CN102796620A - Fixed bed-based continuous catalytic esterification production method - Google Patents
Fixed bed-based continuous catalytic esterification production method Download PDFInfo
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- CN102796620A CN102796620A CN2012102986105A CN201210298610A CN102796620A CN 102796620 A CN102796620 A CN 102796620A CN 2012102986105 A CN2012102986105 A CN 2012102986105A CN 201210298610 A CN201210298610 A CN 201210298610A CN 102796620 A CN102796620 A CN 102796620A
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Abstract
The invention discloses a fixed bed-based continuous catalytic esterification production method. The fixed bed-based continuous catalytic esterification production method comprises the following steps of 1, mixing a raw material and a lower alcohol having a concentration above 99.5%, wherein the raw material is high-acid value waste vegetable and animal oil or a deodorizer distillate which does not contain impurities and has moisture content of 0.05 to 0.5%, 2, merging a mixed material liquid obtained by the step 1 and an acid, heating to a temperature of 50 to 100 DEG C, and carrying out an esterification reaction process by a fixed bed with a highly acidic resin, 3, carrying out on-line neutralization by an alkali solution, 4, carrying out reduced pressure removal of an alcohol and water, and 5, carrying out reduced pressure distillation to obtain a purified low fatty acid ester. The fixed bed-based continuous catalytic esterification production method can reduce a raw material acid value to below 3mgKOH/g only by one step, avoid secondary esterification, reduce a use amount of a solvent by 50%, reduce energy consumption and solvent consumption by 50%, avoid resin regeneration treatment and realize a service life above 2 years.
Description
Technical field
The present invention relates to a kind of improved fixed bed continuous catalysis esterification production method, relate in particular to biofuel and natural VE industry, belong to the oil and fat chemical field.
Background technology
Be the raw material production fatty acid methyl ester with oil from high acid value waste animal and plant fat---biofuel and be in the raw material production natural VE process with DD oil (deodorization distillate); Need the free fatty acids in the raw material is converted into fatty acid methyl ester or ethyl ester with methyl alcohol or ethanol synthesis under an acidic catalyst effect, this an acidic catalyst of manufacturing enterprise relates generally to liquid acid at present---the vitriol oil and highly acidic resin.Domestic literature and related patent U.S. Patent No. are about more with these two catalyst esterification techniques reports; Relative merits separately being arranged: liquid acid---the catalytic esterification technology that the vitriol oil is made catalyzer has the catalytic activity height, can once acid value be dropped to below the 3mgKOH/g, but equipment is had very strong corrosion; Produce great amount of wastewater; And there is side reaction to produce, batch production, labour intensity is bigger; With the highly acidic resin is the fixed-bed catalytic esterification techniques realization continuous production of filler, and side reaction is few, non-wastewater discharge; Equipment is not had corrosion, but catalytic activity is low, need carry out the secondary esterification could drop to acid value below the 3mgKOH/g; The methyl alcohol usage quantity is big; Resin causes the resin activity to reduce because impurity such as adsorpting pigment stop up the resin duct after operation for some time simultaneously, need carry out activating and regenerating to resin, thereby increase production stage.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of fixed bed continuous catalysis esterification production method is provided.
Technical scheme of the present invention is summarized as follows:
A kind of fixed bed continuous catalysis esterification production method is characterized in that comprising the steps:
(1) be that the ratio of 1:0.1-1 is mixed with the quality percentage composition raw material at the lower alcohol more than 99.5% in mass ratio, said raw material is for removing impurity, oil from high acid value waste animal and plant fat or the deodorization distillate of the quality percentage composition of moisture below 0.05-0.5%;
(2) be that mixed liquor that the ratio of 1:0.00025-0.0025 obtains step (1) mixes with acid and is heated to 50-100 ℃ in mass ratio; Carry out esterification through the fixed bed that highly acidic resin is housed then; Flow rate control is at 0.1-1 times of resin volume per hour, and pressure-controlling is at 0.05-0.2MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 7-8;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained purified lipid acid low-carbon-ester.
Said lower alcohol is methyl alcohol or ethanol.
Said acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or Phenylsulfonic acid.
The model of said highly acidic resin is: D061, NKC-9, HD-8, D002, D006,005CR, CAT601, C005 or CAT600.
Said alkali lye is that mass concentration is that aqueous sodium hydroxide solution or the mass concentration of 10%-30% is the potassium hydroxide aqueous solution of 10%-30%.
The present invention improves the fixed-bed catalytic esterification techniques; Both overcome the equipment corrosion that liquid acid brings and the shortcoming of large amount of sewage discharging, overcome again the solvent usage quantity that single fixed-bed catalytic technology brings big, need carry out twice esterification, resin contaminated need regeneration and work-ing life short shortcoming.Method of the present invention can make below the disposable 3mgKOH/g of dropping to of raw material acid value, does not need the secondary esterification, and the solvent usage quantity reduces 50%, and energy consumption and solvent consumption reduce by 50%, and resin does not need manipulation of regeneration, and can reach more than 2 years work-ing life.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) in mass ratio be the ratio of 1:0.8 with raw material and quality percentage composition in the methanol mixed more than 99.5%, said raw material is for removing impurity, the quality percentage composition of moisture is the deodorization distillate of 78.2mgKOH/g in the acid value below 0.05%;
(2) be that mixed liquor that the ratio of 1:0.001 obtains step (1) mixes with sulfuric acid and is heated to 80 ℃ in mass ratio; Carry out esterification through the fixed bed that D061 type highly acidic resin is housed then; Flow rate control is at 0.5 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 7, alkali lye is that mass concentration is 20% aqueous sodium hydroxide solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty acid methyl ester.Acid value is 1.8mgKOH/g.
Embodiment 2
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) in mass ratio be the ratio of 1:0.5 with raw material and quality percentage composition in the methanol mixed more than 99.5%, said raw material is for removing impurity, the quality percentage composition of moisture is the deodorization distillate of 85.4mgKOH/g in the acid value below 0.1%;
(2) be the ratio of 1:0.002 mixed liquor and mixed in hydrochloric acid that step (1) is obtained in mass ratio and be heated to 90 ℃; Carry out esterification through the fixed bed that NKC-9 type highly acidic resin is housed then; Flow rate control is at 0.4 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 8, alkali lye is that mass concentration is 30% aqueous sodium hydroxide solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty acid methyl ester.Acid value is 2.1mgKOH/g.
Embodiment 3
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) in mass ratio be the ratio of 1:0.1 with raw material and quality percentage composition in the methanol mixed more than 99.5%, said raw material is for removing impurity, the quality percentage composition of moisture is the swill oil of 15.3mgKOH/g in the acid value below 0.3%;
(2) be that mixed liquor that the ratio of 1:0.0025 obtains step (1) mixes with nitric acid and is heated to 70 ℃ in mass ratio; Carry out esterification through the fixed bed that HD-8 type highly acidic resin is housed then; Flow rate control is at 0.6 times of resin volume per hour, and pressure-controlling is at 0.15MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 7, alkali lye is that mass concentration is 10% aqueous sodium hydroxide solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty acid methyl ester.Acid value is 0.9mgKOH/g.
Embodiment 4
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) in mass ratio be the ratio of 1:0.3 with raw material and quality percentage composition in the methanol mixed more than 99.5%, said raw material is for removing impurity, the quality percentage composition of moisture is the deodorization distillate of 65.1mgKOH/g in the acid value below 0.5%;
(2) be that mixed liquor that the ratio of 1:0.00025 obtains step (1) mixes with phosphoric acid and is heated to 100 ℃ in mass ratio; Carry out esterification through the fixed bed that D002 type highly acidic resin is housed then; Flow rate control is at 0.1 times of resin volume per hour, and pressure-controlling is at 0.05MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 8, alkali lye is that mass concentration is 30% aqueous sodium hydroxide solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty acid methyl ester.Acid value is 1.9mgKOH/g.
Embodiment 5
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) in mass ratio be the ratio of 1:0.4 with raw material and quality percentage composition in the methanol mixed more than 99.5%, said raw material is for removing impurity, the quality percentage composition of moisture is the swill oil of 11.5mgKOH/g in the acid value below 0.05%
(2) be that mixed liquor that the ratio of 1:0.0004 obtains step (1) mixes with Phenylsulfonic acid and is heated to 50 ℃ in mass ratio; Carry out esterification through the fixed bed that D006 type highly acidic resin is housed then; Flow rate control is at 1 times of resin volume per hour, and pressure-controlling is at 0.2MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 7, alkali lye is that mass concentration is 20% potassium hydroxide aqueous solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty acid methyl ester.Acid value is 0.6mgKOH/g.
Embodiment 6
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) be that the ratio of 1:0.7 is mixed with the quality percentage composition raw material at the ethanol more than 99.5% in mass ratio, said raw material is for removing impurity, and the quality percentage composition of moisture is the acidifying oil of 110.1mgKOH/g in the acid value below 0.1%;
(2) be that mixed liquor that the ratio of 1:0.0006 obtains step (1) mixes with sulfuric acid and is heated to 60 ℃ in mass ratio; Carry out esterification through the fixed bed that 005CR type highly acidic resin is housed then; Flow rate control is at 0.5 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 8, alkali lye is that mass concentration is 30% potassium hydroxide aqueous solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty-acid ethyl ester.Acid value is 2.4mgKOH/g.
Embodiment 7
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) be that the ratio of 1:0.9 is mixed with the quality percentage composition raw material at the ethanol more than 99.5% in mass ratio, said raw material is for removing impurity, and the quality percentage composition of moisture is the deodorization distillate of 100.5mgKOH/g in the acid value below 0.3%;
(2) be the ratio of 1:0.0008 mixed liquor and mixed in hydrochloric acid that step (1) is obtained in mass ratio and be heated to 70 ℃; Carry out esterification through the fixed bed that CAT601 type (also can adopt the CAT600 type) strongly-acid CAT601 resin is housed then; Flow rate control is at 0.5 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 7, alkali lye is that mass concentration is 10% potassium hydroxide aqueous solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty-acid ethyl ester.Acid value is 2.3mgKOH/g.
Embodiment 8
A kind of fixed bed continuous catalysis esterification production method comprises the steps:
(1) be that the ratio of 1:1 is mixed with the quality percentage composition raw material at the ethanol more than 99.5% in mass ratio, said raw material is for removing impurity, and the quality percentage composition of moisture is the acidifying oil of 120.6mgKOH/g in the acid value below 0.5%;
(2) be that mixed liquor that the ratio of 1:0.001 obtains step (1) mixes with nitric acid and is heated to 80 ℃ in mass ratio; Carry out esterification through the fixed bed that C005 type highly acidic resin is housed then; Flow rate control is at 0.4 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 8, alkali lye is that mass concentration is 20% potassium hydroxide aqueous solution;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained the purified fatty-acid ethyl ester.Acid value is 2.6mgKOH/g.
Claims (5)
1. a fixed bed continuous catalysis esterification production method is characterized in that comprising the steps:
(1) be that the ratio of 1:0.1-1 is mixed with the quality percentage composition raw material at the lower alcohol more than 99.5% in mass ratio, said raw material is for removing impurity, oil from high acid value waste animal and plant fat or the deodorization distillate of the quality percentage composition of moisture below 0.05-0.5%;
(2) be that mixed liquor that the ratio of 1:0.00025-0.0025 obtains step (1) mixes with acid and is heated to 50-100 ℃ in mass ratio; Carry out esterification through the fixed bed that highly acidic resin is housed then; Flow rate control is at 0.1-1 times of resin volume per hour, and pressure-controlling is at 0.05-0.2MPa;
(3) solution of handling through step (2) is carried out online neutralization with alkali lye, make the pH value be controlled at 7-8;
(4) alcohol and water is taken off in the feed liquid decompression of handling through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of handling through step (4) is obtained purified lipid acid low-carbon-ester.
2. a kind of fixed bed continuous catalysis esterification production method according to claim 1 is characterized in that said lower alcohol is methyl alcohol or ethanol.
3. a kind of fixed bed continuous catalysis esterification production method according to claim 1 is characterized in that said acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or Phenylsulfonic acid.
4. a kind of fixed bed continuous catalysis esterification production method according to claim 1 is characterized in that the model of said highly acidic resin is: D061, NKC-9, HD-8, D002, D006,005CR, CAT601, C005 or CAT600.
5. a kind of fixed bed continuous catalysis esterification production method according to claim 1 is characterized in that said alkali lye is that mass concentration is that aqueous sodium hydroxide solution or the mass concentration of 10%-30% is the potassium hydroxide aqueous solution of 10%-30%.
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| CN106397189A (en) * | 2016-08-30 | 2017-02-15 | 江西盛伟科技股份有限公司 | Synthesis method of tert-butyl chloroacetate |
| CN110257445A (en) * | 2019-06-28 | 2019-09-20 | 中粮天科生物工程(天津)有限公司 | Biodiesel, the method for natural VE and phytosterol are prepared from plant oil deodorizing distillate |
| CN111534382A (en) * | 2020-04-07 | 2020-08-14 | 宜春大海龟生命科学有限公司 | Optimization method for esterification reaction of deodorized distillate of vegetable oil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106397189A (en) * | 2016-08-30 | 2017-02-15 | 江西盛伟科技股份有限公司 | Synthesis method of tert-butyl chloroacetate |
| CN110257445A (en) * | 2019-06-28 | 2019-09-20 | 中粮天科生物工程(天津)有限公司 | Biodiesel, the method for natural VE and phytosterol are prepared from plant oil deodorizing distillate |
| CN111534382A (en) * | 2020-04-07 | 2020-08-14 | 宜春大海龟生命科学有限公司 | Optimization method for esterification reaction of deodorized distillate of vegetable oil |
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