CN105385506A - Apparatus and method for producing biodiesel through solid base catalysis heterogeneous ester interchange technology - Google Patents
Apparatus and method for producing biodiesel through solid base catalysis heterogeneous ester interchange technology Download PDFInfo
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- CN105385506A CN105385506A CN201510920121.2A CN201510920121A CN105385506A CN 105385506 A CN105385506 A CN 105385506A CN 201510920121 A CN201510920121 A CN 201510920121A CN 105385506 A CN105385506 A CN 105385506A
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000007787 solid Substances 0.000 title claims abstract description 22
- 238000005516 engineering process Methods 0.000 title abstract description 5
- 238000005815 base catalysis Methods 0.000 title abstract description 4
- 150000002148 esters Chemical class 0.000 title abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 215
- 235000011187 glycerol Nutrition 0.000 claims abstract description 107
- 238000000034 method Methods 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 238000003860 storage Methods 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000010775 animal oil Substances 0.000 claims abstract description 6
- 239000002440 industrial waste Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 239000002551 biofuel Substances 0.000 claims description 49
- 241000238634 Libellulidae Species 0.000 claims description 25
- 239000003921 oil Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 238000005809 transesterification reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- OGXRXFRHDCIXDS-UHFFFAOYSA-N methanol;propane-1,2,3-triol Chemical compound OC.OCC(O)CO OGXRXFRHDCIXDS-UHFFFAOYSA-N 0.000 claims description 7
- 239000007792 gaseous phase Substances 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 235000012216 bentonite Nutrition 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- 239000010773 plant oil Substances 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 19
- 239000002585 base Substances 0.000 description 17
- 239000002028 Biomass Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 glycerin fatty acid ester Chemical class 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention an apparatus and a method for producing biodiesel through a solid base catalysis heterogeneous ester interchange technology. The apparatus comprises a raw material mixing tank, a reactor, a liquid separator, a centrifuge, a fluidized bed dryer, an absorbing and filtering device, a biodiesel rectifying tower, a glycerin rectifying tower, a biodiesel storage tank and a glycerin storage tank. The method has obviously higher raw material utilization rate than traditional methods, allows a solid catalyst used in the invention to be recycled, realizes high industrial waste heat utilization rate, allows the purity of the produced biodiesel to reach 96-99%, and is suitable for producing biodiesel in places with high output of plant oil or animal oil to solve the current energy shortage problem.
Description
Technical field
The invention belongs to biomass energy and produce chemical industry technology field, relate to the apparatus and method of the heterogeneous Production of Biodiesel Via Transesterification Method of a kind of catalyzed by solid base.
Background technology
Along with the develop rapidly of world economy and the day by day serious of energy scarcity problem, various countries increase day by day for the demand of the energy.Because traditional fossil fuel energy utilization ratio is low, it is large to pollute and non-renewable, the researchist of various countries substitutes or slows down traditional fossil oil trying to explore to develop the renewable energy resources that are efficient, environmental protection.Other renewable energy sources such as biomass energy, sun power, wind energy become the leading role of world energy sources gradually.Biofuel has good development prospect as a kind of clean biomass energy, its alternative petrochemical diesel fuel, through the development of recent two decades, has become the second largest biomass fuel after ethanol.
Current Europe, the U.S. and Japan etc. can scale operation biofuel to biofuel research country comparatively early.Such as Europe mainly utilizes the rapeseed oil of supply abundance for raw material production biofuel, and European Union has also formulated relevant support policy and corresponding developing goal for production of biodiesel.But in China, start late to the research of biofuel, the problems such as the high and supply of raw materials for production cost is unstable seriously limit the development of China's biofuel.
The main component of biofuel is fatty acid methyl ester, and it obtains by carrying out alcoholysis to animal oil such as renewable resources such as peanut oil, soybean wet goods vegetables oil and pig, ox, sheep.It has that cetane value is high, oxygen level is high, nontoxic renewable, safety is easily transported, not the advantages such as objectionable impurities such as sulfur-bearing, lead, halogen.And biofuel is in harmonious proportion with certain proportion and petrifaction diesel and uses, can oil consumption be reduced, improve dynamic performance.Therefore, biofuel has without the advantage and development potentiality with analogy.
The technology of preparing of conventional biofuel has Physical and chemical method two kinds: Physical mainly comprises direct mixing method and micro emulsion method, and chemical method mainly comprises high-temperature cracking method and ester-interchange method.Direct mixing method and micro emulsion method are that vegetable and animals oils is direct and diesel oil carries out used in combination, but have the shortcomings such as carbon deposit is serious, incomplete combustion, lubricating oil viscosity increase due to obtained biofuel and should not adopt.High-temperature cracking method is under heat or heat and catalyst action, makes a kind of Substance Transformation become another material, although process is simple, not pollution, cracking apparatus is expensive, and reaction process is wayward.Ester-interchange method is the method utilizing low-carbon alcohol to carry out reacting production biofuel with the glycerin fatty acid ester in vegetables oil or animal oil under catalyst action.Mainly comprise four kinds of methods such as liquid base, acid catalysis homogeneous phase ester-interchange method, biological enzyme ester-interchange method, overcritical ester-interchange method, the heterogeneous ester-interchange method of solid catalyst at present.Wherein liquid base, acid catalysis homogeneous phase ester-interchange method raw material pretreatment process complexity, the free fatty acids in reactant and water affect larger on transesterification reaction, and residual alkali can generate soap in diesel oil, and easily result in blockage the problems such as pipeline; Biological enzyme ester-interchange method is because the reaction times is longer, the price of enzyme, and methyl alcohol easily causes the irreversible inactivation of biological enzyme, problems such as the life-span is shorter and being seldom applied in industry; Overcritical ester-interchange method reaction conditions requires High Temperature High Pressure, and facility investment is large, and methyl alcohol is difficult to recycle, and raw material availability is low; The heterogeneous ester-interchange method of solid catalyst is not high to feed quality requirements, and not by the impact of moisture and free fatty acids, equipment corrosion is weak, and catalyzer is easy to be separated and recycling, can not produce waste liquid and the dark favor by investigator.Therefore the present invention proposes a kind of apparatus and method adopting the heterogeneous Production of Biodiesel Via Transesterification Method of catalyzed by solid base, for solving the problems such as the raw material availability existed in current base catalysis homogeneous phase ester exchange process is low, technical process is long, wastewater flow rate is many.
Summary of the invention
Based on the shortcoming of above prior art, the present invention first object is to propose the method that biofuel occurs to produce the heterogeneous transesterify of a kind of catalyzed by solid base.
It is high that the present invention second object is to solve reaction conditions requirement in current base catalysis homogeneous phase ester exchange process, the problems such as raw material availability is low.
The present invention the 3rd object is to solve catalyst separating difficulty in existing technique, the problems such as cyclic utilization rate is low.
The present invention the 4th object be to provide utilize vegetables oil or animal oil, mode that methyl alcohol is raw material production biofuel, solve current China energy scarcity problem.
Technical solution of the present invention is as follows.
A device for the heterogeneous Production of Biodiesel Via Transesterification Method of catalyzed by solid base, comprises raw material mixing tank, reactor, skimmer, whizzer, fluidized bed dryer, absorbing and filtering device, biodiesel rectifying tower, glycerine rectifying tower, biofuel storage tank and glycerine storage tank;
Described raw material mixing tank outlet is connected successively with reactor, skimmer, the outlet of skimmer lower floor is connected with whizzer opening for feed, whizzer first discharge port is connected with dryer feed mouth, moisture eliminator discharge port is connected with reactor second opening for feed, whizzer second discharge port is connected with glycerine rectifying tower opening for feed, skimmer upper strata discharge port, glycerine reservoir outlet are connected with absorbing and filtering device second opening for feed, and absorbing and filtering device discharge port is connected with biodiesel rectifying tower opening for feed; Described biodiesel rectifying tower tower top discharge port is connected with raw material mixing tank the 3rd opening for feed, at the bottom of biodiesel rectifying tower tower, discharge port is connected with biofuel reservoir inlet, glycerine rectifying tower top discharge port is connected with raw material mixing tank the 3rd discharge port, and at the bottom of glycerine rectifying tower, discharge port is connected with glycerine reservoir inlet.
Said apparatus, also comprises feed preheater, methanol glycerol preheater, biodiesel rectifying tower condenser, biodiesel rectifying tower reboiler, glycerine rectifying tower condenser, glycerine rectifying tower reboiler, biofuel condenser, glycerine condenser;
Described feed preheater is connected between raw material mixing tank discharge port and reactor feed mouth by pipeline, and described methanol glycerol preheater is connected between whizzer second discharge port and glycerine rectifying tower opening for feed by pipeline; Described biodiesel rectifying tower condenser one end exports with biodiesel rectifying tower top gaseous phase and is connected, and the other end is connected with the biodiesel rectifying tower trim the top of column mouth of pipe and raw material mixing tank the 3rd opening for feed respectively; Described biodiesel rectifying tower reboiler is connected to liquid-phase outlet at the bottom of biodiesel rectifying tower tower by pipeline and between the import of biodiesel rectifying tower tower spirit phase; Described glycerine rectifying tower condenser one end exports with glycerine rectifying tower top gaseous phase and is connected, and the other end is connected with the glycerine rectifying column top return mouth of pipe and raw material mixing tank the 3rd opening for feed respectively; Described glycerine rectifying tower reboiler is connected to liquid-phase outlet at the bottom of glycerine rectifying tower by pipeline and between the import of glycerine rectifying tower gas phase; Described biofuel condenser to be connected at the bottom of biodiesel rectifying tower tower between discharge port and biofuel storage tank by pipeline; Described glycerine condenser to be connected at the bottom of glycerine rectifying tower between discharge port and glycerine storage tank by pipeline.
In said apparatus, described whizzer is the one in scraper-type whizzer, common link-suspended basket centrifuge, hanging bag centrifuge.
A method for the heterogeneous Production of Biodiesel Via Transesterification Method of catalyzed by solid base, comprises the steps:
Stock oil and the incoming stock mixing tank of methyl alcohol, enter reactor reaction after preheating together with solid base catalyst, then enters skimmer and be separated, be divided into two-layer up and down after leaving standstill;
Wherein, the catalyzer of lower floor, glycerine and methyl alcohol enter whizzer, the isolated catalyzer of whizzer first discharge port enters fluidized bed dryer drying, enter reactor cycles again to utilize, the isolated glycerine of whizzer second discharge port and methyl alcohol enter glycerine rectifying tower, the incoming stock mixing tank recycle of a tower top methanol condensed part, a part is back to glycerine rectifying tower, enters glycerine storage tank after the glycerine preheating material mixing tank distillated at the bottom of glycerine rectifying tower;
Wherein, the coarse biodiesel on upper strata enters absorbing and filtering device, unreacted stock oil in atlapulgite absorption biofuel in absorbing and filtering device, glycerine, unitary and binary glyceride impurity, the glycerine of atlapulgite in glycerine storage tank having adsorbed impurity rinses and realizes regeneration, the waste liquid rinsed is discharged outside absorbing and filtering device, coarse biodiesel after adsorption treatment enters biodiesel rectifying tower rectifying, a tower top methanol condensed part gets back to the recycle of raw material mixing tank, a part is back in biodiesel rectifying tower as phegma, biofuel storage tank is entered after the biofuel preheating material mixing tank distillated at the bottom of tower.
In aforesaid method, described liquid distributing device adopts the form of three skimmer parallel connections, during each rotation, described three skimmers meet: one for charging, one for leave standstill, one for discharging, three processes respectively carry out 1-2.5 hour, within every 3-7.5 hour, carry out charging, leave standstill and the rotation of discharging, number of times is once.
In aforesaid method, the present invention adopts heterogeneous transesterification reaction, and described solid base catalyst comprises for K
2cO
3/ γ-Al
2o
3, CaO/MgO, WO
3/ ZrO
2-Al
2o
3or the one in alkaline bentonites soil, its consumption accounts for the 0.9%-1.6% of stock oil quality.
In aforesaid method, described stock oil is more than one in vegetables oil or animal oil, and described methyl alcohol and stock oil consumption mol ratio are (6-9): 1.
In aforesaid method, the described reactor reaction time is 60-120min, and temperature of reaction is 60-70 DEG C, and reactor mixing speed is 700-900r/min.
In aforesaid method, biodiesel rectifying tower and glycerine rectifying tower tower top methyl alcohol are whole condensation, and a phlegma all part is back in rectifying tower as phegma, and another part is as the incoming stock mixing tank recycle of raw material; At the bottom of biodiesel rectifying tower and glycerine rectifying tower, distillate is all for preheating material mixing tank, then enters storage tank respectively and store, and improves the industrial waste heat utilising efficiency of this technique, reduces energy loss.
In aforesaid method, the glycerine part distillated at the bottom of described glycerine rectifying tower enters storage tank (17) as by product, and another part, for rinsing the atlapulgite of the impurity adsorbed in coarse biodiesel, makes atlapulgite cyclic regeneration.
In aforesaid method, described absorbing and filtering device comprises two containers, during production, one absorbs skimmer for atlapulgite and enters impurity in the coarse biodiesel of adsorption unit, another is for rinsing the atlapulgite adsorbing impurity with byproduct glycerine, atlapulgite is regenerated, thus realizes recycling.
The principle of the invention: production process of the present invention be divided into mixing and preheating, reaction, separation, circulation Four processes, production process is continuous flow procedure.Reactor (3) is entered by preheater (2) preheating after raw material mixing, after reaction certain hour, mixed solution enters skimmer (4), solid base catalyst is separated through centrifugal, dry, glycerine is through centrifugal, rectifying separation, biofuel is through absorbing and filtering, rectifying separation, and gained methyl alcohol, solid base catalyst are circulated to reactor (3) recycle, and the first preheating material of gained biofuel, glycerine cools and enters storage tank.
The present invention and existing technics comparing, have following advantage and effect: (1) solid base catalyst, methanol loop utilize, and raw material availability is improved greatly.(2) through atlapulgite absorption glycerine and unreacted raw material, only remaining methyl alcohol and biofuel and a small amount of impurity, isolate biofuel by rectifying tower (7), thus biofuel purity is higher.(3) present invention process production process is without the need to water-washing step, eliminates the discharge of waste water from root.(4) biofuel distillated from rectifying tower and the first preheating material of glycerine cool and enter storage tank, make hot waste gas obtain utilization, improve capacity usage ratio.(5) present invention process is provided with three skimmers 4, a set of absorbing and filtering device 5, ensure that production process is carried out continuously.
Accompanying drawing explanation
Fig. 1 is the heterogeneous preparing biodiesel by ester interchange device of catalyzed by solid base of the present invention.
In figure, all parts is as follows: raw material mixing tank 1, feed preheater 2, reactor 3, skimmer 4, absorbing and filtering device 5, biodiesel rectifying tower condenser 6, biodiesel rectifying tower 7, biodiesel rectifying tower reboiler 8, glycerine rectifying tower condenser 9, glycerine rectifying tower 10, glycerine rectifying tower reboiler 11, methanol glycerol preheater 12, whizzer 13, fluidized bed dryer 14, glycerine condenser 15, biofuel condenser 16, glycerine storage tank 17, biofuel storage tank 18.
Specific embodiments
Take plam oil as the Production Flow Chart that 40,000 tons of biofuel produced per year by stock oil:
As shown in Figure 1: this technical process main device has: comprise raw material mixing tank 1, reactor 3, skimmer 4, whizzer 13, fluidized bed dryer 14, absorbing and filtering device 5, biodiesel rectifying tower 7, glycerine rectifying tower 10, biofuel storage tank 18 and glycerine storage tank 17;
Described raw material mixing tank 1 outlet is connected successively with reactor 3, skimmer 4, the outlet of skimmer 4 lower floor is connected with whizzer 13 opening for feed, whizzer 13 first discharge port is connected with moisture eliminator 14 opening for feed, moisture eliminator 14 discharge port is connected with reactor 3 second opening for feed, whizzer 13 second discharge port is connected with glycerine rectifying tower 10 opening for feed, skimmer 4 upper strata discharge port, glycerine storage tank 17 discharge port are connected with absorbing and filtering device 5 second opening for feed, and absorbing and filtering device 5 discharge port is connected with biodiesel rectifying tower 7 opening for feed; Described biodiesel rectifying tower 7 tower top discharge port is connected with raw material mixing tank 1 the 3rd opening for feed, at the bottom of biodiesel rectifying tower 7 tower, discharge port is connected with biofuel storage tank 18 opening for feed, glycerine rectifying tower 10 tower top discharge port is connected with raw material mixing tank 1 the 3rd discharge port, and at the bottom of glycerine rectifying tower 10 tower, discharge port is connected with glycerine storage tank 17 opening for feed.Also comprise feed preheater 2, methanol glycerol preheater 12, biodiesel rectifying tower condenser 6, biodiesel rectifying tower reboiler 8, glycerine rectifying tower condenser 9, glycerine rectifying tower reboiler 11, biofuel condenser 16, glycerine condenser 15; Described feed preheater 2 is connected between raw material mixing tank 1 discharge port and reactor 3 opening for feed by pipeline, and described methanol glycerol preheater 12 is connected between whizzer 13 second discharge port and glycerine rectifying tower 10 opening for feed by pipeline; Described biodiesel rectifying tower condenser 6 one end exports with biodiesel rectifying tower 7 top gaseous phase and is connected, and the other end is connected with the biodiesel rectifying tower 7 trim the top of column mouth of pipe and raw material mixing tank 1 the 3rd opening for feed respectively; Described biodiesel rectifying tower reboiler 8 is connected to liquid-phase outlet at the bottom of biodiesel rectifying tower 7 tower by pipeline and between the import of biodiesel rectifying tower 7 tower spirit phase; Described glycerine rectifying tower condenser 9 one end exports with glycerine rectifying tower 10 top gaseous phase and is connected, and the other end is connected with the glycerine rectifying tower 10 trim the top of column mouth of pipe and raw material mixing tank 1 the 3rd opening for feed respectively; Described glycerine rectifying tower reboiler 11 is connected to liquid-phase outlet at the bottom of glycerine rectifying tower 10 tower by pipeline and between the import of glycerine rectifying tower 10 gas phase; Described biofuel condenser 16 to be connected at the bottom of biodiesel rectifying tower 7 tower between discharge port and biofuel storage tank 18 by pipeline; Described glycerine condenser 15 to be connected at the bottom of glycerine rectifying tower 10 tower between discharge port and glycerine storage tank 17 by pipeline.Described whizzer 13 is the one in scraper-type whizzer, common link-suspended basket centrifuge, hanging bag centrifuge.
Plam oil (5417kg/h, molecular weight is 848g/mol) and the incoming stock mixing tank 1 of methyl alcohol (540.54kg/h), after feed preheater 2 is preheated to 65 DEG C, enter reactor 3 react, reactor mixing speed is 800r/min, and adds the solid base catalyst alkali wilkinite (65.00kg/h) that consumption is plam oil quality 1.2%.Then after the reaction of 90min, mixed solution (6473.83kg/h) enters skimmer 4 and is separated, three skimmers circulate the charging carried out hour successively, one hour leave standstill, the discharging of one hour, rotation in three hours once, the solid base catalyst of lower floor after leaving standstill, glycerine and methyl alcohol (total flux 998.54kg/h) enter whizzer 13 (scraper-type whizzer), it is dry that whizzer 13 (scraper-type whizzer) the first discharge port isolated solid base catalyst alkaline bentonites soil (48.20kg/h) enters fluidized bed dryer 14, and then enter reactor 3 recycle, whizzer 13 (scraper-type whizzer) the isolated glycerine of the second discharge port and methyl alcohol (total flux 950.34kg/h) enter glycerine rectifying tower 10, tower top methyl alcohol (98% productive rate, a 423.74kg/h) condensation part incoming stock mixing tank 1 recycle, a part is back to glycerine rectifying tower 10, the glycerine (526.61kg/h) distillated at the bottom of tower is first for preheating material mixing tank 1, glycerine storage tank 17 is entered after cooling.The coarse biodiesel on upper strata and methyl alcohol (total flux 5475.29kg/h) enter absorbing and filtering device 5, two containers circulate successively and carry out absorbing and filtering, regeneration, unreacted stock oil in atlapulgite removing biofuel and glycerine, the impurity such as unitary and binary glyceryl ester, then coarse biodiesel and methyl alcohol (total flux 5348.80kg/h) enter biodiesel rectifying tower 7, tower top methyl alcohol (99.98% productive rate, a 108.11kg/h) condensation part gets back to raw material mixing tank 1 recycle, a part is back to biodiesel rectifying tower 7, biofuel (98% productive rate distillated at the bottom of tower, 5000kg/h) preheating material mixing tank 1, biofuel storage tank 18 is entered after cooling.
In case of the present invention, wastewater discharge is 0 ton, has had very large improvement to improve compared with producing a large amount of waste water in traditional mode of production biodiesel processes.Meanwhile, carrying out preliminary energy balance to this technical process, can be able to plam oil be that to produce water of condensation consumption in the technique of 40,000 tons of biofuel per year be 6.2 × 10 to stock oil
4kg/h, required steam consumption is 7 × 10
4kg/h, total energy requirement is 7.4 × 10
6kJ/h
Case of the present invention is just in order to describe the case cited by Production Flow Chart of the present invention in detail, instead of the restriction to the invention process method, for affiliated person skilled in art, corresponding variation can be done in above-mentioned requirements, cannot enumerate here.All in spirit of the present invention and amendment done in principle, equivalent replacement waits and all should belong within protection scope of the present invention.
Claims (10)
1. the device of the heterogeneous Production of Biodiesel Via Transesterification Method of catalyzed by solid base, it is characterized in that, comprise raw material mixing tank (1), reactor (3), skimmer (4), whizzer (13), fluidized bed dryer (14), absorbing and filtering device (5), biodiesel rectifying tower (7), glycerine rectifying tower (10), biofuel storage tank (18) and glycerine storage tank (17);
Described raw material mixing tank (1) outlet and reactor (3), skimmer (4) connects successively, the outlet of skimmer (4) lower floor is connected with whizzer (13) opening for feed, whizzer (13) first discharge port is connected with moisture eliminator (14) opening for feed, moisture eliminator (14) discharge port is connected with reactor (3) second opening for feed, whizzer (13) second discharge port is connected with glycerine rectifying tower (10) opening for feed, skimmer (4) upper strata discharge port, glycerine storage tank (17) discharge port is connected with absorbing and filtering device (5) second opening for feed, absorbing and filtering device (5) discharge port is connected with biodiesel rectifying tower (7) opening for feed, described biodiesel rectifying tower (7) tower top discharge port is connected with raw material mixing tank (1) the 3rd opening for feed, at the bottom of biodiesel rectifying tower (7) tower, discharge port is connected with biofuel storage tank (18) opening for feed, glycerine rectifying tower (10) tower top discharge port is connected with raw material mixing tank (1) the 3rd discharge port, and at the bottom of glycerine rectifying tower (10) tower, discharge port is connected with glycerine storage tank (17) opening for feed.
2. the device of the heterogeneous Production of Biodiesel Via Transesterification Method of catalyzed by solid base according to claim 1, it is characterized in that, also comprise feed preheater (2), methanol glycerol preheater (12), biodiesel rectifying tower condenser (6), biodiesel rectifying tower reboiler (8), glycerine rectifying tower condenser (9), glycerine rectifying tower reboiler (11), biofuel condenser (16), glycerine condenser (15);
Described feed preheater (2) is connected between raw material mixing tank (1) discharge port and reactor (3) opening for feed by pipeline, and described methanol glycerol preheater (12) is connected between whizzer (13) second discharge port and glycerine rectifying tower (10) opening for feed by pipeline; Described biodiesel rectifying tower condenser (6) one end exports with biodiesel rectifying tower (7) top gaseous phase and is connected, and the other end is connected with biodiesel rectifying tower (7) the trim the top of column mouth of pipe and raw material mixing tank (1) the 3rd opening for feed respectively; Described biodiesel rectifying tower reboiler (8) is connected to liquid-phase outlet at the bottom of biodiesel rectifying tower (7) tower by pipeline and between the import of biodiesel rectifying tower (7) tower spirit phase; Described glycerine rectifying tower condenser (9) one end exports with glycerine rectifying tower (10) top gaseous phase and is connected, and the other end is connected with glycerine rectifying tower (10) the trim the top of column mouth of pipe and raw material mixing tank (1) the 3rd opening for feed respectively; Described glycerine rectifying tower reboiler (11) to be connected at the bottom of glycerine rectifying tower (10) tower between liquid-phase outlet and glycerine rectifying tower (10) gas phase import by pipeline; Described biofuel condenser (16) to be connected at the bottom of biodiesel rectifying tower (7) tower between discharge port and biofuel storage tank (18) by pipeline; Described glycerine condenser (15) to be connected at the bottom of glycerine rectifying tower (10) tower between discharge port and glycerine storage tank (17) by pipeline.
3. the device of the heterogeneous Production of Biodiesel Via Transesterification Method of a kind of catalyzed by solid base according to claim 1, is characterized in that, described whizzer (13) is scraper-type whizzer, one in common link-suspended basket centrifuge, hanging bag centrifuge.
4. utilize the method for device production biofuel described in any one of claim 1-3, it is characterized in that, comprise the steps:
Stock oil and the incoming stock mixing tank of methyl alcohol (1), enter reactor (3) reaction together with solid base catalyst after preheating, then enter skimmer (4) and be separated, be divided into two-layer up and down after leaving standstill;
Wherein, the catalyzer of lower floor, glycerine and methyl alcohol enter whizzer (13), it is dry that the isolated catalyzer of whizzer (13) first discharge port enters fluidized bed dryer (14), enter reactor (3) recycle again, the isolated glycerine of whizzer (13) second discharge port and methyl alcohol enter glycerine rectifying tower (10), incoming stock mixing tank (1) recycle of a tower top methanol condensed part, a part is back to glycerine rectifying tower (10), glycerine storage tank (17) is entered after the glycerine preheating material mixing tank (1) distillated at the bottom of glycerine rectifying tower (10) tower,
Wherein, the coarse biodiesel on upper strata enters absorbing and filtering device (5), unreacted stock oil in atlapulgite absorption biofuel in absorbing and filtering device (5), glycerine, unitary and binary glyceride impurity, the glycerine of atlapulgite in glycerine storage tank (17) having adsorbed impurity rinses and realizes regeneration, the waste liquid rinsed discharges absorbing and filtering device (5) outward, coarse biodiesel after adsorption treatment enters biodiesel rectifying tower (7) rectifying, a tower top methanol condensed part gets back to raw material mixing tank (1) recycle, a part is back in biodiesel rectifying tower (7) as phegma, biofuel storage tank (18) is entered after the biofuel preheating material mixing tank (1) distillated at the bottom of tower.
5. method according to claim 3, it is characterized in that, described liquid distributing device (4) adopts the form of three skimmer parallel connections, during each rotation, described three skimmers meet: one for charging, one for leave standstill, one for discharging, three processes respectively carry out 1-2.5 hour, and within every 3-7.5 hour, carry out charging, leave standstill and the rotation of discharging, number of times is once.
6. method according to claim 3, it is characterized in that, the present invention adopts heterogeneous transesterification reaction, and described solid base catalyst comprises for K
2cO
3/ γ-Al
2o
3, CaO/MgO, WO
3/ ZrO
2-Al
2o
3or the one in alkaline bentonites soil, its consumption accounts for the 0.9%-1.6% of stock oil quality; Described stock oil is more than one in vegetables oil or animal oil, and described methyl alcohol and stock oil consumption mol ratio are (6-9): 1.
7. method according to claim 3, it is characterized in that, described reactor (3) reaction times is 60-120min, and temperature of reaction is 60-70 DEG C, and reactor (3) mixing speed is 700-900r/min.
8. method according to claim 3, it is characterized in that, biodiesel rectifying tower (7) and glycerine rectifying tower (10) tower top methyl alcohol are whole condensation, a phlegma all part is back in rectifying tower as phegma, and another part is as the incoming stock mixing tank recycle of raw material; At the bottom of biodiesel rectifying tower (7) and glycerine rectifying tower (10) tower, distillate is all for preheating material mixing tank (1), then enters storage tank respectively and store, and improves the industrial waste heat utilising efficiency of this technique, reduces energy loss.
9. method according to claim 3, it is characterized in that, the glycerine part distillated at the bottom of described glycerine rectifying tower (10) tower enters storage tank (17) as by product, another part, for rinsing the atlapulgite of the impurity adsorbed in coarse biodiesel, makes atlapulgite cyclic regeneration.
10. method according to claim 3, it is characterized in that, described absorbing and filtering device (5) comprises two containers, during production, one absorbs skimmer for atlapulgite and enters impurity in the coarse biodiesel of adsorption unit, another is for rinsing the atlapulgite adsorbing impurity with byproduct glycerine, atlapulgite is regenerated, thus realizes recycling.
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