CN116036998A - Reaction device and method for producing biodiesel by transesterification method - Google Patents
Reaction device and method for producing biodiesel by transesterification method Download PDFInfo
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- CN116036998A CN116036998A CN202111260904.4A CN202111260904A CN116036998A CN 116036998 A CN116036998 A CN 116036998A CN 202111260904 A CN202111260904 A CN 202111260904A CN 116036998 A CN116036998 A CN 116036998A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 149
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000003225 biodiesel Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 122
- 239000002994 raw material Substances 0.000 claims abstract description 100
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 125000004185 ester group Chemical group 0.000 claims abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- 239000000835 fiber Substances 0.000 claims description 76
- 239000003054 catalyst Substances 0.000 claims description 53
- 239000004519 grease Substances 0.000 claims description 53
- 239000003921 oil Substances 0.000 claims description 53
- 235000019198 oils Nutrition 0.000 claims description 50
- 239000012528 membrane Substances 0.000 claims description 39
- 239000010410 layer Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010495 camellia oil Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920006306 polyurethane fiber Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 241001048891 Jatropha curcas Species 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 6
- 238000006276 transfer reaction Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 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
- 241000221089 Jatropha Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The utility model discloses a reaction device and a method for producing biodiesel by an ester exchange method. The reaction device comprises a micro-channel mixing device I, a micro-channel mixing device II and a transesterification reactor. The transesterification reaction method is as follows: the method comprises the steps of taking a mixed material I with a molar ratio of low-carbon alcohol to triglyceride being more than or equal to 3:1 as a main reaction material and entering from a feed inlet of a transesterification reactor, and taking a mixed material II with a molar ratio of low-carbon alcohol to triglyceride being less than 3:1 as an enhanced mass transfer material and introducing the mixed material I and the mixed material II into the transesterification reactor to perform efficient transesterification reaction in the reactor. According to the utility model, through improving the mixing state and the mixing feeding mode of the triglyceride and the low-carbon alcohol, the mass transfer in the whole transesterification reaction process is enhanced, the mass transfer reaction rate and the single-pass conversion rate of raw materials of the ester and the low-carbon alcohol of a difficult-to-dissolve system are improved, the reaction residence time is shortened, and the production efficiency of biodiesel by the transesterification method is improved.
Description
Technical Field
The utility model belongs to the field of biodiesel production, and particularly relates to a reaction device and a production method for obtaining biodiesel by utilizing transesterification.
Background
The biodiesel has the advantages of good engine low-temperature starting performance, low sulfur content, no aromatic hydrocarbon causing environmental pollution, high flash point, good safety performance, high cetane number, good lubricating performance and the like.
At present, the industrial biodiesel is produced by a transesterification method, which is to replace glycerol in triglycol ester in raw oil by using low-carbon alcohols such as methanol under the action of a catalyst to obtain biodiesel; the transesterification reaction is the core of the whole process, the prior art is mainly based on a triglycol ester raw material and methanol as an immiscible system, and the mixing and dissolving of two phases are difficult, so that the transesterification process has the problems of low liquid-liquid mass transfer reaction rate, easy phase separation, long time for the reaction to reach the established conversion rate and the like.
CN1919973a forms a set of continuous device for preparing biodiesel by using a loop turbulence reactor, raw materials enter from the bottom of the loop turbulence reactor, react in the loop turbulence reactor, the reacted mixture is discharged from the top of the reactor, and a part of the material returns to a circulation mixing pump to enter the reactor again, so as to realize the circulation of the raw materials for multiple forced mixing, and larger energy consumption and special reactor structure are needed for realizing.
The CN101550349 is prepared by adopting a supercritical technology, the proper molar ratio of grease to methanol is homogeneous under the supercritical condition, the transesterification reaction is carried out, the pressure is controlled to be 8-40 MPA, the temperature is controlled to be 300-450 ℃, the time for converting the biological grease into the biodiesel is shortened, the reaction efficiency is improved, but the supercritical biodiesel is high in energy consumption and equipment investment because the biology needs to be carried out under the high-temperature and high-pressure condition, and the problems of coke formation blockage and the like are easily caused under the high-temperature condition.
CN1952046a proposes a method for producing biodiesel by transesterification, which is to introduce principle oil and low-carbon alcohol which participate in the reaction into a transesterification reactor provided with an ultrasonic wave transmitting device according to the reaction metering ratio, and react under proper conditions. The method aims to improve the intersolubility of raw oil and alcohol through the introduction of ultrasonic waves, improve the mass transfer reaction rate of immiscible two phases and shorten the reaction time, but an ultrasonic generating device in the method is difficult to industrialize, and the whole mixed system of materials is realized on an industrial device to the same degree of uniformity.
CN201625532U discloses a high shear emulsification reaction device for preparing biodiesel from waste grease, which comprises a reaction kettle, a motor and an emulsifying machine, wherein the motor is fixed outside the reaction kettle, the emulsifying machine comprises an outer sleeve, a rotor and a stator, the outer sleeve, the rotor and the stator are all coaxial hollow cylinders, one end of the outer sleeve penetrates through the shell of the reaction kettle and is fixed on the shell of the motor, and the other end of the outer sleeve is connected with the stator; one end of a main shaft of the motor is fixedly connected with the rotor; the rotor and the stator outer wall are provided with a plurality of through grooves penetrating through the outer wall along the axial direction, and the rotor is positioned in the hollow inner cavity of the stator. The utility model mainly carries out strong shearing emulsification on the reaction materials so as to hope to improve the material mixing, on one hand, the improvement degree by adopting a mechanical shearing mode is limited, and on the other hand, the high shearing emulsification reactor is a full-mixing reactor, so that the single pass conversion rate and the production efficiency are lower.
Through the analysis, the problems of low transesterification mass transfer reaction rate, easy phase separation, long reaction residence time, low raw material conversion rate and the like caused by the fact that triglyceride and low-carbon alcohol are not mutually dissolved in the biodiesel reaction process are solved, and although a plurality of new processes and new devices are proposed by current researchers, the transesterification reaction condition is not improved obviously, and the problems are further solved by adopting effective processes and devices.
Disclosure of Invention
Aiming at the defects of the prior art, the utility model provides a reaction device and a method for producing biodiesel by using a transesterification method.
The utility model relates to a reaction device for producing biodiesel by an ester exchange method, which comprises a micro-channel mixing device I, a micro-channel mixing device II and an ester exchange reactor;
the micro-channel mixing equipment I is used for mixing the raw materials of the transesterification reaction to form main reaction feeding materials, wherein the molar ratio of the low-carbon alcohol to the triglyceride (hereinafter referred to as the molar ratio of alcohol to oil) in the main reaction feeding materials is more than or equal to 3, preferably 3-15;
the micro-channel mixing equipment I is of a shell-and-tube structure, and an inorganic membrane tube bundle is arranged in the shell; the inlet end of the inorganic membrane tube bundle is communicated with a low-carbon alcohol pipeline, the cavity in the shell outside the ceramic membrane tube bundle is communicated with a raw material grease pipeline, and the outlet end of the inorganic membrane tube bundle is a mixed material I outlet; the low-carbon alcohol diffuses from the inner cavity of the shell to the oil ester in the inorganic membrane tube through the tube wall pore canal of the inorganic membrane tube, and forms a uniform mixed material I as main reaction feeding under the action of the shearing force of the high-flow-rate raw material grease in the tube;
the micro-channel mixing equipment II is used for mixing the raw materials of the transesterification reaction into reinforced mass transfer feeding materials, and the mole ratio of alcohol to oil in the reinforced mass transfer materials is less than 3.
The micro-channel mixing equipment II comprises a micro-channel assembly and a shell, wherein the micro-channel assembly is fixed in the shell, and an inlet is formed in one end of the shell and is communicated with a low-carbon alcohol and raw material grease pipeline; the other end is provided with a mixed material II outlet; the microchannel assembly comprises a plurality of stacked thin sheets, lipophilic fiber filaments and hydrophilic fiber filaments filled between the cracks of the adjacent thin sheets, a plurality of microchannels are formed between the fiber filaments, and the fiber filaments are clamped and fixed through the thin sheets; the low-carbon alcohol and the raw material oil are cut and mixed by fiber filaments in micro-channel mixing equipment II to form a mixed material II which is used as a reinforced mass transfer feed;
the top, bottom or side of the transesterification reactor is provided with a main reaction feed inlet, the bottom, top or side of the tower reactor is provided with a discharge outlet, and the reactor body is provided with a reinforced mass transfer material inlet; the mixed material I outlet of the micro-channel mixing device I is connected with the main reaction feed inlet through a pipeline, and the mixed material II outlet of the micro-channel mixing device II is connected with the reinforced mass transfer material inlet.
In the device, the number of the micro-channel mixing equipment I and the micro-channel mixing equipment II can be set according to actual needs, and 1-3 micro-channel mixing equipment I and micro-channel mixing equipment II are generally set to meet the reaction needs.
In the device, the inorganic membrane tube bundles of the micro-channel mixing equipment I can be one or more of ceramic membranes, metal/ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes, glass membranes and the like; the aperture on the wall of the inorganic membrane tube is 10 nm-1 mu m; the particle size d1 of the triglyceride phase in the mixture I is 100-900 μm, preferably 300-500 μm.
In the device, a micro-channel component in a shell of the micro-channel mixing equipment II is divided into a feeding end and a discharging end along the crack direction, a feeding distribution space is arranged between a material inlet and the feeding end, a discharging distribution space is arranged between a material outlet and the discharging end, and other ends of the micro-channel component except the feeding end and the discharging end are in sealing connection with the shell.
The microchannel assembly comprises a plurality of stacked thin sheets, and lipophilic fiber filaments and hydrophilic fiber filaments filled between the cracks of the adjacent thin sheets, wherein a plurality of microchannels are formed between the fiber filaments, and the fiber filaments are clamped and fixed through the thin sheets; the quantity ratio of the lipophilic fiber filaments to the hydrophilic fiber filaments filled between the adjacent sheet seams is 1: 50-1: 1, a step of; the fiber filaments can be arranged in a single layer or multiple layers, preferably 1-50 layers, more preferably 1-5 layers, and hydrophilic fiber filaments in any layer are uniformly distributed among the lipophilic fiber filaments; preferably, the number ratio of the lipophilic fiber filaments to the hydrophilic fiber filaments in any one layer is 1: 50-1: 1. when the fiber yarns are arranged in multiple layers, the projection of two adjacent layers of fiber yarns along the vertical direction of the sheet is preferably a net structure; the mesh shape in the mesh structure can be any shape, such as one or more of a polygon, a circle, an ellipse, etc.; in each layer of fiber filaments, the spacing between adjacent fiber filaments is generally 0.5-50 μm, preferably the fiber filaments are distributed at equal intervals, and the fiber filaments are arranged along any one of the transverse direction, the longitudinal direction or the oblique direction of the surface of the sheet; the filaments may be of any curvilinear shape, preferably a periodically varying curvilinear shape, such as wavy, zigzag, etc., preferably the filaments of the same layer are of the same shape, more preferably the filaments of all layers are of the same shape.
In the microchannel module, the diameter of the fiber is generally 0.5 to 50 μm, preferably 0.5 to 5 μm, more preferably 0.5 to 1 μm. The lipophilic fiber yarn is generally selected from at least one of polyester fiber yarn, nylon fiber yarn, polyurethane fiber yarn, polypropylene fiber yarn, polyacrylonitrile fiber yarn and polyvinyl chloride fiber yarn, or fiber yarn with surface subjected to lipophilic treatment by a physical or chemical method; the hydrophilic fiber yarn is generally selected from carboxyl (-COOH), amido (-CONH-) and amino (-NH) in main chain or side chain 2 Polymer with hydrophilic groups such as (-), or hydroxyl (-OH), and the more hydrophilic groups, the better the hydrophilicity, such as polypropylene fiber, polyamide fiber, acrylic fiber, or fiber yarn from materials hydrophilic treated by physical or chemical methods.
In the microchannel assembly, the thickness of the sheet is generally 0.05mm to 5mm, preferably 0.1 to 1.5mm. The material of the sheet is generally determined by the nature of the overcurrent material and the operating conditions, and may be any of metal, ceramic, organic glass, polyester, etc., preferably stainless steel (SS 30403, SS 30508, SS32168, SS 31603) among metals. The shape of the sheet may be any of rectangle, square, polygon, circle, ellipse, fan, etc., preferably rectangle or square. The size and number of the flakes can be designed and adjusted according to the actual needs of the reaction.
In the device, the transesterification reactor is one or a combination of a plurality of kettle type reactors, tower type reactors or tubular type reactors; the reactors are connected in parallel or in series; at least one mixed material formed by the micro-channel mixing equipment II is introduced into the transesterification reactor as an intensified mass transfer material.
The utility model also provides a method for producing biodiesel by using the transesterification method, which comprises the following steps:
(1) The low-carbon alcohol with the alcohol-oil molar ratio more than or equal to 3 and the raw material oil enter micro-channel mixing equipment I, the low-carbon alcohol is diffused into the raw material oil in the inorganic membrane tube from the cavity in the shell through the tube wall pore canal of the inorganic membrane tube, and the low-carbon alcohol and the raw material oil form a uniform mixed material I under the action of the shearing force of the high-flow-rate raw material oil in the tube to serve as main reaction feeding;
(2) The low-carbon alcohol with the molar ratio of alcohol to oil less than 3 and raw material oil enter micro-channel mixing equipment II, and mixed materials II are formed by cutting and mixing fiber filaments in the micro-channel mixing equipment II to be used as reinforced mass transfer feeding materials;
(3) The main reaction feed and the intensified mass transfer feed are introduced into a transesterification reactor, transesterification reaction is carried out under the action of a catalyst, and reaction products flow out from the outlet of the reactor to be separated.
In the method of the present utility model, the raw oil is generally derived from animal oil or vegetable oil, and the acid value may be generally from 0 to 130mgKOH/g of fatty acid and/or oil, preferably one or more of refined vegetable oils such as jatropha oil, rapeseed oil, soybean oil, linseed oil, peanut oil, palm oil, tea seed oil, etc.
In the method of the utility model, the low-carbon alcohol is one or more of fatty alcohols with 1-6 carbon atoms, preferably methanol.
In the method of the utility model, the operating conditions of the microchannel mixing device I are as follows: the temperature is between normal temperature and 150 ℃, and the pressure is between 0.5 and 3.0MpaG.
In the method of the utility model, the operating conditions of the microchannel mixing device II are as follows: the temperature is between normal temperature and 150 ℃ and the pressure is between 0.5 and 3.0MpaG.
In the method, the intensified mass transfer feed accounts for 1 to 30 weight percent of the total feed quantity of the reactor.
In the method of the utility model, the transesterification reaction conditions are as follows: the reaction pressure is 0.5-2.0 MPaG, and the reaction temperature is 100-150 ℃; the mol ratio of the triglyceride to the low-carbon alcohol in the raw oil is 1:3-1:15.
In the process of the utility model, the total residence time of the transesterification reactor is from 0.5 to 7 hours, preferably from 0.5 to 3.5 hours; during this time, the conversion was not less than 98.5%.
In the method of the utility model, the transesterification reaction adopts an alkaline catalyst, and can be one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, barium oxide, sodium methoxide or diethylamine. Wherein the dosage of the alkaline catalyst is 0.5-10wt% of the dosage of the triglyceride. The basic catalyst may be added directly to the main reaction feed and/or the enhanced mass transfer material.
In the method, in a mixed material I formed by the micro-channel mixing equipment I, the particle size d1 of triglyceride drops is 100-900 mu m, preferably, the dispersion uniformity is more than or equal to 80 percent, and at the moment, when entering a reactor, the method can keep the low-carbon alcohol/triglyceride two phases from phase separation within the reaction residence time, improve the mass transfer reaction rate, and achieve better reaction effect and triglyceride conversion rate; in a mixed material II formed by the micro-channel mixing equipment II, the particle size d2 of triglyceride drops is smaller than 100 mu m, preferably 0.1-50 mu m, and when the triglyceride drops are introduced between the reactors as a reinforced mass transfer material, the triglyceride drops can rapidly break through a phase interface to be transferred to the surface of a catalyst when the transesterification reaction occurs due to the small particle size and dense triglyceride molecules, so that the purpose of further reinforcing the mass transfer of the reaction is achieved.
In the method of the utility model, the addition amount of the mixed material II is 1 to 30 weight percent of the total material (the total amount of triglyceride, methanol and liquid catalyst phase) of the reactor; when the mixture II is fed in a plurality of strands, the amount of the individual strands fed in the reactor from the inlet to the outlet is preferably increased gradually. Of course, the lower alcohol/triglyceride molar ratio may be reduced or unchanged in the direction from the inlet to the outlet within the reactor. Here, as the transesterification reaction proceeds, the triglyceride molecules are gradually consumed, and the mass transfer driving force in the reaction process is gradually reduced, and since the molar quantity of low carbon alcohol in the reactor is far greater than that of the triglyceride phase, the concentration of the triglyceride molecules is low, so that the triglyceride molecules on the surface of the catalyst are gradually reduced, and the reinforced mass transfer material with high triglyceride content is replenished between the catalyst bed layers, the phase interface can be rapidly broken through to timely replenish the consumed triglyceride in the reaction, so that the higher transesterification reaction rate is maintained.
In the method, in the micro-channel mixing equipment I, the molar ratio of the low-carbon alcohol to the triglyceride is generally 3:1-15:1, and the properly high alcohol-oil molar ratio can ensure the mass transfer reaction rate in the transesterification process, but the reactor volume is larger, so long as the alcohol-oil molar ratio in the reactor is maintained to be more than or equal to 3; in the micro-channel mixing equipment II, the molar ratio of alcohol to oil is generally 1:10-1:0.33, the molar ratio of alcohol to oil in the material is lower, namely the proportion content of triglyceride is higher, and the material can quickly break through a phase interface as a reinforced mass transfer material and be transferred to the surface of a catalyst to supplement the triglyceride consumed by the reaction, so that the surface of the catalyst always maintains a large amount of low-carbon alcohol/triglyceride homogeneous phases rich in triglyceride molecules, thereby improving the transesterification reaction rate and the conversion rate.
In the process of transesterification in biodiesel production, the problems of mutual incompatibility of raw oil and methanol, easy phase separation in the reaction process, low reaction rate, low conversion rate and long residence time exist. The prior art lacks efficient two-phase mixing processes and equipment. According to the utility model, through the micro-channel mixing equipment I, most of raw material oil, methanol and a liquid catalyst are subjected to micro-mixing according to a certain proportion, so that two phases can be kept uniform and not split in the reaction process of reaction feeding in a reactor, and in this case, the mole number of the methanol and the liquid catalyst in the reactor is kept larger than that of the triglyceride, so that continuous mass transfer of the raw material oil (triglyceride) and the methanol and the liquid catalyst in the reactor is realized; and then through a micro-channel mixing device II, the triglyceride drops in the mixed feed are adhered and spread along the surface of the fiber, and are repeatedly and forcedly cut into micron-sized particles by the fiber, and the mixed materials contain dense olefin drops and smaller-sized triglyceride drops which are used as reinforced mass transfer materials, so that the aim of reinforcing mass transfer is fulfilled, the molar ratio of total methanol to triglyceride is reduced, part of triglyceride, methanol and a liquid catalyst are microscopically mixed in another proportion, the drop size (d 1) of the triglyceride in the formed mixed materials I is smaller than the drop size (d 2) of the triglyceride phase in the mixed materials II, and the droplet density of the triglyceride phase in the mixed materials I is smaller than the droplet density of the triglyceride phase in the mixed materials II. The concentration of the triglyceride droplets herein refers to the number of triglyceride microdroplets dispersed in a mixture of methanol and liquid catalyst per unit volume.
Drawings
FIG. 1 is a schematic diagram of a reaction apparatus for producing biodiesel by transesterification according to the present utility model.
Fig. 2 is a schematic diagram of a microchannel assembly within a microchannel mixing device II.
Wherein 1 is raw material grease I,2 is low-carbon alcohol and liquid catalyst I,3 is microchannel mixing equipment I,4 is shell of shell-and-tube inorganic membrane mixer, 5 is inorganic membrane tube bundle, 6 is shell space outside the inorganic membrane tube bundle, 7 is mixed material I,8 is raw material grease II,9 is low-carbon alcohol and liquid catalyst II,10 is microchannel mixing equipment II,11 is microchannel assembly, 12 is microchannel shell, 13 is microchannel sheet, 14 is gap between microchannel sheets, 15 is hydrophilic fiber yarn, 16 is lipophilic fiber yarn, 17 is mixed material II, 18, 19, 20 are reinforced mass transfer materials respectively introduced into the transesterification reactor in a first, second and third strand, 21 is transesterification reactor, 22 is material distributor, and 23 is transesterification reaction product.
Detailed Description
The utility model will now be described in more detail with reference to the accompanying drawings and examples, which are not intended to limit the utility model thereto.
The dispersion size and the dispersion effect of the triglyceride liquid drops in the low-carbon alcohol are obtained through a high-speed camera, and the uniformity of dispersed phase particles is obtained through selecting a plurality of characteristic particles, so that the smaller the particle size is, the higher the uniformity is, and the better the mixing and dispersion effects are. For this reason, the method for measuring the mixing and dispersing effect of the present example and comparative example is as follows: under the same condition, the dispersed phase triglyceride and the continuous phase low-carbon alcohol phase are mixed by different mixing and dispersing methods (such as a conventional static mixer, a micro-channel mixing device I and a micro-channel mixing device II) under the same condition, at least 10 groups of mixed material samples are obtained by each group of methods, the particle size of the dispersed phase in the mixed material samples is shot by using a British IX I-SPEED 5 high-SPEED camera, particles in a photo are added, the percentage content of the particles with various sizes is calculated, and a normal distribution map of the particles with various sizes is obtained, so that the particle uniformity is obtained. Here, the reaction conversion= (mass of reacted triglycerides in the raw material/mass of total triglycerides in the raw material) ×100%.
Taking the attached figure 1 as an example, the reaction device and the method for producing biodiesel by the transesterification method of the utility model are as follows: firstly, introducing raw material oil 1 and low-carbon alcohol into channel mixing equipment I3 according to the proportion that the molar ratio of the alcohol to the oil is more than or equal to 3 to form a mixed material I7, wherein the raw material oil 1 is introduced into a shell space 6 of the micro-channel mixing equipment I3, the low-carbon alcohol and the liquid catalyst 2 are introduced into an inorganic membrane tube bundle 5, the raw material oil 1 penetrates into the inorganic membrane tube from outside the inorganic membrane tube through the wall of the inorganic membrane tube, and the raw material oil 1 and the liquid catalyst are forcedly mixed under the high-speed shearing action of the low-carbon alcohol and the liquid catalyst to form the mixed material I7, and the mixed material I7 is taken as a main reaction material to enter an ester exchange reactor 21 to undergo ester exchange reaction in the reactor; the other part of raw material oil II 8 and low-carbon alcohol and liquid catalyst II 9 are introduced into channel mixing equipment II according to the proportion that the molar ratio of alcohol to oil is less than 3, hydrophilic fiber filaments 15 and lipophilic fiber filaments 16 filled between the gaps 14 are continuously cut for a plurality of times after passing through the gaps 14 between the micro-channel thin sheets 13 in the micro-channel assembly 11 arranged in the micro-channel mixing equipment II 10, and then the mixture II 17 is formed and respectively used as first, second and third reinforced mass transfer materials 18, 19 and 20 to be introduced into a transesterification reactor 21, so that the reinforced mass transfer materials can rapidly supplement triglyceride consumed in the reaction process, the purpose of reinforcing mass transfer is achieved, and the materials for completing the transesterification reaction leave as reaction products 22.
The raw oil used in the comparative examples and examples of the present utility model was tung oil, and the properties thereof are shown in table 1.
TABLE 1 Properties of the feedstock
| Sequence number | Project | Index (I) |
| 1 | Color ( |
Yellow: 35, red: less than or equal to 3.0 |
| 2 | Smell of | Has natural normal smell of tung oil and no foreign odor |
| 3 | Transparency (standing for 24h,20 ℃ C.) | Transparent and transparent |
| 4 | Acid value/mg (KOH). G -1 | 3.0 |
| 5 | Moisture and volatile, wt% | 0.10 |
Example 1
By adopting the transesterification process, raw materials for transesterification are raw material grease, methanol and an alkaline catalyst (the properties of the raw material grease are shown in table 1), the raw material grease, the methanol and the alkaline catalyst are led into a micro-channel mixing device I, wherein the molar ratio of the raw material grease to the methanol is 6:1, the raw material grease is led into the shell side of the micro-channel mixing device I, the methanol and the liquid alkaline catalyst are led into the tube side of the micro-channel mixing device I, a mixture material I formed by the micro-channel mixing device I is taken as a main reaction material and enters a two-stage transesterification reactor to carry out transesterification, the first-stage reactor is a tower reactor, the size of the reactor is phi 200 multiplied by 800mm, the second-stage reactor is a tubular reactor, and the size of the reactor is phi 80 multiplied by 6400mm; raw oil and methanol are mixed by micro-channel mixing equipment II to form a mixed material II in a molar ratio of 1:1, and the mixed material II is respectively introduced into a tower reactor and a tubular reactor as an enhanced mass transfer material to enhance the transesterification reaction process, and a reaction effluent leaves the reactor and enters a separation unit.
In the micro-channel mixing equipment II, the thin sheet in the micro-channel mixing component is made of stainless steel, the thickness of the thin sheet is 1.2mm, 5 layers of metal fiber wires with the diameter of 5 mu m and 1 layer of ceramic fiber wires with the diameter of 5 mu m are filled between the thin sheet cracks, and the fiber wires are distributed at equal intervals, and the interval is 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing.
The transesterification process operating conditions were as follows:
grease feed amount: 3.6kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 2.0MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 2.5%;
the process-enhanced mass transfer material added to the column reactor was 25.6wt% of the total reaction feed, and the process-enhanced mass transfer material added to the tubular reactor was 5.2wt% of the total reaction feed.
The operating conditions of the microchannel mixing device I were as follows: the temperature is 120-125 ℃, and the pressure is 2.0MPaG; the operating conditions of the microchannel mixing device II were as follows: the temperature was 120℃and the pressure was 2.0MPaG.
Under the reaction conditions, the conversion rate of raw materials in the primary transesterification is 96.30%, and the conversion rate of raw materials in the secondary transesterification is 98.7%; the primary transesterification residence time was 0.87 hours and the secondary transesterification residence time was 1.11 hours.
Example 2
In this example, the reaction materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II were the same as in example 1. Unlike example 1, this example changes the transesterification reaction conditions on the one hand and adjusts the introduction position and the introduction amount of the mass transfer enhancing material appropriately on the other hand.
The transesterification process operating conditions were as follows:
grease feed amount: 3.6kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 1.8MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 2.5%;
the process-enhanced mass transfer material added to the column reactor was 16.6wt% of the total reaction feed, and the process-enhanced mass transfer material added to the tubular reactor was 8.0wt% of the total reaction feed.
Under the reaction condition, the conversion rate of the raw materials in the primary transesterification is 97.10 percent, and the conversion rate of the raw materials in the secondary transesterification is 98.8 percent; the primary transesterification residence time was 0.87 hours and the secondary transesterification residence time was 1.11 hours.
Example 3
By adopting the transesterification process, raw materials for transesterification are raw material grease, methanol and an alkaline catalyst (the properties of the raw material grease are shown in table 1), the raw material grease, the methanol and the alkaline catalyst are led into a micro-channel mixing device I, wherein the molar ratio of the raw material grease to the methanol is 5:1, the raw material grease is led into the shell side of the micro-channel mixing device I, the methanol and the liquid alkaline catalyst are led into the tube side of the micro-channel mixing device I, a mixture material I formed by the micro-channel mixing device I is taken as a main reaction material and enters a two-stage transesterification reactor to carry out transesterification, the first-stage reactor is a tower reactor, the size of the reactor is phi 200 multiplied by 800mm, the second-stage reactor is a tubular reactor, and the size of the reactor is phi 80 multiplied by 6400mm; raw oil and methanol are mixed by micro-channel mixing equipment II to form a mixed material II in a molar ratio of 1:2, and the mixed material II is respectively introduced into a tower reactor and a tubular reactor as an enhanced mass transfer material to enhance the transesterification reaction process, and a reaction effluent leaves the reactor and enters a separation unit.
In the micro-channel mixing equipment II, the thin sheet in the micro-channel mixing component is made of stainless steel, the thickness of the thin sheet is 1.0mm, 3 layers of glass fiber filaments with the diameter of 1 mu m and 1 layer of ceramic fiber filaments with the diameter of 5 mu m are filled between the thin sheet cracks, and the fiber filaments are distributed at equal intervals with the interval of 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing.
The transesterification process operating conditions were as follows:
grease feed amount: 3.6kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 2.0MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 2.5%;
the process-enhanced mass transfer material added to the column reactor was 20.0wt% of the total reaction feed, and the process-enhanced mass transfer material added to the tubular reactor was 3.6wt% of the total reaction feed.
The operating conditions of the microchannel mixing device I were as follows: the temperature is 120-125 ℃, and the pressure is 2.0MPaG; the operating conditions of the microchannel mixing device II were as follows: the temperature was 120℃and the pressure was 2.0MPaG.
Under the reaction conditions, the conversion rate of raw materials in the primary transesterification is 97.0%, and the conversion rate of raw materials in the secondary transesterification is 98.9%; the primary transesterification residence time was 1.01 hours and the secondary transesterification residence time was 1.30 hours.
Example 4
In this example, the reaction materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II were the same as in example 3. Unlike example 3, this example changed the feed amount and transesterification reaction conditions on the one hand and appropriately adjusted the introduction position and the introduction amount of the mass transfer enhancing material on the other hand.
The transesterification process operating conditions were as follows:
grease feed amount: 4.0kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 2.0MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 3.0%;
the process-enhanced mass transfer material added to the column reactor was 22.4wt% of the total reaction feed, and the process-enhanced mass transfer material added to the tubular reactor was 3.2wt% of the total reaction feed.
Under the reaction conditions, the conversion rate of raw materials in the primary transesterification is 96.8%, and the conversion rate of raw materials in the secondary transesterification is 99.1%; the primary transesterification residence time was 1.01 hours and the secondary transesterification residence time was 1.30 hours.
Example 5
According to the transesterification process, raw materials for transesterification are raw material grease, methanol and an alkaline catalyst, the raw material grease, the methanol and the alkaline catalyst are led into a micro-channel mixing device I, wherein the molar ratio of the raw material grease to the methanol is 8:1, the raw material grease is led into the shell side of the micro-channel mixing device I, the methanol and the liquid alkaline catalyst are led into the tube side of the micro-channel mixing device I, a mixture material I formed by the micro-channel mixing device I is taken as a main reaction material to enter a two-stage transesterification reactor for transesterification, wherein the first-stage reactor is a tower reactor, the size of the reactor is phi 200 multiplied by 800mm, the second-stage reactor is a tubular reactor, and the size of the reactor is phi 80 multiplied by 6400mm; raw oil and methanol are mixed by micro-channel mixing equipment II to form a mixed material II in a molar ratio of 1:1, and the mixed material II is respectively introduced into a tower reactor and a tubular reactor as an enhanced mass transfer material to enhance the transesterification reaction process, and a reaction effluent leaves the reactor and enters a separation unit.
In the micro-channel mixing equipment II, the thin sheet in the micro-channel mixing component is made of stainless steel, the thickness of the thin sheet is 1.5mm, 8 layers of stainless steel fiber wires with the diameter of 5 mu m and 2 layers of ceramic fiber wires with the diameter of 5 mu m are filled between the thin sheet cracks, and the fiber wires are distributed at equal intervals, and the distance is 1 mu m. The fiber yarn is in a curve shape with a wavy line periodically changing.
The transesterification process operating conditions were as follows:
grease feed amount: 4.0kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 2.0MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 2.5%;
the process-enhanced mass transfer material added to the column reactor was 21.6wt% of the total reaction feed, and the process-enhanced mass transfer material added to the tubular reactor was 1.5wt% of the total reaction feed.
The operating conditions of the microchannel mixing device I were as follows: the temperature is 120-125 ℃, and the pressure is 2.0MPaG; the operating conditions of the microchannel mixing device II were as follows: the temperature was 120℃and the pressure was 2.0MPaG.
Under the reaction conditions, the conversion rate of raw materials in the primary transesterification is 97.8%, and the conversion rate of raw materials in the secondary transesterification is 98.9%; the primary transesterification residence time was 0.611 hours and the secondary transesterification residence time was 0.782 hours.
Example 6
In this example, the reaction materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II were the same as in example 5. Unlike example 3, this example changed the feed amount and transesterification reaction conditions on the one hand and appropriately adjusted the introduction position and the introduction amount of the mass transfer enhancing material on the other hand.
The transesterification process operating conditions were as follows:
grease feed amount: 4.0kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 1.8MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 3.0%;
the process-enhanced mass transfer material added to the column reactor was 17.5wt% of the total reaction feed, and the process-enhanced mass transfer material added to the tubular reactor was 6.4wt% of the total reaction feed.
Under the reaction condition, the conversion rate of raw materials in the primary transesterification is 97.3%, and the conversion rate of raw materials in the secondary transesterification is 98.8%; the primary transesterification residence time was 0.611 hours and the secondary transesterification residence time was 0.782 hours.
Comparative example 1
The method comprises the steps of adopting a conventional biodiesel product transesterification reaction device and a conventional biodiesel product transesterification reaction method, wherein raw materials for transesterification are raw material grease, methanol and an alkaline catalyst (the properties of the raw material grease are shown in table 1), firstly introducing the raw material grease, the methanol and the alkaline catalyst into a stirring kettle for stirring and mixing for 15-20 minutes, and then pumping the raw material grease and the alkaline catalyst into a two-stage reactor by a feed pump to perform transesterification, wherein the primary reactor is a tower reactor, the reactor size is phi 200 multiplied by 1200mm, the secondary reactor is a tubular reactor, and the reactor size is phi 80 multiplied by 12800mm.
The reactor operating conditions were as follows:
raw material oil feed amount: 1.5kg/h;
the reaction temperature is 120-125 ℃;
the reaction pressure was 2.0MPaG;
alcohol to oil molar ratio: 8-10 (the molecular weight of the oil is 880, the following is the same)
The alkali catalyst comprises the following raw material grease in mass percentage: 2.5%.
Under the reaction conditions, the conversion rate of the raw materials at the outlet of the primary reactor is 75.2 percent, and the conversion rate of the raw materials at the outlet of the secondary reactor is 87.4 percent; the primary transesterification residence time (based on total material) was 2.02 hours and the secondary transesterification residence time (based on total material) was 3.44 hours.
Comparative example 2
The method comprises the steps of adopting a conventional biodiesel product transesterification reaction device and a conventional biodiesel product transesterification reaction method, wherein raw materials for transesterification reaction are raw material grease, methanol and an alkaline catalyst, firstly, introducing the raw material grease, the methanol and the alkaline catalyst into an impinging stream reactor for impinging and mixing for 5-10 minutes, and then pumping the raw material grease, the methanol and the alkaline catalyst into a two-stage reactor for transesterification reaction by using a feed pump, wherein the primary reactor is a tower reactor, the reactor size is phi 200 multiplied by 1200mm, the secondary reactor is a tubular reactor, and the reactor size is phi 80 multiplied by 12800mm.
The reactor operating conditions were as follows:
raw material oil feed amount: 1.8kg/h;
the reaction temperature is 120-125 ℃;
the reaction pressure was 2.0MPaG;
alcohol to oil molar ratio: 8-10 (oil molecular weight: 880)
The alkali catalyst comprises the following raw material grease in mass percentage: 2.5%.
Under the reaction conditions, the conversion rate of the raw materials at the outlet of the primary reactor is 87.2 percent, and the conversion rate of the raw materials at the outlet of the secondary reactor is 90.5 percent; the primary transesterification residence time (based on total material) was 1.68 hours and the secondary transesterification residence time (based on total material) was 2.87 hours.
Comparative example 3
The conventional transesterification process is used, except that the microchannel mixing device I of the process of the utility model is used in the process of mixing the starting materials. Raw materials for transesterification are raw material grease, methanol and an alkaline catalyst (the properties of the raw material grease are shown in table 1), the raw material grease, the methanol and the alkaline catalyst are led into a micro-channel mixing device I, wherein the raw material grease/methanol is led into the shell side of the micro-channel mixing device I in a molar ratio of 8:1, the methanol and the liquid alkaline catalyst are led into the tube side of the micro-channel mixing device I, a mixture I formed by the micro-channel mixing device I is taken as a main reaction material to enter a two-stage transesterification reactor for transesterification, wherein the first-stage reactor is a tower reactor, the reactor size is phi 200 multiplied by 1200mm, the second-stage reactor is a tubular reactor, the reactor size is phi 80 multiplied by 12800mm, and a reaction effluent leaves the reactor and enters a separation unit.
The transesterification process operating conditions were as follows:
grease feed amount: 2.2kg/h;
reaction temperature: 120-125 ℃;
reaction pressure: 2.0MPaG;
the alkali catalyst comprises the following raw material grease in mass percentage: 2.5%;
the operating conditions of the microchannel mixing device I were as follows: the temperature is 120-125 ℃, and the pressure is 2.0MPaG; the operating conditions of the microchannel mixing device II were as follows: the temperature was 120℃and the pressure was 2.0MPaG.
Under the reaction conditions, the conversion rate of raw materials in the primary transesterification is 87.30 percent, and the conversion rate of raw materials in the secondary transesterification is 94.2 percent; the primary transesterification residence time was 1.35 hours and the secondary transesterification residence time was 2.85 hours.
Claims (23)
1. A reaction device for producing biodiesel by an ester exchange method is characterized by comprising a micro-channel mixing device I, a micro-channel mixing device II and an ester exchange reactor;
the micro-channel mixing equipment I is of a shell-and-tube structure, and an inorganic membrane tube bundle is arranged in the shell; the inlet end of the inorganic membrane tube bundle is communicated with a low-carbon alcohol pipeline, the cavity in the shell outside the ceramic membrane tube bundle is communicated with a raw material grease pipeline, and the outlet end of the inorganic membrane tube bundle is a mixed material I outlet; the low-carbon alcohol diffuses from the inner cavity of the shell to the triglyceride in the inorganic membrane tube through the tube wall pore canal of the inorganic membrane tube, and forms a uniform mixed material I as main reaction feeding under the shearing force action of the high-flow-rate raw material grease in the tube;
the micro-channel mixing equipment II comprises a micro-channel assembly and a shell, wherein the micro-channel assembly is fixed in the shell, and an inlet is formed in one end of the shell and is communicated with a low-carbon alcohol and raw material grease pipeline; the other end is provided with a mixed material II outlet; the microchannel assembly comprises a plurality of stacked thin sheets, lipophilic fiber filaments and hydrophilic fiber filaments filled between the cracks of the adjacent thin sheets, a plurality of microchannels are formed between the fiber filaments, and the fiber filaments are clamped and fixed through the thin sheets; the low-carbon alcohol and the raw material oil are cut and mixed by fiber filaments in micro-channel mixing equipment II to form a mixed material II which is used as a reinforced mass transfer feed;
the top, bottom or side of the transesterification reactor is provided with a main reaction feed inlet, the bottom, top or side of the tower reactor is provided with a discharge outlet, and the reactor body is provided with a reinforced mass transfer material inlet; the mixed material I outlet of the micro-channel mixing device I is connected with the main reaction feed inlet through a pipeline, and the mixed material II outlet of the micro-channel mixing device II is connected with the reinforced mass transfer material inlet.
2. The reaction apparatus of claim 1, wherein: the micro-channel mixing equipment I is used for mixing the transesterification raw materials to form main reaction feeding materials, wherein the molar ratio of the low-carbon alcohol to the triglyceride in the main reaction feeding materials is more than or equal to 3, preferably 3-15; the micro-channel mixing equipment II is used for mixing the raw materials of the transesterification reaction into reinforced mass transfer feeding materials, and the mole ratio of alcohol to oil in the reinforced mass transfer materials is less than 3.
3. The reaction apparatus of claim 1, wherein: the number of the micro-channel mixing equipment I and the micro-channel mixing equipment II is respectively 1-3.
4. The reaction apparatus of claim 1, wherein: the inorganic membrane tube bundles of the micro-channel mixing equipment I are one or more of ceramic membranes, metal/ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes or glass membranes; the aperture on the wall of the inorganic membrane tube is 10 nm-1 μm.
5. The reaction apparatus of claim 1, wherein: the micro-channel component in the micro-channel mixing equipment II shell is divided into a feeding end and a discharging end along the crack direction, a feeding distribution space is arranged between the material inlet and the feeding end, a discharging distribution space is arranged between the material outlet and the discharging end, and other ends of the micro-channel component except the feeding end and the discharging end are in sealing connection with the shell.
6. The reaction apparatus of claim 1, wherein: the quantity ratio of the lipophilic fiber filaments to the hydrophilic fiber filaments filled between the adjacent sheet seams is 1: 50-1: 1.
7. the reaction apparatus of claim 1, wherein: the diameter of the fiber filaments is generally 0.5 to 50. Mu.m, preferably 0.5 to 5. Mu.m, more preferably 0.5 to 1. Mu.m; the lipophilic fiber yarn is at least one selected from polyester fiber yarn, nylon fiber yarn, polyurethane fiber yarn, polypropylene fiber yarn, polyacrylonitrile fiber yarn and polyvinyl chloride fiber yarn, or fiber yarn with surface subjected to lipophilic treatment by a physical or chemical method; the hydrophilic fiber yarn is selected from one or more of high molecular polymers of which the main chain or side chain contains hydrophilic groups such as carboxyl, amido, amino or hydroxyl.
8. The reaction apparatus of claim 1, wherein: the fiber filaments are arranged in a single layer or multiple layers, preferably 1-50 layers, more preferably 1-5 layers; hydrophilic fiber filaments in any layer are uniformly distributed among the lipophilic fiber filaments; the number ratio of the lipophilic fiber yarn to the hydrophilic fiber yarn in any layer is 1: 50-1: 1.
9. the reaction apparatus of claim 1, wherein: in each layer of fiber filaments, the adjacent fiber filaments are arranged at intervals of 0.5-50 μm, preferably at equal intervals.
10. The reaction apparatus of claim 8, wherein: when the fiber yarns are arranged in multiple layers, the projection of two adjacent layers of fiber yarns along the vertical direction of the sheet is a net structure.
11. The reaction apparatus of claim 1, wherein: in the microchannel assembly, the thickness of the thin sheet is 0.05 mm-5 mm, preferably 0.1-1.5 mm; the sheet is made of any one of metal, ceramic, organic glass and polyester material.
12. The reaction apparatus of claim 1, wherein: the transesterification reactor is one or a combination of more of a kettle type reactor, a tower type reactor or a tubular type reactor; the reactors are connected in parallel or in series; at least one mixed material formed by the micro-channel mixing equipment II is introduced into the transesterification reactor as an intensified mass transfer material.
13. A method of using the reaction apparatus of claim 1 for producing biodiesel by transesterification, comprising the steps of: (1) The low-carbon alcohol with the alcohol-oil molar ratio more than or equal to 3 and the raw material oil enter micro-channel mixing equipment I, the low-carbon alcohol is diffused into the raw material oil in the inorganic membrane tube from the cavity in the shell through the tube wall pore canal of the inorganic membrane tube, and the low-carbon alcohol and the raw material oil form a uniform mixed material I under the action of the shearing force of the high-flow-rate raw material oil in the tube to serve as main reaction feeding; (2) The low-carbon alcohol with the molar ratio of alcohol to oil less than 3 and raw material oil enter micro-channel mixing equipment II, and mixed materials II are formed by cutting and mixing fiber filaments in the micro-channel mixing equipment II to be used as reinforced mass transfer feeding materials; (3) The main reaction feed and the intensified mass transfer feed are introduced into a transesterification reactor, transesterification reaction is carried out under the action of a catalyst, and reaction products flow out from the outlet of the reactor to be separated.
14. The method according to claim 13, wherein: the raw oil is one or more of jatropha curcas oil, rapeseed oil, soybean oil, linseed oil, peanut oil, palm oil and tea seed oil.
15. The method according to claim 13, wherein: the lower alcohol is one or more of aliphatic alcohols with 1-6 carbon atoms, preferably methanol.
16. The method according to claim 13, wherein: the operating conditions of the microchannel mixing device I were as follows: the temperature is between normal temperature and 150 ℃, and the pressure is between 0.5 and 3.0MpaG.
17. The method according to claim 13, wherein: the operating conditions of the microchannel mixing device II were as follows: the temperature is between normal temperature and 150 ℃ and the pressure is between 0.5 and 3.0MpaG.
18. The method according to claim 13, wherein: the reinforced mass transfer feed accounts for 1-30wt% of the total feed amount of the reactor.
19. The method according to claim 13, wherein: the transesterification reaction conditions are as follows: the reaction pressure is 0.5-2.0 MPaG, and the reaction temperature is 100-150 ℃; the molar ratio of the triglyceride to the lower alcohol is 1:3-1:15.
20. The method according to claim 13, wherein: the total residence time of the transesterification reactor is from 0.5 to 7 hours, preferably from 0.5 to 3.5 hours.
21. The method according to claim 13, wherein: the transesterification reaction adopts an alkaline catalyst, and is selected from one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, barium oxide, sodium methoxide or diethylamine; the dosage of the alkaline catalyst is 0.5 to 10 percent of the dosage of the triglyceride; the alkaline catalyst is added directly to the main reaction feed and/or the enhanced mass transfer material.
22. The method according to claim 13, wherein: in the mixed material I formed by the micro-channel mixing equipment I, the particle diameter d1 of the raw material oil drops is 100-900 mu m, and the dispersion uniformity is preferably more than or equal to 80%; in the mixed material II formed by the micro-channel mixing equipment II, the particle size d2 of the raw material grease liquid drops is smaller than 100 mu m, preferably 0.1-50 mu m.
23. The method according to claim 13, wherein: when the mixture II is fed in a plurality of strands, the amount of the mixture in the reactor from the inlet to the outlet is preferably increased gradually.
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