CN102703222B - Method for separating mixed fatty acid by separating wall distillation tower - Google Patents
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Abstract
The invention discloses a method for separating mixed fatty acid by a separating wall distillation tower, belonging to the technical field of oil chemical industry. A vertical wall is arranged inside a conventional distillation tower so as to divide the distillation tower into four areas, wherein an area I is a common rectifying section, an area II is a feeding section, an area III is a lateral discharging section, and an area IV is a common stripping section; a material inlet is formed on the middle part of the area II; a light component outlet is formed on the top of the area I; a first product outlet is formed on the upper part of the area I; a second product outlet is formed on the middle part of the area III; a heavy component outlet is formed at the bottom of the area IV; mixed crude fatty acid is preheated and enters the distillation tower from the area II, and light components are distilled off from the top of the distillation tower; C16 fatty acid fraction with the content of greater than 95% is obtained from the upper part of the common rectifying section I; a second product is taken out from the middle part of the lateral discharging section III; and fatty acids with the number of carbon atoms of more than 20 and impurities are removed from the tower kettle of the separating wall distillation tower. The process is shortened, equipment investment is reduced, the separation efficiency is improved, and energy is saved by more than 10%.
Description
Technical field
The invention belongs to the oil chemical technology field.Be specifically related to a kind of partition wall rectifying tower lipid acid light to containing, heavy constituent impurity that uses and make with extra care the method for purifying.
Background technology
Oil and fat chemical is the chemical industry derived from from natural fats and oils, the history of more than 100 year is arranged, be still to have so far the chemical industry of vitality sustainable development, its basic material---grease is renewable resources, and its chemical deep processed product has good biological degradability.Oil and fat chemical refers to take the animal and plant grease as raw material process physical reaction, the chemical reaction a series of new chemical of generation and derivative, as lipid acid, glycerine, fatty alcohol and soap etc., they are through nearly hundred kinds of the derived products such as the various surfactants that further processing can be made into, all kinds of soap, glycerine, be widely used in the relevant field of national economy, as daily-use chemical industry, articles for washing, fertilizer (perfume (or spice)) soap, plastics, rubber, coating, weaving etc.
The hair plam oil mixes with palm-kernel oil and solves the mixing croude fatty acids through high-temperature high pressure water, or mao plam oil becomes winterized stearin by hydrogenation under the effect of catalyzer, and winterized stearin is hydrolyzed and obtains thick and stiff resin acid.Impurity in croude fatty acids or thick and stiff resin acid is mainly some lower-boiling impurities as light lipid acid, moisture content, ketone, aldehyde, free glycerol etc. and high-boiling-point impurity as high boiling point lipid acid and pigment, glyceryl ester, oxidation of fat acid, unsaponifiables, partially polymerized lipid acid etc.
Croude fatty acids or thick and stiff resin acid that hair plam oil and palm-kernel oil are raw material production.The hair plam oil mixes with palm-kernel oil through high temperature and high pressure hydrolysis gained mixing croude fatty acids, croude fatty acids contains C12-C20 lipid acid, after refining removal light impurities C12, C14 and heavy constituent C20 and above impurity, obtain C16 and C18 lipid acid, wherein C18 lipid acid is oleic acid, linolic acid and stearic mixture.Hair plam oil and palm-kernel oil are under catalyst action, by heating, with hydrogen, in reactor, reacted, grease after filtration is winterized stearin, winterized stearin is after hydrolysis, can obtain thick and stiff resin acid, thick and stiff resin acid contains C12-C20 lipid acid, after refining removal light impurities C12, C14 and heavy constituent C20 and above impurity, obtain C16 and C18 stearic acid, can obtain the stearic acid of different grades by C18 content.
The process for purification adopted now is mainly to adopt rectificating method to be separated, and by two rectifying tower, lower-boiling impurity, high-boiling-point impurity is removed, and this separation method material needs Repeat-heating, and energy consumption is higher.
Summary of the invention
The invention provides the processing method of the refining mixed fatty acid of a kind of partition wall rectifying tower, purpose is again in the above-mentioned shortcoming that overcomes existing installation and technology, provide a kind of lipid acid light to containing, heavy constituent impurity to carry out the technique of rectification and purification, adopt this technique to there is good energy-saving effect, the good product quality obtained.
The objective of the invention is to be achieved through the following technical solutions:
The method of the refining mixed fatty acid of a kind of partition wall rectifying tower, adopt the partition wall rectifying tower, one vertical wall is set in the conventional rectification tower, this vertical wall is divided into four zones by tower, the zone I is public rectifying section, the zone II is feed zone, and regional III is side line extraction section, and regional IV is public stripping section; Material inlet is positioned at regional II middle part, and the light constituent discharge port is arranged at regional I top, promising the 1st outlet for product in regional I top; There is the 2nd outlet for product at III middle part, zone; IV bottom, zone is the heavy constituent discharge port; Mix croude fatty acids and enter in tower from regional II after preheating, light constituent wherein steams from tower top; Obtain from first outlet for product on public rectifying section I top the C16 lipid acid fraction that content is greater than 95%, from tower side line extraction section III middle part extraction the 2nd product, from the tower reactor of partition wall rectifying tower, remove lipid acid and the impurity more than C20.
Wherein said light constituent comprises C12 lipid acid, C14 lipid acid and a small amount of C16 lipid acid fraction.
In wherein said the first product, the massfraction of C18 lipid acid is more than 80%, and all the other are C16 lipid acid.
In wherein said partition wall rectifying tower, the length of vertical wall is determined according to actual tower height and processing system, generally, the 30%-60% that wherein said height is the tower body total height, the partition wall rectifying tower can be packing tower, can be also tray column.
Wherein said partition wall rectifying tower has 20-50 piece theoretical stage, and wherein public rectifying tower number of theoretical plate is the 8-10 piece, and the number of theoretical plate of feed zone and side line extraction section is the 6-15 piece, and the number of theoretical plate of public stripping section IV is the 10-15 piece.The number of theoretical plate of preferred partition wall rectifying tower feed zone and side line extraction section is the 10-15 piece,
Raw material is from the charging of partition wall rectifying tower feed zone 3-8 piece plate, and working pressure is 0.002-0.004bar, and reflux ratio can be controlled in 70-120 according to tower top load and product purity.
Advantage of the present invention: with existing conventional distillation tower, compare, the present invention realized equipment integration and energy integrated.When croude fatty acids is separated, by the process simplification that originally at least needs two towers to realize, be only to need a tower just can complete.Therefore shortened technical process, reduced facility investment, improved separation efficiency, can save energy more than 10%.
The accompanying drawing explanation
The dividing wall column process flow diagram that wherein Fig. 1 is separation of fatty acids, wherein: I, public rectifying section; II, feed zone; III, side line extraction section; IV, public stripping section.D, tower top discharging; S, the 1st product discharge; M, side line extraction section the 2nd product discharge; W, tower reactor discharging.
Embodiment
The device that the present invention adopts is the partition wall rectifying tower, and a vertical wall is set in the conventional rectification tower, and this vertical wall is divided into four zones by tower, and regional I is public rectifying section, and regional II is feed zone, and regional III is side line extraction section, and regional IV is public stripping section.
The present invention implements like this: mix croude fatty acids and enter in tower from regional II after preheating, light constituent wherein (C12, C14 and a small amount of C16 fraction) steams from tower top.Obtain from first outlet for product on public rectifying section I top the C16 fraction that content is greater than 95%, from tower side line extraction section III middle part extraction the 2nd product, (the C18 massfraction is more than 80%, all the other are C16 lipid acid), remove lipid acid and the impurity more than C20 from the tower reactor of partition wall rectifying tower.
embodiment 1
The hair plam oil mixes with palm-kernel oil through high temperature and high pressure hydrolysis gained mixing croude fatty acids.Form croude fatty acids 12500kg/h as shown in table 1 and enter the partition wall rectifying tower, partition wall rectifying tower number of theoretical plate is 30, wherein public rectifying tower number of theoretical plate is 8, and the number of theoretical plate of feed zone and side line extraction section is 12, and the number of theoretical plate of public stripping section IV is 10.Working pressure is 0.002bar, and the trim the top of column ratio is controlled at 80.Raw material is from the 5th plate charging of partition wall rectifying tower feed zone, and raw material is the bubble point charging.
Table 1 croude fatty acids composition (massfraction, %)
| Lauric acid | TETRADECONIC ACID | Palmiticacid | Stearic acid | Oleic acid | Linolic acid | Eicosanoic acid | High boiling material |
| 0.65 | 0.65 | 44.2 | 4.5 | 39.1 | 10.1 | 0.6 | 1.7 |
Croude fatty acids is entered from the feed zone II, at feed zone, carry out pre-separation, make light constituent, intermediate component and intermediate component, heavy constituent carry out initial gross separation.Light constituent, intermediate component enter the public rectifying section I of partition wall top to be separated, and intermediate component, heavy constituent enter the public stripping section IV of partition wall below and further separate.From removed overhead light constituent C12(lauric acid), the C14(TETRADECONIC ACID) and a small amount of C16 fraction (Palmiticacid), 173 ℃ of tower top temperatures, tower top discharging D extraction flow is 327kg/h, C12(lauric acid in overhead extraction) massfraction be 8.8%, the C14(TETRADECONIC ACID) massfraction be 4.2%, C16(Palmiticacid) massfraction be 86.2%.Be rich in the cut of C16 from the first discharge port S extraction on public rectifying section I top, the extraction flow is 3774.2 kg/h, wherein C16(Palmiticacid) massfraction be 95.3%, can be directly as product, sell or as the raw material of soapmaking base.Side line extraction section the 2nd outlet for product extraction intermediate component M, the extraction flow is 8300kg/h, component is C16 fraction (Palmiticacid), its massfraction is 19.4%, all the other for massfraction be greater than 80% C18 lipid acid (wherein stearic massfraction be 8%, the massfraction of oleic acid be 57.8% and linoleic massfraction be 14.8%), but hydrogenation obtains high-quality stearic acid or as the raw material of soapmaking base.Remove lipid acid (eicosanoic acid) and the impurity W more than C20 from the tower reactor of partition wall rectifying tower, can be used as plant asphalt.
The energy consumption of novel process is 3652kW, and the energy consumption of former technique is 4338kW, can save energy 15.8%.
embodiment 2
The hair plam oil mixes with palm-kernel oil through high temperature and high pressure hydrolysis gained mixing croude fatty acids.Form croude fatty acids 12500kg/h as shown in table 2 and enter the partition wall rectifying tower, partition wall rectifying tower number of theoretical plate is 30, wherein public rectifying tower number of theoretical plate is 8, and the number of theoretical plate of feed zone and side line extraction section is 12, and the number of theoretical plate of public stripping section IV is 10.Working pressure is 0.004bar, and control of reflux ratio is 85.Raw material is from the 7th plate charging of partition wall rectifying tower feed zone, and raw material is the bubble point charging.
Table 2 croude fatty acids composition (massfraction, %)
| Lauric acid | TETRADECONIC ACID | Palmiticacid | Stearic acid | Oleic acid | Linolic acid | Eicosanoic acid | High boiling material |
| 0.4 | 1.1 | 44.0 | 5.1 | 37.5 | 10.5 | 0.4 | 1.0 |
Croude fatty acids is entered from the feed zone II, at feed zone, carry out pre-separation, make light constituent, intermediate component and intermediate component, heavy constituent carry out initial gross separation.Light constituent, intermediate component enter the public rectifying section I of partition wall top to be separated, and intermediate component, heavy constituent enter the public stripping section IV of partition wall below and further separate.From removed overhead light constituent C12(lauric acid), the C14(TETRADECONIC ACID) and a small amount of C16 fraction (Palmiticacid), 178 ℃ of tower top temperatures, overhead extraction flow D is 320kg/h, C12(lauric acid in overhead extraction) massfraction be 5.5%, the C14(TETRADECONIC ACID) massfraction be 6.7%, C16 fraction (Palmiticacid) massfraction is 87.2%.Be rich in the cut of C16 from the first outlet for product extraction on public rectifying section I top, the extraction flow is 3781kg/h, wherein C16(Palmiticacid) massfraction be 95.1%, can be directly as product, sell or as the raw material of soapmaking base.Side line extraction section the 2nd outlet for product extraction intermediate component M, the extraction flow is 8300kg/h, the massfraction that intermediate component is C16 fraction (Palmiticacid) is 19.6%, all the other for massfraction be greater than 80% C18 lipid acid (wherein stearic massfraction be 7.3%, the massfraction of oleic acid be 57.7% and linoleic massfraction be 15.4%), but hydrogenation obtains high-quality stearic acid or as the raw material of soapmaking base.Remove lipid acid (eicosanoic acid) and the impurity more than C20 from the tower reactor of partition wall rectifying tower, can be used as plant asphalt.
The energy consumption of novel process is 5539kW, and the energy consumption of former technique is 6287kW, can save energy 11.9%.
embodiment 3
The hair plam oil, under catalyst action, is reacted with hydrogen by heating in reactor, and the grease after filtration is winterized stearin, and winterized stearin, after hydrolysis, can obtain thick and stiff resin acid.Thick and stiff resin acid forms as shown in table 3.
The thick and stiff resin acid of table 3 forms
| Lauric acid | TETRADECONIC ACID | Palmiticacid | Stearic acid | Eicosanoic acid | High boiling material |
| 0.65 | 1.35 | 43.1 | 52.5 | 0.8 | 1.6 |
Form thick and stiff resin acid 7500kg/h as shown in table 3 and enter the partition wall rectifying tower, partition wall rectifying tower number of theoretical plate is 30, wherein public rectifying tower number of theoretical plate is 9, and the number of theoretical plate of feed zone and side line extraction section is 12, and the number of theoretical plate of public stripping section IV is 10.Working pressure is 0.002bar, and control of reflux ratio is 57.Raw material is from the 7th plate charging of partition wall rectifying tower feed zone, and raw material is the bubble point charging.
Thick and stiff resin acid is entered from the feed zone II, at feed zone, given separation, make light constituent, intermediate component and intermediate component, heavy constituent carry out initial gross separation.Light constituent, intermediate component enter the public rectifying section I of partition wall top to be separated, and intermediate component, heavy constituent enter the public stripping section IV of partition wall below and further separate.From removed overhead light constituent C12(lauric acid), the C14(TETRADECONIC ACID) and a small amount of C16 fraction (Palmiticacid), 163 ℃ of tower top temperatures, the overhead extraction flow is 240kg/h, C12(lauric acid in overhead extraction) massfraction be 8.1%, the C14(TETRADECONIC ACID) massfraction be 8.3%, C16 fraction (Palmiticacid) massfraction is 83.7%.Be rich in the cut of C16 from the first outlet for product extraction on public rectifying section I top, the extraction flow is 2256.5 kg/h, wherein C16(Palmiticacid) massfraction be 95.1%, can be directly as product, sell or as the raw material of soapmaking base.Side line extraction section the 2nd outlet for product extraction intermediate component M, the extraction flow is 4950kg/h, the massfraction that intermediate component is C16 fraction (Palmiticacid) is 17.9%, C18(stearic acid) massfraction be 80.3%, can obtain high-quality stearic acid.Remove lipid acid (eicosanoic acid) and the impurity more than C20 from the tower reactor of partition wall rectifying tower, can be used as plant asphalt.
The energy consumption of novel process is 3586kW, and the energy consumption of former technique is 4134kW, can save energy 13.3%.
Claims (2)
1. the method for the refining mixed fatty acid of a partition wall rectifying tower, it is characterized in that adopting the partition wall rectifying tower, one vertical wall is set in the conventional rectification tower, this vertical wall is divided into four zones by tower, the zone I is public rectifying section, the zone II is feed zone, and regional III is side line extraction section, and regional IV is public stripping section; Material inlet is positioned at regional II middle part, and the light constituent discharge port is arranged at regional I top, and the first outlet for product is arranged at regional I top; There is the second outlet for product at III middle part, zone; IV bottom, zone is the heavy constituent discharge port; Mix croude fatty acids and enter in tower from regional II after preheating, light constituent wherein steams from tower top; Obtain from first outlet for product on public rectifying section I top the C16 lipid acid fraction that content is greater than 95%, from tower side line extraction section III middle part extraction the second product, from the tower reactor of partition wall rectifying tower, remove lipid acid and the impurity more than C20;
Wherein said light constituent comprises C12 lipid acid, C14 lipid acid and a small amount of C16 lipid acid fraction;
In wherein said the second product, the massfraction of C18 lipid acid is more than 80%, and all the other are C16 lipid acid;
In wherein said partition wall rectifying tower, the height of vertical wall is determined according to actual tower height and processing system, the 30%-60% that described height is the tower body total height, and the partition wall rectifying tower is packing tower or tray column;
Wherein said partition wall rectifying tower has 20-50 piece theoretical stage, and wherein public rectifying tower number of theoretical plate is the 8-10 piece, and the number of theoretical plate of feed zone and side line extraction section is the 6-15 piece, and the number of theoretical plate of public stripping section IV is the 10-15 piece;
Raw material is from the charging of partition wall rectifying tower feed zone 3-8 piece plate, and working pressure is 0.0002-0.0004MPa, and reflux ratio is controlled at 70-120 according to tower top load and product purity.
2. a kind of partition wall rectifying tower according to claim 1 is made with extra care the method for mixed fatty acid, and the number of theoretical plate of wherein said partition wall rectifying tower feed zone and side line extraction section is the 10-15 piece.
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| EP4212226A1 (en) * | 2022-01-17 | 2023-07-19 | Sulzer Management AG | Plant and process for fractionating fatty acid mixtures |
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| CN103396894B (en) * | 2013-08-24 | 2015-02-11 | 陈春林 | Fatty acid rectification separation method |
| CN104946405A (en) * | 2014-03-26 | 2015-09-30 | 如皋市双马化工有限公司 | Technology for improving C18 content of stearic acid |
| CN104311410B (en) * | 2014-10-13 | 2016-02-03 | 南京大学 | A kind of method of continuous treating lipid acid |
| CN106554270A (en) * | 2016-11-04 | 2017-04-05 | 上海化工研究院 | A kind of processing method of monoxone by-product crystalline mother solution |
| WO2018109644A1 (en) * | 2016-12-12 | 2018-06-21 | Sabic Global Technologies B.V. | Process for distillation of fatty acids from palm kern oil for minimum waste |
| CN115043869A (en) * | 2022-06-08 | 2022-09-13 | 宁夏福瑞硅烷材料有限公司 | Method for preparing high-purity vinyl trimethoxy silane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417930A (en) * | 2008-11-28 | 2009-04-29 | 湖南阿斯达生化科技有限公司 | Method and apparatus for separating and purifying ethyl vanillin by decompression and continuous distillation in dividing wall column |
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| JP5620504B2 (en) * | 2009-10-20 | 2014-11-05 | ダウ グローバル テクノロジーズ エルエルシー | Downstream recovery of nitroalkanes using a dividing wall column |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101417930A (en) * | 2008-11-28 | 2009-04-29 | 湖南阿斯达生化科技有限公司 | Method and apparatus for separating and purifying ethyl vanillin by decompression and continuous distillation in dividing wall column |
Non-Patent Citations (2)
| Title |
|---|
| 王永福.脂肪酸分离技术的研究进展.《日用化学工业》.2002,第32卷(第3期),58-60. |
| 脂肪酸分离技术的研究进展;王永福;《日用化学工业》;20020630;第32卷(第3期);58-60 * |
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| EP4212226A1 (en) * | 2022-01-17 | 2023-07-19 | Sulzer Management AG | Plant and process for fractionating fatty acid mixtures |
| WO2023135304A1 (en) * | 2022-01-17 | 2023-07-20 | Sulzer Management Ag | Plant and process for fractionating fatty acid mixtures |
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