry out ester exchange reaction production biodiesel.Reaction finishes rear catalyst and automatically separates with product, and does not need washing operation, thereby has realized the cleaner production of biodiesel, has reduced significantly the production cost of biodiesel.
By the catalysis for preparing biodiesel oil of solid catalyst, reaction temperature and reaction pressure have all obtained reduction to a certain degree, and what especially reaction pressure declined is larger, can under methyl alcohol undercritical conditions, carry out the production of biodiesel.Reaction temperature and pressure drop have reduced device fabrication cost and operation easier on the one hand, have saved on the other hand equipment component manufacturing cost, have improved the price advantage of biodiesel product.This catalyst is insensitive to the moisture in raw material and free acid, thereby increase the range of choice of raw material, there is reaction speed fast, conversion ratio advantages of higher, have the advantage of Mcgyan technology concurrently, and equipment is more intensive simultaneously, three-dimensional small and exquisite, can carry out vehicle-mounted mobile production, thereby break away from the production model in traditional chemical plant.
The present invention has the following advantages compared with traditional biological diesel production technique:
1. because methyl alcohol in course of reaction is in supercriticality, grease is had to good solvability, add solid ZrO
2the catalytic action of polycrystalline foamed ceramics catalyst, reaction completed in tens minutes, and can produce continuously, had improved greatly the production efficiency of biodiesel, to reducing costs, improved product competitiveness in the market very favourable.
2. the requirement of this raw materials technology is lower, and catalyst is insensitive to raw material Free Acid content, moisture.Reaction finishes afterproduct and separates with catalyst is automatic, product and catalyst separation step are reduced, and product does not need washing just can obtain meeting the product of biodiesel B100 national standard, and production cost is further reduced, and has reduced the pollution to environment simultaneously yet.
3. solid ZrO
2polycrystalline foamed ceramics catalyst greatly reduces reaction temperature and pressure, thereby greatly reduces the manufacture requirement of production equipment, and reaction just can realize the conversion ratio of 98% left and right for tens minutes, has higher transformation efficiency.
4. by heat exchanger, the heat reclaiming is used for to feeding preheating, rectifying column waste heat is heated for Methanol Recovery simultaneously, realized the recycling of heat, further reduced energy consumption and cost.
5. be integrated in the flat board of 2～3 square metres, make device smaller and more exquisite efficient, conveniently carry out vehicle-mounted mobile transportation, can play certain mitigation for field operations energy recharge, the cost that also can avoid raw material and product to transport back and forth simultaneously.
Tubular reactor of the present invention is the internal structure through particular design, is a kind of variant of fixed bed reactors, has programming rate fast, be heated evenly, in reaction, moderate pressure is easily controlled, and material mixes at inside reactor, resistance to mass tranfer is little, there is no the advantages such as back-mixing.By the high catalytic stability of foamed ceramics catalyst and long service life, do not need frequently more catalyst changeout, successfully solve the extra cost that fixed-bed reactor brings due to frequent replacing decaying catalyst.
Accompanying drawing explanation
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; 4-alcohol road check-valves; 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 destilling tower overhead collection tank; 23-Methanol Recovery tank; 24-on-condensible gas collecting tank; 25-condenser; 26-methanol loop pump; 27-raw material low-carbon alcohols storage tank; 28-glycerin separator; 29-crude glycerine storage tank; 30-Liquid level adjusting valve; 31-fatty acid methyl ester 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 is surveyed mouth; 40-upper end end socket; 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 end temperature sensor; 53-heating furnace.
The specific embodiment
Describe the present invention below in conjunction with accompanying drawing, the description of this part is only exemplary and explanatory, should not have any restriction to protection scope of the present invention.
The preparation facilities of a kind of biodiesel as shown in Figure 1, comprises sampling system A, reaction system B, methyl alcohol flash system C, methanol recovery system D, glycerine piece-rate system E, fatty acid methyl ester distillation system F and relevant control system;
Sampling system A: comprise gas sampling pipeline and Liquid sample introduction pipeline, wherein Liquid sample introduction pipeline is divided into again glyceride stock sample introduction pipeline and reaction low-carbon alcohols sample introduction pipeline.Liquid sample introduction pipeline is connected with high-pressure metering pump 1 and 2 by pipeline, and gas sampling pipeline is controlled flow by spinner flowmeter 5 and electromagnetic flowmeter 6.And between sampling system and reaction system, be provided with heat exchanger 9, and be connected with the preheater 11 in reaction system B by pipeline, reactor lower end thermal material is carried out to heat recovery, for reactor heating upper end cold feed, to improve the utilization ratio of whole system to heat.
Reaction system B: formed by preheater 11 and tubular reactor 14, wherein preheater 11 comprises regenerator section and mixing of materials part, described mixing of materials part is static mixer, material through preheating laggard enter static mixer enter tubular reactor 14 after mixing.Tubular reactor 14 is specially designed internal structure, as shown in Figure 2, this device has larger draw ratio (>200), can make material content constantly change on flow direction, and with the perpendicular interface of flow direction on all parameters comprise that content, pressure, flow velocity and temperature etc. all remain unchanged; And being provided with gas distributor 42 at charging aperture place, main purpose is to be uniformly distributed low carbon alcohol vapor, makes its fully wetting catalyst surface and inner duct, increases gas-liquid-solid three-phase contact, improves reaction efficiency.Reacted product separates by the catalyst grid 46 of bottom of device with catalyst, and this catalyst grid 46 is that sieve aperture is between porous pressure-resistant materials such as 200～500 order multilayer stainless steel sintered meshwork assemblies or ventilative steel.
Methyl alcohol flash system C: be made up of pressure-reducing valve 16 and flash tank 17, this system adopts adiabatic flash with recovery section methyl alcohol, reduces the pressure of methanol recovery system D and saves part energy consumption and production cost.By condenser 18, gas phase and liquid phase are carried out to condensation respectively, gas condenser reclaims flash gas condensation, and through 23 recyclings of Methanol Recovery tank, liquid condenser will be sent into methyl alcohol destilling tower reboiler 19 after product condensation.
Methanol recovery system D: by distillation, unreacted low-carbon alcohols is recovered to Methanol Recovery tank 23, recycles through methanol loop pump 26, to improve methyl alcohol service efficiency, save production cost, remove the product introduction glycerine piece-rate system E separation of glycerin after methyl alcohol.
Glycerine piece-rate system E: utilize the difference between each density of fraction, reclaim glycerine by gravity settling separation, after sedimentation, upper strata is methyl esters layer, and lower floor is glycerin layer, by height and the mass flow that enters rectifying column 31 of fluid level control valve gate control methyl esters layer.
Fatty acid methyl ester distillation system F: obtain biodiesel by fatty acid methyl ester rectifying column 31 purifies and separates, unreacted raw oil material is by grease circulating pump 33 circular responses, to improve the transformation efficiency of whole system, adopt the vavuum pump of rectification under vacuum to be also responsible for package unit provides and vacuumizes simultaneously.
Control system: be responsible for the startup of whole system and stop, and popping one's head in and instrument is controlled operations such as reaction temperature, pressure, vapo(u)rizing temperatures by each temperature and pressure.
The concrete operation step of above-mentioned process units is as follows:
1. sample introduction operation
Methyl alcohol in raw material low-carbon alcohols storage tank 27 and raw oil material storage tank 34 and raw oil material by volume 1:1～5:1 pump into by high-pressure metering pump the preheater that static mixer is housed and carry out preheating, be preheating to 200～250 ℃ laggard enter static mixer mix, be connected with tubular reactor 14 with check-valves by pipeline.
2. operation
The interior filling solid catalyst of tubular reactor 14, carry out rational loadings setting with experimental data according to actual needs, this technique inner catalyst is excessive, consider reserved raw material blending space and actual heating pipe range, this technique filling 2/5～4/5, by 260～285 ℃ of computer program control heating-up temperatures and 8～12MPa pressure and inlet amount.
This solid catalyst is respectively 85.38～91.42% ZrO by weight content
2, 6.75～9.72% Al
2o
3with 2.68～4.16% TiO
2form; Adopt following process preparation: take in proportion ZrO
2, Al
2o
3, TiO
2powder, puts into after ball mill ball milling 24～36h, adds appropriate NaCl, NaHCO
3powder and Ludox, after fully mixing, granulating and forming, dries 12～24h for 105～120 ℃, is transferred to roasting in Muffle furnace, and 500～600 ℃ of insulation 1～2h, are warmed up to 1550～1800 ℃, and insulation 2～4h is cooling, to obtain final product.
3. lock out operation
This step comprises methyl alcohol flash distillation operation and glycerine lock out operation, wherein in product excessive methyl alcohol at 2～3MPa, at 80～120 ℃ by entering flash tank after pressure-reducing valve, thereby realize the recovery of most of methyl alcohol, after condensation, enter Methanol Recovery tank 23.Glycerine separates by glycerin separator 28, and under the effect of gravity, glycerine and fatty acid methyl ester and unreacted grease AUTOMATIC ZONING, because glycerol density is compared with being positioned at greatly lower floor.
4. purification process
Enter methyl alcohol Distallation systm D from methyl alcohol flash system C product out, near residual methanol distill to remove product at 65～80 ℃ of temperature methyl alcohol boiling point in, after condenser 21 condensations, collect the methyl alcohol of returning from condenser 21 and condenser 25 with Methanol Recovery tank 23, pump into raw material low-carbon alcohols storage tank 27 by methanol loop pump 26 and recycle.The product that glycerine piece-rate system E flows out is by fluid level control valve control flow, enter fatty acid methyl ester rectifying column and carry out the purification operations of biodiesel product, the glycerin component of removing unreacted grease and sneaking into, 200～350 ℃ of products of tower top flow into rectifying column tower top product storage tank 36 after condenser 35 condensations, unreacted oil component and the glycerine composition of bringing on a small quantity are stayed in rectifying column reboiler 32, pumping into raw oil material storage tank 34 through grease circulating pump 33 recycles, products obtained therefrom is proceeded to the special storage tank 37 of biodiesel, obtain meeting the biodiesel product of BD100 standard.
Tubular reactor 14 of the present invention, under the effect of gas distributor, catalyst grid and porous particle catalyst, making full use of supercritical methanol is fully mixed reaction mass to the solvability of grease, ester exchange reaction activation energy has obtained reduction to a certain degree under the catalytic action of catalyst simultaneously, thereby make reaction temperature and pressure all obtain reduction to a certain degree, reaction rate is accelerated, the transformation efficiency of having realized biodiesel 98% in tens minutes, effectively reduces energy consumption and cost.
The present invention carries out heat recovery by heat exchanger 9 is set to the hot fluid of tubular reactor 14 discharge ends, for heating the cold material that feed system A pumps into, realize recycling of excessive methanol by condenser 21, condenser 25 and methanol loop pump 26 simultaneously, made energy consumption and production cost in production process obtain reduction to a certain degree.
The present invention adopts fixed-bed tube reactor, has simple to operately, and programming rate is fast, and automaticity is high, the catalyst feature such as can be recycled, and package unit is integrated on the flat board of 2～3 square metres simultaneously, facilitates vehicle-mounted transport.This raw materials technology does not need to carry out pretreatment in addition, applied widely, and applicable raw material is produced nearby, conservation freight and processing cost, and the biodiesel stable in properties of producing.
The present invention adopts solid catalyst, and reaction temperature and pressure are compared low with the supercritical process that does not use catalyst, thereby has saved a large amount of device fabrication costs, in device fabrication cost and requirement, has larger advantage.Compared with traditional biodiesel production method, pretreatment of raw material and later stage washing operation are saved, not only save pretreatment cost and also reduced the pollution to environment, saved pretreatment of raw material cost and sewage disposal expense, there is larger production cost advantage.
embodiment 1
Adopt preparation facilities and the corresponding preparation method of above-mentioned biodiesel to proceed as follows:
1. press ZrO
288.47%, Al
2o
38.22%, TiO
23.31% weight proportion takes ZrO
2, Al
2o
3, TiO
2powder, puts into after ball mill ball milling 24h, adds appropriate NaCl, NaHCO
3powder and Ludox, after fully mixing, granulating and forming, dries 12h for 120 ℃, is transferred to roasting in Muffle furnace, and 500 ℃ of insulation 1h, are warmed up to 1550 ℃, and insulation 2h is cooling, obtains solid catalyst, and packs the solid catalyst preparing into tubular reactor.
2. by high-pressure metering pump, low-carbon alcohols alcohol and vegetable oil are pumped in preheater according to volume ratio 1:1, be preheating to 200 ℃, the material after preheating enters static mixer fully to be mixed, and described vegetable oil is wilson dogwood oil, and low-carbon alcohols is methyl alcohol.
3. mixed material enters in the tubular reactor of constant temperature and pressure, at 8MPa, under 285 ℃ of conditions, carries out ester exchange reaction, reaction time 15min, and grease conversion ratio is 96.5%.
4. product pressure after heat exchange drops to 3MPa by 8MPa, temperature drops to 80 ℃ by 285 ℃, be recycled in methyl alcohol collecting tank by the methyl alcohol of flash distillation approximately 98%, residue methyl alcohol utilizes methyl alcohol destilling tower to reclaim that (distillation pressure is normal pressure, temperature is 80 ℃), the methyl alcohol of recovery pumps into low-carbon alcohols storage tank by methanol loop pump and recycles.
5. remove the product introduction glycerin separator after methyl alcohol, gravitational settling glycerine, after leaving standstill, upper strata methyl esters layer enters methyl esters rectifying column by fluid level control valve, collect 200～350 ℃ of products of rectifying column tower top and be wanted biodiesel, in tower bottom reboiler, unreacted grease and residual glycerine component are guided methyl alcohol destilling tower by the road into, for the heating of methyl alcohol destilling tower, then get back to raw oil material storage tank cycling and reutilization.Lower floor's glycerine flows into crude glycerine storage tank by fluid level control valve control mutually, and in crude glycerine component, glycerol content is 94%.
embodiment 2
Adopt preparation facilities and the corresponding preparation method of above-mentioned biodiesel to proceed as follows:
1. press ZrO
285.38%, Al
2o
39.72% and TiO
22.68% takes ZrO
2, Al
2o
3, TiO
2powder, puts into after ball mill ball milling 36h, adds appropriate NaCl, NaHCO
3powder and Ludox, after fully mixing, granulating and forming, dries 24h for 105 ℃, is transferred to roasting in Muffle furnace, and 500 ℃ of insulation 2h, are warmed up to 1800 ℃, and insulation 4h is cooling, obtains solid catalyst, and packs the solid catalyst preparing into tubular reactor.
2. by high-pressure metering pump, low-carbon alcohols and vegetable oil are pumped in preheater according to volume ratio 5:1, be preheating to 230 ℃, the material after preheating enters static mixer fully to be mixed, and described vegetable oil is wilson dogwood oil, and low-carbon alcohols is methyl alcohol.
3. mixed material enters in the tubular reactor of constant temperature and pressure, at 8MPa, under 260 ℃ of conditions, carries out ester exchange reaction, reaction time 15min, and grease conversion ratio is 97.2%
4. product pressure after heat exchange drops to 3MPa by 8MPa, temperature drops to 80 ℃ by 285 ℃, be recycled in methyl alcohol collecting tank by the methyl alcohol of flash distillation approximately 98%, residue methyl alcohol utilizes methyl alcohol destilling tower to reclaim that (distillation pressure is normal pressure, temperature is 80 ℃), the methyl alcohol of recovery pumps into low-carbon alcohols storage tank by methanol loop pump and recycles.
5. remove the product introduction glycerin separator after methyl alcohol, gravitational settling glycerine, after leaving standstill, upper strata methyl esters layer enters methyl esters rectifying column by fluid level control valve, collect 200～350 ℃ of products of rectifying column tower top and be wanted biodiesel, unreacted grease and residual glycerine component in tower bottom reboiler are guided methyl alcohol destilling tower by the road into, for the heating of methyl alcohol destilling tower, then get back to raw oil material storage tank cycling and reutilization.Lower floor's glycerine flows into crude glycerine storage tank by fluid level control valve control mutually, and in crude glycerine component, glycerol content is 95.5%.
embodiment 3
Adopt preparation facilities and the corresponding preparation method of above-mentioned biodiesel to proceed as follows:
1. press 91.42% ZrO
2, 6.75% Al
2o
3with 4.16% TiO
2ratio takes ZrO
2, Al
2o
3, TiO
2powder, puts into after ball mill ball milling 30h, adds appropriate NaCl, NaHCO
3powder and Ludox, after fully mixing, granulating and forming, dries 18h for 110 ℃, is transferred to roasting in Muffle furnace, and 550 ℃ of insulation 1.2h, are warmed up to 1670 ℃, and insulation 3h is cooling, obtains solid catalyst, and packs the solid catalyst preparing into tubular reactor.
2. by high-pressure metering pump, low-carbon alcohols alcohol and vegetable oil are pumped in preheater according to volume ratio 3:1, be preheating to 250 ℃, the material after preheating enters static mixer fully to be mixed, and described vegetable oil is wilson dogwood oil, and low-carbon alcohols is methyl alcohol.
3. mixed material enters in the tubular reactor of constant temperature and pressure, at 10MPa, under 275 ℃ of conditions, carries out ester exchange reaction, reaction time 11min, and grease conversion ratio is 98.3%
4. product pressure after heat exchange drops to 2.5MPa by 10MPa, temperature drops to 90 ℃ by 285 ℃, be recycled in methyl alcohol collecting tank by the methyl alcohol of flash distillation approximately 98%, residue methyl alcohol utilizes methyl alcohol destilling tower to reclaim that (distillation pressure is normal pressure, temperature is 65～80 ℃), the methyl alcohol of recovery pumps into low-carbon alcohols storage tank by methanol loop pump and recycles.
Remove the product introduction glycerin separator after methyl alcohol, gravitational settling glycerine, after leaving standstill, upper strata methyl esters layer enters methyl esters rectifying column by fluid level control valve, collect 200～350 ℃ of products of rectifying column tower top and be wanted biodiesel, unreacted grease and residual glycerine component in tower bottom reboiler are guided methyl alcohol destilling tower by the road into, for the heating of methyl alcohol destilling tower, then get back to raw oil material storage tank cycling and reutilization.Lower floor's glycerine flows into crude glycerine storage tank by fluid level control valve control mutually, and in crude glycerine component, glycerol content is 97.6%.
Claims (9)
1. for the preparation of a catalyst for biodiesel, be respectively 85.38～91.42% ZrO by weight content
2, 6.75～9.72% Al
2o
3with 2.68～4.16% TiO
2form.
2. catalyst as claimed in claim 1, is characterized in that: the weight content of this catalyst component is respectively ZrO
288.47%, Al
2o
38.22%, TiO
23.31%.
3. a preparation method for catalyst as claimed in claim 1, comprises following process: take in proportion ZrO
2, Al
2o
3, TiO
2powder, puts into after ball mill ball milling 24～36h, adds appropriate NaCl, NaHCO
3powder and Ludox, after fully mixing, granulating and forming, dries 12～24h for 105～120 ℃, is transferred to roasting in Muffle furnace, and 500～600 ℃ of insulation 1～2h, are warmed up to 1550～1800 ℃, and insulation 2～4h is cooling, obtains solid catalyst.
4. a preparation technology for biodiesel, comprises the following steps:
(1). glyceride stock and low-carbon alcohols by volume 1:1～5:1 mix, and are heated to 200～250 ℃;
(2). the mixed material after preheating enters in the tubular reactor of loading catalyst as claimed in claim 1, under 260～285 ℃ and 8～12MPa, carries out ester exchange reaction;
(3). reacted material, at 2～3MPa, is carried out to flash distillation at 80～120 ℃;
(4). the material after flash distillation is distillation at normal pressure and 65～80 ℃, reclaims methyl alcohol;
(5). after standing separation glycerine, upper strata product enters rectifying column, collects 200～350 ℃ of products, is biodiesel.
5. preparation technology as claimed in claim 4, it is characterized in that: described ester exchange reaction completes in tubular reactor, wherein said catalyst accounts for 2/5～4/5 volume of whole tubular reactor, the remaining space of this tubular reactor by mineral wool, ceramic bead or/and glass marble fill.
6. preparation technology as claimed in claim 5, is characterized in that: the draw ratio of described tubular reactor is greater than 200.
7. preparation technology as claimed in claim 4, is characterized in that: this preparation technology completes in as lower device, and this device comprises the sampling device, heat-exchanger rig, reaction unit, flash vessel, condenser, distiller, the rectifying column that connect successively; Described reaction unit is communicated with and is formed by preheater and tubular reactor.
8. preparation technology as claimed in claim 7, is characterized in that: between described sampling device and described reaction unit, be provided with heat exchanger.
9. preparation technology as described in claim 4 or 5, is characterized in that: described tubular reactor is made up of upper end end socket, straight tube body, heating furnace and lower end end socket, and upper end end socket and lower end end socket are fixedly connected on respectively the two ends of straight tube body; Heating furnace is located at the periphery of straight tube body; Top in this straight tube body is provided with gas distributor, and bottom is provided with catalyst grid; In this upper end end socket, be provided with feed pipe, in this lower end end socket, be provided with discharge nozzle.
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