CN102796620B - Fixed bed-based continuous catalytic esterification production method - Google Patents
Fixed bed-based continuous catalytic esterification production method Download PDFInfo
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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
Take oil from high acid value waste animal and plant fat as the raw material production fatty acid methyl ester---biofuel and take DD oil (deodorization distillate) in raw material production natural VE process, free fatty acids in raw material need be converted into to fatty acid methyl ester or ethyl ester with methyl alcohol or ethanol synthesis under an acidic catalyst effect, this acidic catalyst of manufacturing enterprise relates generally to liquid acid at present---the vitriol oil and highly acidic resin.Domestic literature and Patents are about more with these two catalyst esterification techniques reports, relative merits separately being arranged: liquid acid---it is high that catalytic esterification technology that the vitriol oil is made catalyzer has catalytic activity, can once acid value be dropped to below 3mgKOH/g, but equipment is had to very strong corrosion, produce a large amount of waste water, and there is side reaction to produce, batch production, labour intensity is larger; The fixed-bed catalytic esterification techniques that the highly acidic resin of take is filler is realized producing continuously, side reaction is few, non-wastewater discharge, corrosion-free to equipment, but catalytic activity is low, and need to carry out the secondary esterification could drop to acid value below 3mgKOH/g, the methyl alcohol usage quantity is large, resin causes the resin activity decreased because the impurity such as adsorpting pigment stop up the resin duct after operation for some time simultaneously, need to carry out activating and regenerating to resin, thereby increase production stage.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the 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, described 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) mixed liquor step (1) obtained for the ratio of 1:0.00025-0.0025 in mass ratio mixes with acid and is heated to 50-100 ℃, then carry out esterification by the fixed bed that highly acidic resin is housed, 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 processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 7-8;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining lipid acid low-carbon-ester.
Described lower alcohol is methyl alcohol or ethanol.
Described acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or Phenylsulfonic acid.
The model of described highly acidic resin is: D061, NKC-9, HD-8, D002, D006,005CR, CAT601, C005 or CAT600.
Described alkali lye is the potassium hydroxide aqueous solution that the mass concentration aqueous sodium hydroxide solution that is 10%-30% or mass concentration are 10%-30%.
The present invention improves the fixed-bed catalytic esterification techniques, both overcome equipment corrosion that liquid acid brings and the shortcoming of large amount of sewage discharge, overcome again the solvent usage quantity that single fixed-bed catalytic technology brings large, need to 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 illustrated.
Embodiment 1
A kind of fixed bed continuous catalysis esterification production method, comprise the steps:
(1) be in mass ratio the ratio of 1:0.8 by raw material and quality percentage composition in the methanol mixed more than 99.5%, described raw material is for removing impurity, the deodorization distillate that the quality percentage composition of moisture is 78.2mgKOH/g in the acid value below 0.05%;
(2) mixed liquor for the ratio of 1:0.001, step (1) obtained in mass ratio mixes with sulfuric acid and is heated to 80 ℃, then carry out esterification by the fixed bed that D061 type highly acidic resin is housed, flow rate control is at 0.5 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 7, alkali lye is the aqueous sodium hydroxide solution that mass concentration is 20%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty acid methyl ester.Acid value is 1.8mgKOH/g.
Embodiment 2
A kind of fixed bed continuous catalysis esterification production method, comprise the steps:
(1) be in mass ratio the ratio of 1:0.5 by raw material and quality percentage composition in the methanol mixed more than 99.5%, described raw material is for removing impurity, the deodorization distillate that the quality percentage composition of moisture is 85.4mgKOH/g in the acid value below 0.1%;
(2) mixed liquor and mixed in hydrochloric acid step (1) obtained for the ratio of 1:0.002 in mass ratio also is heated to 90 ℃, then carry out esterification by the fixed bed that NKC-9 type highly acidic resin is housed, flow rate control is at 0.4 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 8, alkali lye is the aqueous sodium hydroxide solution that mass concentration is 30%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty acid methyl ester.Acid value is 2.1mgKOH/g.
Embodiment 3
A kind of fixed bed continuous catalysis esterification production method, comprise the steps:
(1) be in mass ratio the ratio of 1:0.1 by raw material and quality percentage composition in the methanol mixed more than 99.5%, described raw material is for removing impurity, the swill oil that the quality percentage composition of moisture is 15.3mgKOH/g in the acid value below 0.3%;
(2) mixed liquor for the ratio of 1:0.0025, step (1) obtained in mass ratio mixes with nitric acid and is heated to 70 ℃, then carry out esterification by the fixed bed that HD-8 type highly acidic resin is housed, flow rate control is at 0.6 times of resin volume per hour, and pressure-controlling is at 0.15MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 7, alkali lye is the aqueous sodium hydroxide solution that mass concentration is 10%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty acid methyl ester.Acid value is 0.9mgKOH/g.
Embodiment 4
A kind of fixed bed continuous catalysis esterification production method, comprise the steps:
(1) be in mass ratio the ratio of 1:0.3 by raw material and quality percentage composition in the methanol mixed more than 99.5%, described raw material is for removing impurity, the deodorization distillate that the quality percentage composition of moisture is 65.1mgKOH/g in the acid value below 0.5%;
(2) mixed liquor for the ratio of 1:0.00025, step (1) obtained in mass ratio mixes with phosphoric acid and is heated to 100 ℃, then carry out esterification by the fixed bed that D002 type highly acidic resin is housed, flow rate control is at 0.1 times of resin volume per hour, and pressure-controlling is at 0.05MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 8, alkali lye is the aqueous sodium hydroxide solution that mass concentration is 30%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty acid methyl ester.Acid value is 1.9mgKOH/g.
Embodiment 5
A kind of fixed bed continuous catalysis esterification production method, comprise the steps:
(1) be in mass ratio the ratio of 1:0.4 by raw material and quality percentage composition in the methanol mixed more than 99.5%, described raw material is for removing impurity, the swill oil that the quality percentage composition of moisture is 11.5mgKOH/g in the acid value below 0.05%
(2) mixed liquor for the ratio of 1:0.0004, step (1) obtained in mass ratio mixes with Phenylsulfonic acid and is heated to 50 ℃, then carry out esterification by the fixed bed that D006 type highly acidic resin is housed, flow rate control is at 1 times of resin volume per hour, and pressure-controlling is at 0.2MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 7, alkali lye is the potassium hydroxide aqueous solution that mass concentration is 20%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty acid methyl ester.Acid value is 0.6mgKOH/g.
Embodiment 6
A kind of fixed bed continuous catalysis esterification production method, comprise 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, described raw material is for removing impurity, the acidification oil that the quality percentage composition of moisture is 110.1mgKOH/g in the acid value below 0.1%;
(2) mixed liquor for the ratio of 1:0.0006, step (1) obtained in mass ratio mixes with sulfuric acid and is heated to 60 ℃, then carry out esterification by the fixed bed that 005CR type highly acidic resin is housed, flow rate control is at 0.5 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 8, alkali lye is the potassium hydroxide aqueous solution that mass concentration is 30%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty-acid ethyl ester.Acid value is 2.4mgKOH/g.
Embodiment 7
A kind of fixed bed continuous catalysis esterification production method, comprise 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, described raw material is for removing impurity, the deodorization distillate that the quality percentage composition of moisture is 100.5mgKOH/g in the acid value below 0.3%;
(2) mixed liquor and mixed in hydrochloric acid step (1) obtained for the ratio of 1:0.0008 in mass ratio also is heated to 70 ℃, then carry out esterification by the fixed bed that CAT601 type (also can adopt the CAT600 type) strongly-acid CAT601 resin is housed, flow rate control is at 0.5 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 7, alkali lye is the potassium hydroxide aqueous solution that mass concentration is 10%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty-acid ethyl ester.Acid value is 2.3mgKOH/g.
Embodiment 8
A kind of fixed bed continuous catalysis esterification production method, comprise 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, described raw material is for removing impurity, the acidification oil that the quality percentage composition of moisture is 120.6mgKOH/g in the acid value below 0.5%;
(2) mixed liquor for the ratio of 1:0.001, step (1) obtained in mass ratio mixes with nitric acid and is heated to 80 ℃, then carry out esterification by the fixed bed that C005 type highly acidic resin is housed, flow rate control is at 0.4 times of resin volume per hour, and pressure-controlling is at 0.1MPa;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 8, alkali lye is the potassium hydroxide aqueous solution that mass concentration is 20%;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty-acid ethyl ester.Acid value is 2.6mgKOH/g.
Claims (3)
1. a fixed bed continuous catalysis esterification production method, is characterized in that comprising the steps:
(1) be in mass ratio the ratio of 1:0.1-1 by raw material and quality percentage composition in the methanol mixed more than 99.5%, described raw material is for removing impurity, the quality percentage composition of moisture is at oil from high acid value waste animal and plant fat or deodorization distillate below 0.5%;
(2) mixed liquor step (1) obtained for the ratio of 1:0.00025-0.0025 in mass ratio mixes with acid and is heated to 50-100 ℃, then carry out esterification by the fixed bed that highly acidic resin is housed, flow rate control is at 0.1-1 times of resin volume per hour, and pressure-controlling is at 0.05-0.2MPa; The model of described highly acidic resin is: D061, NKC-9, HD-8, D002, D006,005CR, CAT601, C005 or CAT600;
(3) solution of processing through step (2) is neutralized online with alkali lye, make the pH value be controlled at 7-8;
(4) the de-alcohol and water of feed liquid decompression to processing through step (3), making moisture controlled is below 0.1% at the quality percentage composition;
(5) the feed liquid underpressure distillation of processing through step (4) is obtained to refining fatty acid methyl ester.
2. a kind of fixed bed continuous catalysis esterification production method according to claim 1, is characterized in that described acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or Phenylsulfonic acid.
3. a kind of fixed bed continuous catalysis esterification production method according to claim 1, is characterized in that described alkali lye is the potassium hydroxide aqueous solution that the mass concentration aqueous sodium hydroxide solution that is 10%-30% or mass concentration are 10%-30%.
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