CN118207045A - Method for preparing fatty acid ester by adopting solid catalyst - Google Patents
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Abstract
The present invention provides a method for producing fatty acid esters, comprising: mixing grease and C1-C6 monohydric alcohol in a reactor in the presence of a composite oxide catalyst, reacting at the reaction temperature of 60-200 ℃ and the pressure of 0.1-2 Mpa, and separating fatty acid ester from the reacted material, wherein the catalyst has the following general formula: cuMn aAlbOc, wherein a, b and c respectively represent the atomic numbers of Mn, al and O, and the value range is as follows: wherein a=0.01 to 1.5, b=0.2 to 2, and c is the number of oxygen atoms to satisfy the compound charge neutrality requirement. The method adopts a solid catalyst, can treat oil with high acid value and high impurity under the conditions of lower temperature and pressure, and can obtain the biodiesel with high yield through one-step reaction.
Description
The application is a 201510031336.9 divisional application.
Technical Field
The present invention relates to a method for preparing fatty acid ester (i.e. biodiesel) by reacting grease and monohydric alcohol.
Background
Biodiesel can be produced by transesterification of fats and oils with monohydric alcohols, with fatty acid esters, as well as mono-, di-, and glycerins, as well as unreacted alcohols and fats and oils (i.e., triglycerides) in the reaction product. In the prior art, the preparation methods of biodiesel can be classified into an acid catalysis method, a base catalysis method, an enzyme catalysis method and a supercritical method.
CN1473907A is produced by using vegetable oil refining leftovers and edible recovered oil as raw materials, the catalyst is compounded by sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid and other inorganic and organic acids, and the processes of acidification, impurity removal, continuous dehydration, esterification, layering, reduced pressure distillation and the like are carried out, the continuous vacuum dehydration pressure is 0.08-0.09 Mpa, the temperature is 60-95 ℃, the dehydration is carried out until the water content is below 0.2%, the catalyst addition amount in the esterification step is 1-3%, the esterification temperature is 60-80 ℃, and the reaction time is 6 hours. And neutralizing the product after the reaction to remove the catalyst, then layering to remove water, and distilling the product after the water under reduced pressure to obtain the biodiesel.
The acid catalysis has the problem of slow reaction speed compared with the base catalysis, and a large amount of waste acid is generated, so that the environment is polluted.
JP9-235573 discloses a method for producing a diesel fuel from waste edible oil and methanol in the presence of sodium hydroxide, but natural oils and fats generally contain free fatty acids, and in the case where the free fatty acids are large, fatty acid soaps are produced by using an alkali metal catalyst, so that the alkali metal catalyst is excessive and separation of the fatty acid ester layer from the glycerin layer becomes difficult,
DE3444893 discloses a process in which the free fatty acids are esterified with alcohols with acid catalysts at atmospheric pressure at 50 to 120 ℃, the oils are pre-esterified and then transesterified with alkali metal catalysts, but the remaining acid catalyst is neutralized with alkali and the amount of alkali metal catalyst is increased. The pre-esterification is adopted, so that the processing flow is prolonged, the equipment investment and the energy consumption are greatly increased, in addition, the alkaline catalyst is required to be removed from the product, and a large amount of wastewater is generated. Recovery of glycerol is difficult.
US5713965A discloses a process for the preparation of fatty acid methyl esters, i.e. diesel fuels, by reacting fats and oils with alcohols in the presence of lipases as solvents.
CN1472280a discloses a method for producing biodiesel by catalyzing a biological transesterification reaction in the presence of a biological enzyme by using fatty acid ester as an acyl acceptor. The disadvantages of using enzyme catalysts are: long reaction time, low efficiency, expensive enzyme and easy inactivation in high-purity methanol.
CN1111591C discloses a method for preparing fatty acid ester by reacting grease and monohydric alcohol, the method comprises reacting methanol with grease to obtain fatty acid ester, under the conditions of 270-280 ℃ and 11-12 Mpa, the formation rate of fatty acid methyl ester is 55-60%, and the formation rate of fatty acid methyl ester is lower.
Disclosure of Invention
The invention provides a method for preparing fatty acid ester, which adopts a solid catalyst, can treat oil with high acid value and high impurity under the conditions of lower temperature and pressure, and can obtain biodiesel with high yield through one-step reaction.
The method for preparing the fatty acid ester provided by the invention comprises the following steps: the composite oxide is used as catalyst, grease is mixed with C 1～C6 monohydric alcohol, the reaction is carried out at the temperature of 60-200 ℃ and the pressure of 0.1-2 Mpa, and fatty acid ester is separated from the reacted material.
The main component of the grease is fatty acid triglyceride, including various animal and vegetable grease, and oil in substances from microorganisms, algae and the like. Vegetable fats and oils such as soybean oil, rapeseed oil, peanut oil, sunflower seed oil, palm oil, coconut oil, and fatty-based materials derived from the fruits, stems, leaves, branches and roots of other various crops and wild plants (including wood pulp floating oil produced in the papermaking process). Animal oils and fats such as lard, tallow, sheep oil, fish oil, etc. The oil may be unrefined oil, refined oil, acidified oil, frying oil, waste oil, and the like.
The process of the present invention is particularly suitable for oils and fats having high impurities and high acid numbers, for example, the acid number may be from 0.1 to 200mgKOH/g, preferably from 10 to 150mgKOH/g. The raw oil can be pretreated by adopting the method of the invention.
The monohydric alcohol refers to monohydric aliphatic alcohol with 1-6 carbon atoms, and can be saturated alcohol or unsaturated alcohol. Such as methanol, ethanol, propanol, isopropanol, allyl alcohol, n-butanol and isomers thereof, pentanol and isomers thereof, and the like. Alcohols alone or in mixtures thereof may be used. Methanol or ethanol is preferred.
The catalyst of the invention has the following general formula:
CuMnaAlbOc
wherein a, b and c respectively represent the atomic numbers of Mn, al and O, and the value ranges are as follows: wherein a=0.01 to 1.5, preferably 0.04 to 1.0, b=0.2 to 2, preferably 0.2 to 1.5, and c is the number of oxygen atoms to meet the charge neutrality requirement of the compound.
The preparation method of the catalyst is a coprecipitation method, and the method comprises the following steps: dissolving water soluble salts of Cu, mn and Al (preferably nitrate of Cu, mn and Al) in a certain proportion in deionized water to prepare a mixed solution, precipitating with alkali to pH=4-11, preferably pH=5-10 at 10-80 ℃, preferably 20-50 ℃, aging for 0-5 hours, preferably 1-3 hours, filtering, washing, collecting precipitate, drying at 70-200 ℃, preferably 100-150 ℃ for 2-30 hours, and roasting at 300-900 ℃, preferably 300-700 ℃ for 2-30 hours to obtain the catalyst used by the invention.
The soluble salt may be solution containing Cu, mn and Al metal salts, or solution containing one or two metal salts, or the latter solution may be prepared by precipitating several solutions containing different metal salts with alkali, mixing the solutions, and aging. The soluble salts of Cu, mn and Al are preferably nitrate salts. The alkali can be ammonium carbonate, ammonium bicarbonate, ammonia water, sodium carbonate, sodium hydroxide, potassium hydroxide and the like, and is preferably ammonium carbonate, ammonium bicarbonate or ammonia water. The concentration of the lye is 5 to 40 wt.%, preferably 10 to 35 wt.%.
When the catalyst is prepared, ammonium carbonate, ammonium bicarbonate and ammonia water are used as precipitants, so that the consumption of washing water in the preparation of the catalyst can be greatly reduced, the washing times are reduced, and the production efficiency of the catalyst is improved.
Specifically, the present invention can employ an autoclave or a fixed bed (tubular reactor), if an autoclave is employed, the fat, the alcohol and the catalyst are charged into the autoclave, the reaction is carried out under stirring, if a tubular reactor is employed, preferably the fat and the monohydric alcohol are fed in from the lower portion of the tubular reactor, the reaction product is discharged from the upper end of the tubular reactor to obtain a reaction crude product, the monohydric alcohol is distilled from the reaction crude product, the mixed ester phase (containing fatty acid ester, monoglyceride, diglyceride, unreacted triglyceride) and glycerin are separated, and the mixed ester phase and glycerin are distilled to obtain high-purity fatty acid ester and glycerin, respectively.
According to the process of the present invention, if an autoclave is used, the catalyst is added in an amount of 0.01% to 7%, preferably 0.1% to 3%, more preferably 0.5% to 2% by weight of the fat. If a tubular reactor is used, the liquid hourly space velocity is from 0.1 to 9h -1, preferably from 0.1 to 3h -1, more preferably from 0.1 to 1h -1.
The reactor temperature is 100-200 ℃, preferably 120-170 ℃, the pressure is 0.1-2 Mpa, preferably 0.3-1.2 Mpa, and the mass ratio of monohydric alcohol to grease is 0.05-2: 1, preferably 0.1 to 1.5:1.
The higher the temperature, the higher the conversion of the reaction, since the higher the temperature is in favor of the reaction from the kinetic point of view, but above 300℃the darker the color of the reaction product, the more char is produced and the decomposition of glycerol is also caused, so that the reactor temperature should be < 300℃and preferably 100-200 ℃.
The higher the pressure, the more advantageous the reaction, but the higher the pressure, the more the equipment investment and the operating costs are increased, so the pressure is 0.1 to 2MPa, preferably 0.3 to 1.2MPa.
The mass ratio of the monohydric alcohol to the grease in the method can be changed in a large range, and too high mass ratio of the methanol to the grease can greatly increase the recovery amount of the methanol, increase the energy consumption and the operation cost of the device and reduce the utilization rate of equipment. Therefore, the mass ratio of the monohydric alcohol to the grease is 0.05-2: 1, preferably 0.1 to 1.5:1.
The method is applicable to raw oil with wide range of acid value and wide range of acid value, and is applicable to high acid value and high impurity oil.
The invention combines the composite metal oxide solid catalyst with a low-pressure and low-temperature reaction mode, and can obtain the biodiesel with high yield through one-step reaction. In the one-step reaction process, the oil material is subjected to both esterification and transesterification.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto.
Examples 1 to 3 are preparations of catalysts.
Example 1
35.5G of Cu (NO 3)2.3H2 O (chemical purity) and 57g of 50% Mn (NO 3)2 aqueous solution (chemical purity) in Beijing chemical plant), 79g of Al (NO 3)3.9H2 O (chemical purity) in Beijing chemical plant) are dissolved in 500ml of deionized water, ammonia water (23 wt% in Beijing chemical plant) is added dropwise under stirring, aging is carried out for 1 hour until the pH of the solution is 8+ -0.4, then the solution is filtered, washed once, the precipitate is collected, dried for 2 hours at 200 ℃, and roasted for 2 hours at 300 ℃ to obtain the catalyst A, namely CuMn 0.9 Al1.5O4.2.
Example 2
52.2G of Cu (NO 3)2.3H2 O (chemical purity) and 47g of 50% Mn (NO 3)2 aqueous solution (chemical purity) and 17g of Al (NO 3)3.9H2 O (chemical purity) and preparing solution A. Na 2CO3 (20 wt.%) (chemical purity) are prepared into solution B. 200ml of deionized water are filled in a 1000ml beaker,
Adding the two solutions A and B into a beaker while stirring, controlling the dropping speed of A, B to ensure that the PH is always kept at 5.5+/-0.5, aging for 1 hour after titration, filtering, washing with water for multiple times, collecting precipitate, drying at 120 ℃ for 3 hours, and roasting at 740+/-40 ℃ for 2 hours to obtain the catalyst B, namely CuMn 0.46Al0.2O1.76.
Example 3
52.2G of Cu (NO 3)2.3H2 O) (chemical purity of Beijing chemical plant), 17.1g of 50% Mn (NO 3)2 aqueous solution (chemical purity of Beijing chemical plant), 74.9g of Al (NO 3)3.9H2 O) (chemical purity of Beijing chemical plant) are dissolved in 500ml of deionized water to prepare solution A. Ammonia water (23 wt%) is prepared into solution B. 200ml of deionized water is filled into a 1000ml beaker, A, B solutions are simultaneously added into the beaker under stirring, the dripping speed of A, B is controlled to keep the PH at 9+/-0.5 all the time, after titration, the mixture is aged for 1 hour, then filtered, washed once, precipitate is collected, dried for 2 hours at 120 ℃, and baked for 2 hours at 450+/-40 ℃ to obtain the catalyst C CuMn 0.21Al0.9O2.42.
Example 4
Adding waste oil with an acid value of 40mgKOH/g and methanol into an autoclave together, wherein the mass ratio of the alcohol to the oil is 0.17:1, adding a catalyst A with the weight of 0.6% of the oil, reacting for 1 hour under the conditions of the temperature of the autoclave being 130 ℃, the pressure being 0.4Mpa and the stirring speed being 200 r/min, obtaining a reaction crude product, distilling, removing excessive methanol at the bottom of the autoclave being less than 150 ℃, recycling and reusing the methanol, separating the residual materials to obtain a glycerin phase, and then carrying out reduced pressure distillation on the obtained mixed ester phase to obtain the biodiesel with the yield of 93.3%.
Example 5
Adding waste oil with an acid value of 40mgKOH/g and methanol into an autoclave together, wherein the mass ratio of the alcohol to the oil is 0.19:1, adding a catalyst B with the weight of 0.6% of the oil, reacting for 1 hour under the conditions of the temperature of the autoclave being 140 ℃, the pressure being 0.9Mpa and the stirring speed being 200 r/min, obtaining a reaction crude product, distilling, removing excessive methanol at the bottom of the autoclave being less than 150 ℃, recycling and reusing the methanol, separating the residual materials to obtain a glycerin phase, and then carrying out reduced pressure distillation on the obtained mixed ester phase to obtain the biodiesel with the yield of 90.5%.
Example 6
Adding acidified oil with an acid value of 122mgKOH/g and methanol into an autoclave together, wherein the mass ratio of the alcohol to the oil is 0.17:1, adding a catalyst C with the weight of 0.9% of the oil, reacting for 1 hour under the conditions of the temperature of the autoclave being 140 ℃, the pressure being 0.9Mpa and the stirring speed being 400 r/min to obtain a crude reaction product, distilling the crude reaction product, removing excessive methanol at the bottom of the autoclave being less than 150 ℃, recycling and reusing the methanol, separating the residual materials to obtain a glycerin phase, and then carrying out reduced pressure distillation on the obtained mixed ester phase to obtain the biodiesel with the yield of 89%.
Example 7
Adding waste oil with an acid value of 91mgKOH/g and methanol into an autoclave together, wherein the mass ratio of the alcohol to the oil is 0.17:1, adding a catalyst C with the weight of 0.4% of the oil, reacting for 2.5 hours under the conditions of the temperature of the autoclave being 110 ℃, the pressure being 0.2Mpa and the stirring speed being 200 r/min, obtaining a crude reaction product, distilling, removing excessive methanol at the bottom of the autoclave being less than 150 ℃, recycling and reusing the methanol, separating the residual materials to obtain a glycerin phase, and then carrying out reduced pressure distillation on the obtained mixed ester phase to obtain the biodiesel with the yield of 60%.
Example 8
5.2 G of catalyst B with granularity of 26-40 meshes is put into a tubular reactor made of stainless steel with internal diameter of 8 mm and length of 391 mm, waste grease with acid value of 97mg KOH/g is taken as raw material, oil and methanol continuously enter the tubular reactor from the lower part of the tubular reactor under the conditions of alcohol oil quality ratio of 0.25 and liquid hourly space velocity of 0.4h -1, reaction temperature of 140 ℃ and pressure of 0.9Mpa, reaction product flows out from the upper end of the tubular reactor, unreacted methanol is distilled out from the crude reaction product, the crude reaction product stands still to separate glycerin phase, and the biodiesel yield of 89% is obtained by decompressing and rectifying the ester phase.
Example 9
5G of catalyst A with granularity of 26-40 meshes is filled into a tubular reactor made of stainless steel with internal diameter of 8 mm and length of 391 mm, waste grease with acid value of 52mg KOH/g is taken as a raw material, oil and methanol continuously enter the tubular reactor from the lower part of the tubular reactor under the conditions of alcohol oil quality ratio of 0.2 and liquid hourly space velocity of 0.6h -1, reaction temperature of 130 ℃ and pressure of 0.7Mpa are carried out, reaction products flow out from the upper end of the tubular reactor, unreacted methanol is distilled out from the crude reaction products, the crude reaction products are stood for separation of glycerin phase, and the biodiesel yield of 92% is obtained by decompressing and rectifying ester phase.
Claims (10)
1. A method of preparing a fatty acid ester comprising: mixing grease and C1-C6 monohydric alcohol in a reactor in the presence of a composite oxide catalyst, reacting at the reaction temperature of 60-200 ℃ and the pressure of 0.1-2 MPa, and separating fatty acid ester from the reacted material, wherein the catalyst has the following general formula: cuMn aAlbOc, wherein a, b and c respectively represent the atomic numbers of Mn, al and O, and the value range is as follows: wherein a=0.01 to 1.5, b=0.2 to 2, c is the number of oxygen atoms to meet the compound neutrality requirement, the grease is waste grease or acidified grease, and the acid value is 10 to 150mgKOH/g.
2. The method according to claim 1, wherein the acid value of the oil or fat is 52 to 122mgKOH/g.
3. The method according to claim 1, wherein the monohydric alcohol is a monohydric aliphatic alcohol having 1 to 6 carbon atoms.
4. The process of claim 1 wherein in the catalyst formula a = 0.04-1.0 and b = 0.2-1.5, c is the number of oxygen atoms required to meet the compound's electroneutrality.
5. The process according to claim 1, wherein the reactor is an autoclave or a tubular reactor.
6. The process according to claim 1, wherein the catalyst is added in an amount of 0.01 to 7% by weight of the fat if an autoclave is used.
7. The process according to claim 1, wherein, if a tubular reactor is used, the liquid hourly space velocity is from 0.1 to 9h -1.
8. The process according to claim 1, wherein the reactor temperature is 120 to 170 ℃.
9. The method according to claim 1, wherein the pressure is 0.3 to 1.2MPa.
10. The method according to claim 1, wherein the mass ratio of monohydric alcohol to grease is 0.05-2: 1.
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| CN202410511428.6A CN118207045A (en) | 2015-01-22 | 2015-01-22 | Method for preparing fatty acid ester by adopting solid catalyst |
| CN201510031336.9A CN105861162A (en) | 2015-01-22 | 2015-01-22 | Preparation method of aliphatic ester by using solid catalyst |
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| CN111411129B (en) * | 2019-01-04 | 2021-10-01 | 清华大学 | Adding decomposable ammonium salt to improve the process of preparing biodiesel by enzymatic oil |
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| CN101096615B (en) * | 2006-06-29 | 2010-07-21 | 中国石油化工股份有限公司 | Process for preparing fatty acid esters |
| CN101480619A (en) * | 2009-01-05 | 2009-07-15 | 北京化工大学 | Method for preparing acidified solid catalyst for synthesizing biodiesel |
| CN102199493A (en) * | 2010-03-23 | 2011-09-28 | 华东理工大学 | Environmentally-friendly preparation method for biological diesel oil under catalysis of solid base |
| KR20140006030A (en) * | 2011-02-14 | 2014-01-15 | 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 | Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts |
| CN102807922A (en) * | 2011-05-31 | 2012-12-05 | 中国石油化工股份有限公司 | Preparation method for fatty acid ester |
| US8624073B1 (en) * | 2013-02-05 | 2014-01-07 | Cpc Corporation, Taiwan | Homogeneous catalysts for biodiesel production |
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