CN102628007A - Method for producing low carbonyl value fatty alcohol by using high acid value oil - Google Patents
Method for producing low carbonyl value fatty alcohol by using high acid value oil Download PDFInfo
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- CN102628007A CN102628007A CN2012101208313A CN201210120831A CN102628007A CN 102628007 A CN102628007 A CN 102628007A CN 2012101208313 A CN2012101208313 A CN 2012101208313A CN 201210120831 A CN201210120831 A CN 201210120831A CN 102628007 A CN102628007 A CN 102628007A
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Abstract
The invention discloses a method for producing low carbonyl value fatty alcohol by using high acid value oil. The high acid value oil and methanol undergo an esterification reaction at the temperature of 100 DEG C to 130 DEG C, methanol is added again, and an alcoholysis reaction is carried out at the temperature of 68 DEG C to 76 DEG C to obtain crude fatty acid methyl ester; fatty alcohol is obtained after the crude fatty acid methyl ester undergoes ester distillation, hydrogenation and alcohol distillation; and the fatty alcohol passes through a decarbonylation value fixed bed reactor, wherein the reaction temperature is controlled at 70 DEG C to 90 DEG C and the ratio of circulation amount and discharging amount is 3:1 to 5:1, and products are obtained after discharging. The method of the invention overcomes problems that acid value of the esterification reaction is hard to decrease when the high acid value oil is used as an alternative raw material in production of fatty alcohol, yield of the fatty acid methyl ester is effected, the products have high content of carbonyl and odour and the like, providing a practical method for producing the low carbonyl value fatty alcohol by using the high acid value oil, improving quality of products and significantly reducing production cost.
Description
Technical field
The present invention relates to a kind of working method of Fatty Alcohol(C12-C14 and C12-C18), particularly a kind of method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production.
Background technology
At present natural fatty alcohol is a main raw material with natural fats and oils, lipid acid etc. usually, produce through operations such as esterification, alcoholysis, hydrogenation, rectifying, and these greases is mainly from import, and cost is higher.
The high-acid value grease that comprises acidifying oil from Oleum Cocois, palm-kernel wet goods oil and fat refining after lingering section through hydrolysis or saponification acidification gained, contain lipid acid and part neutral grease, thereby acid number is higher, but price is lower.
Because the high-acid value grease impurities is more; Therefore general during with the acid catalyst esterification time longer, and the esterification terminal point is difficult to reach the requirement of low acid number, general acid number reach reduce again about 3mgKOH/g just very difficult; And the high material of esterification endpoint acid number can generate soap with alkaline catalysts in follow-up alcoholysis process; The soap that generates can make emulsifying materials, and glycerine separates bad, can influence the yield of intermediate product fatty acid methyl ester.
Can receive certain influence, particularly finished product on the Fatty Alcohol(C12-C14 and C12-C18) quality with high-acid value grease production and have problems such as the higher and smell of carbonyl content, go the equipment of carbonyl content can not accurately control the residual quantity of carbonyl in the existing Fatty Alcohol(C12-C14 and C12-C18) equipment.
When using higher behenic acid carburetion of iodine number or oleic acid carburetion, the alkane of the Fatty Alcohol(C12-C14 and C12-C18) of being produced and iodine number content are higher, and final product quality receives very big influence.Mainly be on fatty acid methyl ester hydrogenation system alcohol and the carbochain double-bond hydrogenation saturated all be thermopositive reaction; Fatty acid methyl ester has focus to exist when fixed bed hydrogenation reacts; Generally more than 20 ℃, the degree of unsaturation of fatty acid methyl ester is high more in its temperature rise, also is that iodine number is high more; Its temperature rise is big more, and the iodine number of soya oil acid methyl ester or cotton oil acid methyl esters is up to 100gI
2More than/the 100g.Its temperature rise can reach more than 40 ℃.Focus is to make by product alkane increase in the Fatty Alcohol(C12-C14 and C12-C18) to the harm of producing, and catalyzer is prone to coking, and catalyzer quickens to lose activity.Because raw fatty acid methyl esters iodine number is high, the Fatty Alcohol(C12-C14 and C12-C18) iodine number is also corresponding to be increased, very big to the final product quality influence, is difficult to satisfy Fatty Alcohol(C12-C14 and C12-C18) client's request for utilization.
Can be used for substituting the production Fatty Alcohol(C12-C14 and C12-C18) though this shows high-acid value grease, reduce cost,, bring a lot of difficult problems, still be difficult to solve to technical study and actual production owing to there are numerous shortcomings.
Summary of the invention
Goal of the invention: to the problems referred to above, the purpose of this invention is to provide a kind of working method that can access high quality finished product Fatty Alcohol(C12-C14 and C12-C18), utilize high-acid value grease production to hang down carbonyl value Fatty Alcohol(C12-C14 and C12-C18).
Technical scheme: a kind of method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production, this method may further comprise the steps:
((1) esterification, alcoholysis: high-acid value grease is carried out esterification at 100 ℃～130 ℃ with methyl alcohol, and then add methyl alcohol and carry out alcoholysis reaction, obtain crude fatty acid methyl ester at 68 ℃～76 ℃;
(2) above-mentioned crude fatty acid methyl ester is carried out ester rectifying, hydrogenation, pure rectification process, obtains Fatty Alcohol(C12-C14 and C12-C18);
(3) above-mentioned Fatty Alcohol(C12-C14 and C12-C18) is through decarbonylation value fixed-bed reactor, and 70 ℃～90 ℃ of control reaction temperature, internal circulating load and load were than 3: 1～5: 1, and discharging is finished product.
The methanol vapor phase of esterification adds, and promptly methyl alcohol is after the volume pump pressurization, and pump is to the methyl alcohol vaporizer, and the methyl alcohol after the vaporization is delivered to the methyl alcohol sparger of reaction kettle bottom, gets into reaction kettle again.Gas-phase methanol contacts more full and uniform in reaction kettle with material, and gas-phase methanol remains high density, therefore; Esterification is more abundant fierce; Speed of response is accelerated, and esterification time shortens a lot, and the high-acid value grease esterification time can shorten more than the half the time; Can drop to below the 1.2mgKOH/g to reacting 3～5 hours esterification endpoint acid number, alcoholysis reaction fatty acid methyl ester yield can improve more than 2%.
The methyl alcohol normal temperature liquid phase of alcoholysis reaction directly adds, and plays the effect to the reaction system cooling in the time of as reactant again, need not in addition with heat-exchange equipment and material cooling.
Esterification and alcoholysis reaction are carried out in same reaction kettle, reduce discharging cooling, charging TRT, enhance productivity, and make therefore after the esterification before the alcoholysis that cooling can enough liquid methanol coolings, have reduced energy consumption.
Decarbonylation base fixed-bed reactor can remove a small amount of carbonyl and the smell that exists in the Fatty Alcohol(C12-C14 and C12-C18); Because the reagent price that the decarbonylation base is consumed is higher; So the employing fixed-bed reactor are controlled the decarbonylation base unit weight through temperature and internal circulating load, can control the carbonyl value and can control the consumption of decarbonylation base reagent again.
When the high-acid value grease that adopts high iodine number during as raw material production, carry out pre-hydrogenation before the hydrogenation in the step (2), catalyzer is a copper-nickel catalyst; 140 ℃～150 ℃ of reacting initial temperatures; 180 ℃～220 ℃ of reaction end temperature, reaction pressure 2.0Mpa～5.0Mpa, 2～5 hours reaction times.The high-acid value grease of high iodine number is produced Fatty Alcohol(C12-C14 and C12-C18), wherein between the iodine number of product fatty acid methyl ester usually greater than 100gI
2In hydrogenation reaction kettle, carry out the pre-hydrogenation reaction before the/100g, hydrogenation earlier,, the iodine number of fatty acid methyl ester is reduced to less than 30gI being lower than under hydrogenation system alcohol temperature of reaction and the reaction pressure condition
2/ 100g, the fatty acid methyl ester of this moment temperature rise in fixed bed hydrogenation system alcohol process can not make hydrogenation byproduct alkane increase in normal range, and the iodine number of product also can be reduced to normal range, and makes catalyzer that the normal life-span arranged.
Beneficial effect: compared with prior art; Advantage of the present invention be overcome high-acid value grease produce as alternative materials in the Fatty Alcohol(C12-C14 and C12-C18) process esterification acid number reduce difficult, influence the fatty acid methyl ester yield, the finished product carbonyl content is higher and problem such as smell; For the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production provides effective method; Improve the quality of products, significantly reduce production costs.
Embodiment
Below in conjunction with specific embodiment; Further illustrate the present invention; Should understand these embodiment only be used to the present invention is described and be not used in the restriction scope of the present invention; After having read the present invention, those skilled in the art all fall within the application's accompanying claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
Embodiment 1: at 10m
3Reaction kettle in drop into acidifying oil 5500kg; Drop into acid catalyst with the methyl alcohol quantitative configuration, heat temperature raising near temperature of reaction the time, with methyl alcohol after the volume pump metering is pressurizeed; Pump is to the methyl alcohol vaporizer; Methyl alcohol after the vaporization is delivered to the methyl alcohol sparger of reaction kettle bottom, carries out esterification with gas phase entering reaction kettle and material, and the water of unreacted methanol and reaction generation gets into methanol recovery system after steaming simultaneously and getting into condenser condenses.120 ℃ of esterification controlled temperature, 3.5 hours reaction times is behind mensuration acid number≤1.2mgKOH/g; Add quantitative normal temperature liquid phase methyl alcohol material is cooled to 68 ℃; Drop into the alkaline catalysts that configures with methyl alcohol in advance, reheat makes neutral grease and methyl alcohol in the material carry out alcoholysis reaction; Temperature of reaction is controlled at 70 ℃, 1 hour reaction times.The crude fatty acid methyl ester that obtains after the alcoholysis is carried out rectifying, obtains smart fatty acid methyl ester, and smart fatty acid methyl ester carries out hydrogenation reaction and obtains Fatty Alcohol(C12-C14 and C12-C18); The volume ratio of hydrogen and smart fatty acid methyl ester is 13000: 1,205 ℃ of temperature, pressure 22MPa; And then rectification and purification; Get into decarbonylation base fixed-bed reactor then, 85 ℃ of control reaction temperature, internal circulating load and load be than 4.5:1, and the carbonyl value of the Fatty Alcohol(C12-C14 and C12-C18) product that obtains is≤30ppm.
It is different that methyl alcohol adds state during below through esterification; Be that general esterification and methanol vapor phase of the present invention adding esterification compares; In reaction kettle, carry out the esterification alcoholysis reaction with high-acid value grease equally, carry out rectification and purification again, 120 ℃ of esterification reaction temperatures; 70 ℃ of alcoholysis reaction temperature, the gained result is following:
This shows that the esterification methanol vapor phase adds when producing Fatty Alcohol(C12-C14 and C12-C18) with high-acid value grease, under same reaction time, material ratio, temperature of reaction situation, the esterification endpoint acid number significantly reduces, and the fatty acid methyl ester yield obviously improves after the alcoholysis; Under, the same reaction temperature situation few in the gas-phase methanol usage quantity, esterification time but obviously shortens, and the esterification endpoint acid number significantly reduces, and the fatty acid methyl ester yield obviously improves after the alcoholysis.
Embodiment 2: basic identical with embodiment 1, difference is: raw materials for production are the behenic acid carburetion or the oleic acid carburetion of high iodine number, after crude fatty acid methyl ester is carried out ester rectifying; Sucked in the hydrogenation still by vacuum; Vacuum hydro-extraction to 110 under agitation ℃ drops into copper-nickel catalyst, after air displacement in the hydrogenation still; Feed hydrogen to still internal pressure 3.0Mpa, stop to heat after being heated to 150 ℃ of still temperature simultaneously.Along with the carrying out of reaction, after rising to 200 ℃, the still temperature no longer rises, and heat-insulation pressure keeping was lowered the temperature after 30 minutes, shed the still internal pressure, opened a small amount of overbottom pressure of bleeder valve utilization with the material press filtration, proceeded subsequent steps such as hydrogenation again.
Claims (5)
1. method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production is characterized in that this method may further comprise the steps:
(1) esterification, alcoholysis: high-acid value grease is carried out esterification at 100 ℃～130 ℃ with methyl alcohol, and then add methyl alcohol and carry out alcoholysis reaction, obtain crude fatty acid methyl ester at 68 ℃～76 ℃;
(2) above-mentioned crude fatty acid methyl ester is carried out ester rectifying, hydrogenation, pure rectification process, obtains Fatty Alcohol(C12-C14 and C12-C18);
(3) above-mentioned Fatty Alcohol(C12-C14 and C12-C18) is through decarbonylation value fixed-bed reactor, and 70 ℃～90 ℃ of control reaction temperature, internal circulating load and load were than 3: 1～5: 1, and discharging is finished product.
2. a kind of method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production according to claim 1; It is characterized in that: the methanol vapor phase of esterification adds; Be that methyl alcohol is after the volume pump pressurization; Pump is to the methyl alcohol vaporizer, and the methyl alcohol after the vaporization is delivered to the methyl alcohol sparger of reaction kettle bottom, gets into reaction kettle again.
3. a kind of method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production according to claim 1, it is characterized in that: the methyl alcohol normal temperature liquid phase of alcoholysis reaction directly adds.
4. a kind of method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production according to claim 1, it is characterized in that: esterification and alcoholysis reaction are carried out in same reaction kettle.
5. a kind of method of utilizing the low carbonyl value Fatty Alcohol(C12-C14 and C12-C18) of high-acid value grease production according to claim 1; It is characterized in that: when the high-acid value grease that adopts high iodine number during as raw material production, carry out pre-hydrogenation before the hydrogenation in the step (2), catalyzer is a copper-nickel catalyst; 140 ℃～150 ℃ of reacting initial temperatures; 180 ℃～220 ℃ of reaction end temperature, reaction pressure 2.0Mpa～5.0Mpa, 2～5 hours reaction times.
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| CN2012101208313A CN102628007A (en) | 2012-04-24 | 2012-04-24 | Method for producing low carbonyl value fatty alcohol by using high acid value oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106398875A (en) * | 2016-11-11 | 2017-02-15 | 禄丰云瑞油脂科技有限公司 | Method for producing stearic acid by using swill-cooked dirty oil |
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| CN106398875A (en) * | 2016-11-11 | 2017-02-15 | 禄丰云瑞油脂科技有限公司 | Method for producing stearic acid by using swill-cooked dirty oil |
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Application publication date: 20120808 |