CN103013676A - Method for reducing biodiesel crude product acid value, and biodiesel preparation method - Google Patents
Method for reducing biodiesel crude product acid value, and biodiesel preparation method Download PDFInfo
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- CN103013676A CN103013676A CN2011102803985A CN201110280398A CN103013676A CN 103013676 A CN103013676 A CN 103013676A CN 2011102803985 A CN2011102803985 A CN 2011102803985A CN 201110280398 A CN201110280398 A CN 201110280398A CN 103013676 A CN103013676 A CN 103013676A
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- acid
- coarse product
- biodiesel coarse
- biodiesel
- alcohol
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 127
- 239000002253 acid Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000012043 crude product Substances 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002551 biofuel Substances 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 14
- -1 alcohol ester Chemical class 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000002608 ionic liquid Substances 0.000 claims description 11
- 150000002632 lipids Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 123
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 84
- 239000003921 oil Substances 0.000 description 36
- 235000019198 oils Nutrition 0.000 description 36
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 235000021588 free fatty acids Nutrition 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- OGXRXFRHDCIXDS-UHFFFAOYSA-N methanol;propane-1,2,3-triol Chemical compound OC.OCC(O)CO OGXRXFRHDCIXDS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
本发明公开了一种降低生物柴油粗产品酸值的方法以及一种生物柴油的制备方法，所述生物柴油粗产品的酸值为3-20mgKOH/g，其中，该方法包括在催化剂的存在下，将所述生物柴油粗产品与一元醇连续接触反应，所述接触反应的条件包括：反应温度为70-220℃，反应压力为0.2-3MPa，所述催化剂的用量为生物柴油粗产品的0.001-0.4重量％。采用本发明的方法在较温和的条件下，并在采用极少的催化剂的条件下能够显著降低具有较高酸值的生物柴油粗产品的酸值，优选能够使生物柴油的酸值达到0.8mgKOH/g以下。The invention discloses a method for reducing the acid value of a crude biodiesel product and a method for preparing biodiesel. The acid value of the crude biodiesel product is 3-20 mgKOH/g, wherein the method comprises the following steps: in the presence of a catalyst , the crude biodiesel product is continuously contacted with a monohydric alcohol, the conditions of the contact reaction include: the reaction temperature is 70-220°C, the reaction pressure is 0.2-3MPa, and the amount of the catalyst is 0.001% of the crude biodiesel product. -0.4% by weight. The method of the present invention can significantly reduce the acid value of the crude biodiesel product with higher acid value under milder conditions and with very few catalysts, preferably the acid value of the biodiesel can reach 0.8mgKOH /g or less.
Description
Technical field
The present invention relates to a kind of method of biodiesel coarse product acid number and a kind of preparation method of biofuel of reducing.
Background technology
Biofuel can be carried out transesterification reaction by raw oil material and monohydroxy-alcohol and be made; fatty acid ester is arranged in the reacting coarse product; also have monoacylglycerol ester, two acyl glyceride, glycerine, and unreacted pure and mild raw oil material (main component is triglyceride level).In the prior art, the preparation method of biofuel can be divided into base catalysis method, acid base catalysis method, enzyme catalysis method and supercritical methanol technology etc.
JP9-235573 discloses the discarded edible oil of a kind of usefulness and methyl alcohol prepare diesel-fuel in the presence of sodium hydroxide method, in natural fats and oils, usually contain free fatty acids, in the situation that free fatty acids is more, use base metal catalysts, can produce fatty acid soaps, base metal catalysts is wanted excessive and is made the fatty acid ester layer separate the difficulty of change with glycerin layer like this.
CN102041177A discloses a kind of method for preparing biofuel, the method comprises take pretreated animal grease, Vegetable oil lipoprotein as stock oil, press 4 in reactor: 1-8: 1 molar ratio of methanol to oil adds methyl alcohol, the vitriol oil that under agitation adds the 3-5 % by weight of stock oil weight, 75 ℃ of lower reactions 2 hours, make in the system acid number below 3mgKOH/g and finish pre-esterification; Then add in the water and washing, dehydration impurity elimination, drying, reenter reactor and be warming up to 75 ℃, under agitation add 3% NaOH methanol solution, make in the system acid number finish transesterify to 1mgKOH/g, get coarse biodiesel after separating lower floor's glycerine methanol solution; Finally by crossing multiple-grade molecular distillation, obtain biofuel.
DE3444893 discloses a kind of method, adopt acid catalyst, under normal pressure, 50-120 ℃, free fatty acids and alcohol are carried out esterification, oil plant is carried out pre-esterification treatment, then carry out transesterification reaction under base metal catalysts, but the acid catalyst of leaving over will neutralize by alkali, the amount of base metal catalysts can increase.
Adopt above-mentioned acid base catalysis method, make that work flow is elongated, energy consumption significantly rises, facility investment increases, and in addition, needs remove basic catalyst from product, has a large amount of waste water to produce, in addition, the recovery of glycerine difficulty.
US5713965A discloses a kind of with the method for lipase as biodiesel, and the method is included under the existence of lipase, as solvent, grease and alcohol reaction is prepared fatty acid methyl ester, i.e. diesel-fuel with hexane.
CN1472280A discloses a kind of method of utilizing the glyceride stock biodiesel synthesis, and the method comprises with short-chain aliphatic ester utilizes the biological enzyme bio-oil to carry out transesterification reaction production biofuel as acyl acceptor.
The deficiency that adopts above-mentioned enzymatic method to exist is: long reaction time, efficient are lower, and enzyme is more expensive, and in high purity methanol easy inactivation.
CN1287572A discloses a kind of method of being made fatty acid alkyl ester by fats, the method is to make grease class and alcohol reaction, in transesterification reaction, add the tri-glyceride that is contained in the grease class and make the alkyl ester of lipid acid, it is characterized in that, in the atmosphere gas of described alcohol one-tenth supercritical state and without a kind of the making it in base metal catalysts or the acid catalyst, react.Described temperature of reaction is 250-300 ℃, and reaction pressure is 3-15Mpa, and the fatty acid methyl ester production rate is 54-60%.The production rate of the fatty acid methyl ester that employing the method prepares is lower, and does not have open how how the monoacylglycerol ester in the reacting coarse product, two acyl glyceride, triglyceride level processing.For adopting the standby biofuel of continuous middle high-pressure legal system, if do not use catalyzer, there is the lower problem of lipid acid monobasic alcohol ester yield.In addition, aforesaid method does not add explanation to processing high acid value with the reaction effect that contains the unrefined oil of high unsaponifiables yet.
Can find by above-mentioned prior art, because the acid number difference of raw oil material is very large, some raw oil material acid numbers can reach 160mgKOH/g, even higher, when using preparing biodiesel by using high acid number feed lipid, general last employing adds the method that alkali neutralizes and falls acid-respons, otherwise, the acid number of biofuel is difficult to remarkable reduction, more is difficult to reach≤standard of 0.8mgKOH/g.
Summary of the invention
The object of the present invention is to provide that a kind of catalyst levels is few, reaction conditions is gentle and can significantly reduce method and a kind of method for preparing biofuel of high acid value biodiesel coarse product acid number.
To achieve these goals, the invention provides a kind of method that reduces the biodiesel coarse product acid number, the acid number of described biodiesel coarse product is 3-20mgKOH/g, wherein, the method is included under the existence of catalyzer, and with described biodiesel coarse product and the reaction of monohydroxy-alcohol Continuous Contact, described catalytic condition comprises: temperature of reaction is 70-220 ℃, reaction pressure is 0.2-3MPa, and the consumption of described catalyzer is the 0.001-0.4 % by weight of biodiesel coarse product.
In addition, the present invention also provides a kind of preparation method of biofuel, wherein, it is that acid falls in the biodiesel coarse product of 3-20mgKOH/g that the method comprises acid number, and the biofuel product that will fall after the acid distills, and the described method that acid is fallen in biodiesel coarse product is method provided by the invention.
Adopt method of the present invention under relatively mild condition, and under the condition that adopts few catalyzer, can significantly reduce the acid number of the biodiesel coarse product with higher acid value.In addition, method of the present invention is specially adapted to fall the acid number reaction to what adopt biodiesel coarse product that foreign matter content raw oil material high, high acid value prepares, when adopting method of the present invention to prepare biofuel, need not the raw oil material of preparation biofuel is carried out pre-treatment, and the acid number of raw oil material is not required.In addition, the method for preparing biofuel of the present invention can make the acid number of biodiesel coarse product effectively be reduced before distillation procedure, preferably can reach the requirement of BD100 standard, and need not after distillation, again to fall acid, thereby greatly simplified operation, improve production efficiency, and reduced energy consumption.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the method of described reduction biodiesel coarse product acid number is included under the existence of catalyzer, be 3-20mgKOH/g with acid number, be preferably biodiesel coarse product and the reaction of monohydroxy-alcohol Continuous Contact of 3-15mgKOH/g, described catalytic condition comprises: temperature of reaction is 70-220 ℃, reaction pressure is 0.2-3MPa, and the consumption of described catalyzer is the 0.001-0.4 % by weight of biodiesel coarse product.
The present inventor is surprised to find that, under relatively mild reaction conditions, the catalyzer that adopts minute quantity namely effectively the catalysis acid number be free fatty acids in the biodiesel coarse product of 3-20mgKOH/g and the esterification of monohydroxy-alcohol, with the acid number of the described biodiesel coarse product of remarkable reduction, the acid number of biofuel crude product is reached below the 0.8mgKOH/g.Infer that reason may be: described catalyzer can tie up to reactant and can be dissolved under lower temperature, the pressure in the reaction system, the performance of described catalyzer is fully played, therefore, can only adopt micro-catalyzer namely can effectively reduce the acid number of biodiesel coarse product.In addition, under described reaction conditions, the water of generation can effectively remove from oil phase, and thermodynamic(al)equilibrium is moved to the product direction, makes reaction more thorough.
Can realize purpose of the present invention according to aforementioned techniques scheme of the present invention, namely according to the present invention, described catalytic condition comprises that temperature of reaction is 70-220 ℃, reaction pressure is 0.2-3MPa, the consumption of described catalyzer is the 0.001-0.4 % by weight of biodiesel coarse product, more abundant for what goal of the invention of the present invention was realized, under the preferable case, described temperature of reaction is 100-190 ℃, more preferably 100-160 ℃, described reaction pressure is 0.3-1Mpa, more preferably 0.4-0.7Mpa, the consumption of described catalyzer is the 0.01-0.2 % by weight of biodiesel coarse product, more preferably 0.02-0.1 % by weight.
According to the present invention, described temperature of reaction raises, reaction conversion ratio is higher, because driven mechanics angle, temperature raises to be conducive to react and carries out, but reaction product is black, have burnt matter to produce, therefore, temperature of reaction is preferably and is less than or equal to 200 ℃, considering cost and effect, described temperature of reaction most preferably are 100-160 ℃.Improve pressure unfavorable to dewatering, make and fall the acid-respons balance and be difficult to move to the product direction, so it is lower that pressure should keep, therefore, described pressure is preferably more than or equals 0.2MPa, considering cost and effect, and described reaction pressure most preferably is 0.4-0.7Mpa.
The present invention is not particularly limited monohydroxy-alcohol and mol ratio in the described biodiesel coarse product of lipid acid monobasic alcohol ester, generally speaking, monohydroxy-alcohol is excessive, under the preferable case, improve monohydroxy-alcohol and the mol ratio in the described biodiesel coarse product of lipid acid monobasic alcohol ester and can further be beneficial to the carrying out of reaction, under the preferable case, described monohydroxy-alcohol with take the mol ratio of the described biodiesel coarse product of lipid acid monobasic alcohol ester as 0.1-9: 1, further under the preferable case, described monohydroxy-alcohol with take the mol ratio of the described biodiesel coarse product of lipid acid monobasic alcohol ester as 0.4-2: 1, most preferably be 0.6-2: 1.
According to the present invention, described catalyzer can be for well known to a person skilled in the art be used to the various catalyzer that fall acid, for example, the most commonly used can be for being selected from sulfuric acid, phosphoric acid, heteropolyacid and the ionic liquid one or more.Wherein, described heteropolyacid can be selected from one or more in phospho-wolframic acid, phospho-molybdic acid and the tungstosilicic acid of phospho-wolframic acid, phospho-molybdic acid, tungstosilicic acid and load.Described ionic liquid is preferably and contains sulfonic ionic liquid.Described ionic liquid can be commercially available, and also can prepare according to the method for well known to a person skilled in the art (for example, described contain sulfonic ionic liquid can prepare according to the disclosed method of CN101759646A).In addition, when adopting ionic liquid as catalyzer, can also add simultaneously FeCl
3, SnCl
4, ZnCl
4And Zn (NO
3)
2In one or more materials with the catalytic activity of the described ionic liquid of further enhancing.More preferably in the situation, considering cost and effect, the present inventor finds to adopt one or more an acidic catalysts in sulfuric acid, phosphoric acid and the heteropolyacid to fall acid under condition of the present invention the acid number of biofuel is reduced to below the 0.8mgKOH/g.
According to the present invention, described monohydroxy-alcohol refers to carbonatoms at the aliphatic monobasic alcohol of 1-6, for example, can be saturated alcohol (straight chain or contain the saturated alcohol of side chain) and/or unsaturated alcohol (straight chain or contain the unsaturated alcohol of side chain).Specifically can be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, vinyl carbinol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol and the isomer thereof one or more, more preferably methyl alcohol and/or ethanol.
According to the present invention, in the presence of catalyzer, described biodiesel coarse product and monohydroxy-alcohol are Continuous Contact reactions, and described Continuous Contact reaction can be carried out in the various reactors that can realize its Continuous Contact, for example, described reaction can be carried out in tubular reactor.Specifically, method provided by the invention adopts tubular reactor, biodiesel coarse product and monohydroxy-alcohol are sent into (send into respectively or its mixture is sent into) described tubular reactor from the bottom feed mouth of described bed tubular reactor, and described trace catalyst can enter reactor with raw material.Before raw material was offered reactor, available preheater also can directly enter reactor with the material preheating, if directly raw material is sent into reactor, so, reactor had both played the effect of preheater, also played the effect of reactor.Under the preferable case, volume space velocity is 0.1-5h during the liquid of described biodiesel coarse product
-1, further under the preferable case, volume space velocity is 0.6-3h during the liquid of described biodiesel coarse product
-1, most preferably be 0.6-2h
-1
According to the present invention, described acid number refers to, in and the quality (mg) of the required KOH of acidic component in the 1 gram organism.What of sample Free Acid (mainly referring to lipid acid) content are the size of acid number reflected.
According to the present invention, it is that acid falls in the biodiesel coarse product of 3-20mgKOH/g that the preparation method of described biofuel comprises acid number, and the biofuel product that will fall after the acid distills, and the described method that acid is fallen in biodiesel coarse product is aforesaid method of the present invention.
According to the present invention, the preparation biodiesel coarse product, particularly acid number is higher, be that the method for the biodiesel coarse product of 3-20mgKOH/g can adopt and well known to a person skilled in the art that any means carries out such as acid number, because the acid number of the biodiesel coarse product that obtains is higher, do not meet national standard, therefore acid-respons need to further fall, therefore, the used raw oil material of preparation biodiesel coarse product is not particularly limited, usually can utilize the higher scrap feed material grease of acid number, on the one hand it is reused, can the acid number of the higher biodiesel coarse product of acid number is reduced to by method of the present invention on the other hand and meets national standard.
For example, in the present invention, described raw oil material can be various raw oil materials, as, acid number is more than or equal to 5mg KOH/g, be generally the glyceride stock of 10-200mg KOH/g, for example, described glyceride stock can be selected from one or more in sewer oil, acidification oil, catering trade abendoned oil and the discarded animal oil.
As mentioned above, method of the present invention is specially adapted to fall the acid number reaction to what adopt biodiesel coarse product that foreign matter content raw oil material high, high acid value prepares, when adopting method of the present invention to prepare biofuel, need not the raw oil material of preparation biofuel is carried out pre-treatment, and the acid number of raw oil material is not required.
Usually; under high-temperature and high-pressure conditions, make raw oil material and monohydroxy-alcohol carry out transesterification in employing and can carry out catalysis without catalyzer; but; the acid number of the biodiesel coarse product that obtains is higher; also can residual monoacylglycerol ester in the crude product, two acyl glyceride, triglyceride level etc., therefore, adopt method of the present invention not only can reduce the acid number of thick product; can also further promote the further reaction of described residue, thereby improve the productive rate of biofuel.The preparation method of described biodiesel coarse product is included under 170-350 ℃, 3-10MPa condition, preferably under 190-230 ℃, 3-6Mpa condition with raw oil material and monohydroxy-alcohol contact reacts, described monohydroxy-alcohol with take the mol ratio of the raw oil material of tri-glyceride as 3-60: 1, be preferably 3-12: 1.
According to the present invention, the method of described underpressure distillation can adopt the method for well known to a person skilled in the art to carry out, the purpose of described underpressure distillation is the heavy impurity of removing wherein, further to obtain the biofuel product of purifying, actual conditions comprises, the temperature of described underpressure distillation can be 100-300 ℃, and pressure is preferably less than 0.1MPa, more preferably less than 0.04Mpa.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will describe the present invention by embodiment.
The measuring method of acid number is GB/T5530-2005 among the following embodiment.
The preparation method of biodiesel coarse product described in the embodiment 1-6 and 9 example: under 253 ℃, 6MPa condition, be 130mgKOH/g with acid number, unsaponifiable matter content is stock oil and the methyl alcohol contact reacts of 3.9 % by weight; Methyl alcohol with take the mol ratio of the stock oil of tri-glyceride as 6: 1, volume space velocity is 1.2h during the liquid of stock oil
-1Obtain the biodiesel coarse product that acid number is 8.5mgKOH/g, and be 0.013MPa with described biodiesel coarse product in vacuum tightness, the tower reactor temperature is to carry out underpressure distillation under 279 ℃ the condition, and the mass yield of biofuel is 85.1% (mass yield of biofuel=(with the quality of the quality/stock oil of the biofuel that obtains after the biodiesel coarse product distillation) * 100%).
Embodiment 1
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, the sulfuric acid of 8.5mgKOH/g is sent in the tubular reactor with acid number, wherein, volume space velocity is 0.6h during the liquid of biodiesel coarse product
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 1.7: 1, take the biodiesel coarse product charging as benchmark, sulphuric acid is 0.02 % by weight of biodiesel coarse product volume, temperature is 160 ℃ in the reactor, pressure is 0.7Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.80mgKOH/g.
Embodiment 2
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, sulfuric acid and the phosphoric acid of 8.5mgKOH/g is sent in the tubular reactor with acid number, wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 1.7: 1, take the biodiesel coarse product charging as benchmark, the add-on of sulfuric acid and phosphoric acid is 0.05 % by weight (weight ratio of sulfuric acid and phosphoric acid 3: 2) of biodiesel coarse product volume, temperature is 140 ℃ in the reactor, pressure is 0.4Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.55mgKOH/g.With obtain fall after the acid product with the biodiesel coarse product preparation example in distill under the identical distillation condition, the mass yield of the biofuel that obtains is 90.2%.
Embodiment 3
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, sulfuric acid and the phosphoric acid of 8.5mgKOH/g is sent in the tubular reactor with acid number, wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 0.6: 1, take the biodiesel coarse product charging as benchmark, the add-on of sulfuric acid and phosphoric acid is 0.2 % by weight (weight ratio of sulfuric acid and phosphoric acid 3: 1) of biodiesel coarse product volume, temperature is 100 ℃ in the reactor, pressure is 0.4Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.61mgKOH/g.
Embodiment 4
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, sulfuric acid and the phosphoric acid of 8.5mgKOH/g is sent in the tubular reactor with acid number, wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 0.6: 1, take the biodiesel coarse product charging as benchmark, the add-on of sulfuric acid is 0.08 % by weight (weight ratio of sulfuric acid and phosphoric acid 9: 1) of biodiesel coarse product volume, temperature is 112 ℃ in the reactor, pressure is 0.5Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.78mgKOH/g.
Embodiment 5
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, the sulfuric acid of 8.5mgKOH/g is sent in the tubular reactor with acid number, wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 1.7: 1, take the biodiesel coarse product charging as benchmark, the add-on of sulfuric acid is 0.02 % by weight of biodiesel coarse product volume, temperature is 187 ℃ in the reactor, pressure is 2.5Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.77mgKOH/g.
Embodiment 6
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, the sulfuric acid of 8.5mgKOH/g is sent in the tubular reactor with acid number, wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 1.7: 1, take the biodiesel coarse product charging as benchmark, the add-on of sulfuric acid is 0.02 % by weight of biodiesel coarse product volume, temperature is 187 ℃ in the reactor, pressure is 1.0Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.75mgKOH/g.
Embodiment 7
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
(acid number is 12.3mgKOH/g with biodiesel coarse product, with the biodiesel coarse product preparation example in distill under the identical distillation condition, the mass yield of biofuel is 83%), methyl alcohol, phospho-wolframic acid is provided in the tubular reactor, wherein, volume space velocity is 1.2h during the liquid of biodiesel coarse product
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 1.9: 1, take the biodiesel coarse product charging as benchmark, the add-on of phospho-wolframic acid is 0.1 % by weight of biodiesel coarse product volume, temperature is 160 ℃ in the reactor, pressure is 0.4Mpa, the acid number of the biofuel product that obtains after the reaction is 1.70mgKOH/g, with obtain fall after the acid product with the biodiesel coarse product preparation example in distill under the identical distillation condition, the mass yield of the biofuel that obtains is 90.1%.
Embodiment 8
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that 4.2mgKOH/g biodiesel coarse product, methyl alcohol, phospho-wolframic acid are provided in the tubular reactor with acid number, wherein, volume space velocity 1.2h during the liquid of biodiesel coarse product
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 1.2: 1, take the biodiesel coarse product charging as benchmark, the phospho-wolframic acid add-on is 0.2 % by weight of biodiesel coarse product, temperature is 160 ℃ in the reactor, pressure is 0.5Mpa, and the acid number of the biofuel product that obtains after the reaction is 0.74mgKOH/g.
Embodiment 9
The present embodiment is used for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
Be that biodiesel coarse product, methyl alcohol, 1-butyl-pyridinium Witco 1298 Soft Acid ionic liquid (preparing according to CN101759646A embodiment 6) and the tin chloride (tin chloride is 7 % by weight of described ionic liquid weight) of 8.5mgKOH/g sent in the tubular reactor with acid number, wherein, volume space velocity is 1h during the liquid of biodiesel coarse product
-1, methyl alcohol and take the mol ratio of the described biodiesel coarse product of fatty acid methyl ester as 7.6: 1, take the biodiesel coarse product charging as benchmark, the ionic liquid add-on is 0.4 % by weight of biodiesel coarse product volume, temperature is 170 ℃ in the reactor, pressure is 0.7Mpa, and the acid number of the biofuel product that obtains after the reaction is 2.49mgKOH/g.
Comparative Examples 1
This Comparative Examples is used for the acid reduction method of the biodiesel coarse product of explanation prior art.
Method according to the disclosed embodiment 1 of CN102041177, oil plant is preheating to 60 ℃ in reactor after, add 500Kg according to oil plant, methyl alcohol adds 83Kg, under agitation add the vitriol oil, vitriol oil add-on is 4 % by weight of oil plant weight, makes temperature of reaction kettle remain on 75 ℃, reacted 2 hours, acid number is 3mgKOH/g in the system.
Can find out from the above results, adopt the method for the present invention can be under relatively mild condition, and under the condition that adopts few catalyzer and the acid number that can significantly reduce the biodiesel coarse product with higher acid value in the higher liquid hourly space velocity (shorter reaction time).
In addition, the method for preparing biofuel of the present invention, select suitable catalyzer and processing condition, can before distillation procedure, effectively reduce the acid number of biodiesel coarse product, more preferably can reach the requirement of BD100 standard, and need not after distillation, again to carry out the loaded down with trivial details acid of falling, and only need by simple underpressure distillation, namely can obtain qualified biofuel product after removing heavy impurity, and can improve the yield of biofuel, thereby greatly simplified operation, improved production efficiency, and reduced energy consumption.
Claims (10)
1. method that reduces the biodiesel coarse product acid number, the acid number of described biodiesel coarse product is 3-20mgKOH/g, it is characterized in that, the method is included under the existence of catalyzer, with described biodiesel coarse product and the reaction of monohydroxy-alcohol Continuous Contact, described catalytic condition comprises: temperature of reaction is 70-220 ℃, and reaction pressure is 0.2-3MPa, and the consumption of described catalyzer is the 0.001-0.4 % by weight of biodiesel coarse product.
2. method according to claim 1, wherein, the consumption of described catalyzer is the 0.01-0.2 % by weight of biodiesel coarse product.
3. method according to claim 1 and 2, wherein, described catalyzer is selected from one or more in sulfuric acid, phosphoric acid, phospho-wolframic acid, phospho-molybdic acid, tungstosilicic acid and the ionic liquid.
4. method according to claim 1, wherein, described reaction is carried out in tubular reactor.
5. according to claim 1 or 4 described methods, wherein, described catalytic condition also comprises: volume space velocity 0.1-5h during the liquid of described biodiesel coarse product
-1, monohydroxy-alcohol with take the mol ratio of the described biodiesel coarse product of lipid acid monobasic alcohol ester as 0.1-9: 1.
6. method according to claim 5, wherein, volume space velocity is 0.6-3h during the liquid of biodiesel coarse product
-1, monohydroxy-alcohol with take the mol ratio of the described biodiesel coarse product of lipid acid monobasic alcohol ester as 0.4-2: 1.
7. method according to claim 1, wherein, temperature of reaction is 100-160 ℃, reaction pressure is 0.3-0.7MPa.
8. method according to claim 5, wherein, described monohydroxy-alcohol is that carbonatoms is the aliphatic monobasic alcohol of 1-6.
9. the preparation method of a biofuel, it is characterized in that, it is that acid falls in the biodiesel coarse product of 3-20mgKOH/g that the method comprises acid number, and the biofuel product that will fall after the acid carries out underpressure distillation, and the described method that acid is fallen in biodiesel coarse product is the described method of any one among the claim 1-8.
10. method according to claim 9, wherein, the preparation method of described biodiesel coarse product is included under 170-350 ℃, 3-10MPa condition, with raw oil material and monohydroxy-alcohol contact reacts; Monohydroxy-alcohol with take the mol ratio of the raw oil material of tri-glyceride as 3-60: 1; The acid number of described raw oil material is 10-200mgKOH/g.
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