CN103980090B - The production method of natural fatty alcohol - Google Patents
The production method of natural fatty alcohol Download PDFInfo
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- CN103980090B CN103980090B CN201410228689.3A CN201410228689A CN103980090B CN 103980090 B CN103980090 B CN 103980090B CN 201410228689 A CN201410228689 A CN 201410228689A CN 103980090 B CN103980090 B CN 103980090B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Abstract
A production method for natural fatty alcohol, comprises purified lipase fatty acid glyceride; By the fatty acid methyl ester of generation by the reactor I and the reactor II that enter two-stage series connection after carbon chain lengths fractionation successively; Hydrogenation products is passed into vaporizer separating methanol; Eventually pass rectification under vacuum and obtain finished product, its technical essential is: the feed hydrogen oil ratio of described reactor I is 5800 ~ 6500, reaction pressure 24.5 ~ 25.5MPa, feed preheat temperature is 200 ~ 202 DEG C, the empty tower gas velocity of reactor I is 0.055 ~ 0.061m/s, the upper temp of reactor I 203 ~ 205 DEG C, middle portion temperature 215 ~ 220 DEG C, temperature of lower is at 216 ~ 225 DEG C; Reaction pressure 24.5 ~ the 25.5MPa of reactor II, empty tower gas velocity is 0.079 ~ 0.092m/s, the upper temp of reactor II 205 ~ 210 DEG C, middle portion temperature 208 ~ 215 DEG C, temperature of lower is at 210 ~ 220 DEG C; The aspect ratio of reactor I is 12 ~ 13; The aspect ratio of reactor II is 14 ~ 15, and reactor I is 1.3 ~ 1.5 with the useful volume ratio of reactor II.The problem such as solve existing production technique production capacity and yield is low, production cost is high, mass space velocity is low.There is the advantage such as hypotoxicity, high yield.
Description
Technical field
The present invention relates to a kind of production method of Long-chain primary alcohols, particularly a kind of production method of natural fatty alcohol.Be take fatty acid methyl ester as raw material specifically, adopt fixed bed hydrogenation technique to prepare the method for fatty alcohol.
Background technology
Natural fatty alcohol mainly refers to the primary alconol of more than six carbon atom, it is the basic material producing the fine chemical products such as softening agent, washing composition and tensio-active agent, is widely used in the fields such as chemical industry, oil, metallurgy, weaving, machinery, mining, building, leather, papermaking, food, medicine, health, daily-use chemical industry.Application prospect is quite wide, and domestic and international market demand also increases year by year.In existing technique, the production method of natural fatty alcohol mainly comprises: fatty acid methyl ester hydrogenation method, oxo synthesis, Ziegler alcohol method and oxidized petroleum wax synthesis secondary alcohol method etc.
Wherein, fatty acid methyl ester hydrogenation method because its process controllability is strong, pollute low and be widely used.The reaction equation of this reaction is:
.This reaction is thermopositive reaction, raw fatty acid methyl esters is in a liquid state, shortening equipment is a Solid Bed adiabatic reactor, the temperature of reactor is not controlled by steam tracing or water of condensation, thus cannot discharge reacting the heat discharged in time, cause the temperature of restive reactor, a series of side reaction can be produced, as generated alkane, cyclic polymer etc.Cause that productive rate reduces, security cannot ensure.For this reason, the method for a kind of preparing fatty alcohol through fixed bed hydrogenation by using fatty acid methyl ester disclosed in CN101633602A had once been invented.The method is mainly the methyl alcohol adding a certain proportion of purity >=99.8wt% at the feed end of interchanger, utilize methyl alcohol emission and absorption reaction heat during the course, make fixed-bed catalytic hydrogenation reaction actuator temperature keep relative constancy, thus decrease the generation of side reaction.
Although the method overcome the shortcoming that adiabatic reactor can not carry out thermal exchange, increase the amount of methyl alcohol in reaction product, will certainly cause reacting counter movement, inhibit the output of fatty alcohol, cause productive rate to reduce.Adds additional the methyl alcohol of purity >=99.8wt%, not only increase production cost, and cause methanol content in workshop air to raise, have a strong impact on the healthy of staff.In addition, in reaction product, methanol content raises, and finished product separation costs can be caused again to raise.Visible, although the method effectively reduces the generation of side reaction, there is shortcomings, cannot the needs of practical in production.For this reason, contriver improves original technique, to overcome above-mentioned defect.
Summary of the invention
The object of this invention is to provide a kind of production method of natural fatty alcohol, the problem such as fundamentally solve existing production technique production capacity and yield is low, production cost is high, reactor mass space velocity is low.It, by adjustment catalyst levels, adopts two reactors with different aspect ratio, has the advantage such as hypotoxicity, high yield.
The technical solution adopted in the present invention is: the production method of this natural fatty alcohol, comprises purified lipase fatty acid glyceride; After alcoholysis by the fatty acid methyl ester of generation by the reactor I and the reactor II that enter two-stage series connection after carbon chain lengths fractionation successively; Hydrogenation products is passed into vaporizer separating methanol; Eventually pass rectification under vacuum and obtain finished product, its technical essential is: the feed hydrogen oil ratio of described reactor I is 5800 ~ 6500, reaction pressure 24.5 ~ 25.5MPa, feed preheat temperature is 200 ~ 202 DEG C, the empty tower gas velocity of reactor I is 0.055 ~ 0.061m/s, the upper temp of reactor I 203 ~ 205 DEG C, middle portion temperature 215 ~ 220 DEG C, temperature of lower is at 216 ~ 225 DEG C; Reaction pressure 24.5 ~ the 25.5MPa of reactor II, empty tower gas velocity is 0.079 ~ 0.092m/s, the upper temp of reactor II 205 ~ 210 DEG C, middle portion temperature 208 ~ 215 DEG C, temperature of lower is at 210 ~ 220 DEG C; The aspect ratio of reactor I is 12 ~ 13; The aspect ratio of reactor II is 14 ~ 15, and reactor I is 1.3 ~ 1.5 with the useful volume ratio of reactor II.
The advantage that the present invention has and positive technique effect are: original Henkel technique adopt two-stage series connection etc. large hydrogenator, restrict by beds vertex temperature, cannot improve reactor mass space velocity, and the catalyzer overwhelming majority in reactor II is wasted.Production method of the present invention is by the aspect ratio of adjustment reactor, operating space is left to the raising of mass space velocity, even if improve reactor mass space velocity, also side reaction will be caused to aggravate because reaction bed temperature is too high, therefore effectively improve the effective rate of utilization of catalyzer, improve production capacity, and it is too fast to avoid beds local heating, the temperature distribution in two-stage reactor is more reasonable.When same production capacity, catalyzer single batch of consumption at least can reduce 17.65wt%, and byproduct growing amount at least reduces 0.12wt%, and hydrogenated products RH value drops to 0.67 ~ 0.88% by 0.79 ~ 1.0%.In addition, production method of the present invention, without the need to adding high purity methanol in the feed, thus avoid that production capacity is low, yield is low, the problem such as methanol concentration rising in environment.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described.
Fig. 1 is process flow diagram of the present invention.
In figure, sequence number illustrates: 1 high-pressure pump, 2 interchanger, 3 preheaters, 4 reactor I, 5 reactor II, 6 water coolers, 7 separators, 8 recycle pumps, A fatty acid methyl ester, B1 recycle hydrogen, the new hydrogen of B2, C hydrogenated products mixture.
Embodiment
Content of the present invention is described in detail according to Fig. 1.The present invention is directed to the Henkel technique of original Henkel technique and raw material plus methanol for contrast, be described in detail.The technique of Henkel explained hereafter natural fatty alcohol mainly comprises the steps such as clarifying grease, high-pressure alcoholysis, alcoholysis product separation, fatty acid methyl ester rectifying, fatty acid methyl ester high-pressure hydrogenation, hydrogenated products separation, fatty alcohol rectifying.Wherein, high-pressure alcoholysis and fatty acid methyl ester hydrogenation step are the cores of Henkel technique, directly affect finished product yield and quality product, glycerin fatty acid ester is changed into fatty acid methyl ester by high-pressure alcoholysis, fatty acid methyl ester generates fatty alcohol after high-pressure hydrogenation, all the other steps are physical sepn, purification process, and above content belongs to known technology field and discusses no longer in detail.
In Henkel technique, two useful volumes are adopted to be 12m
3the reactor (namely the reactor in the present invention refers to adiabatic hydrogenator) of the same specification of (aspect ratio is 16.33), but find in production practice, fatty acid methyl ester hydrogenation reaction mainly concentrates on reactor I, the positive effect that reactor II plays is less, and be thermopositive reaction because fatty acid methyl ester hydrogenation reacts, the heat that major part methyl esters produces after reactor I completes reaction can be taken in reactor II by material and circulating hydrogen, the beds of reactor II and material are after the reaction heat obtaining autoreactor I, again react, when reaction mass flow velocity is certain, heat dissipation capacity is certain, namely the accumulation of heat can be caused, reactor II temperature is forced sharply to raise, thus initiation alkane, the generation of the side reactions such as cyclic polymer.Namely product fatty alcohol continues the alkane that the generation of generation hydrogenation reaction is difficult to be separated, and then affects product yield and quality.For avoiding above-mentioned situation to occur, usual method reduces inlet amount or catalyst levels or adds methyl alcohol in the feed.Those skilled in the art still can obtain the hydrogenated products of high-yield high-quality after can not expecting improving inlet amount.
For this phenomenon, by adjustment reactor aspect ratio and then the empty tower gas velocity affecting reactor, hydrogenation reaction is more concentrated on reactor I, through a large amount of Practical adjustments by final realization, finally determine best reactor aspect ratio and input speed, productive rate is significantly improved.The aspect ratio of reactor I is 12 ~ 13; The aspect ratio of reactor II is 14 ~ 15, and reactor I is 1.3 ~ 1.5 with the useful volume ratio of reactor II.Reactor II comparatively reactor I compares, and aspect ratio is larger, and empty tower gas velocity is faster, material flow is faster in production process, reaction heat is more easily taken out of, therefore empty tower gas velocity is faster, and the empty tower gas velocity of reactor I is 0.055 ~ 0.061m/s, and the empty tower gas velocity of reactor II is 0.079 ~ 0.092m/s.The feed hydrogen oil ratio of reactor I is 5800 ~ 6500, and feed preheat temperature is 200 ~ 202 DEG C, and the reaction pressure of reactor I and reactor II is 24.5 ~ 25.5MPa.
Under the restriction of above-mentioned condition, the top of reactor I, middle part, temperature of lower can be each defined in 203 ~ 205 DEG C, 215 ~ 220 DEG C, 216 ~ 225 DEG C; The top of reactor II, middle part, temperature of lower are each defined in 205 ~ 210 DEG C, 208 ~ 215 DEG C, 210 ~ 220 DEG C.Reactor I and reactor II is closed thermally insulated container, therefore cannot be reached the object of temperature control by other approach.
To produce C
12-14fatty alcohol is example, and this technique relates generally to the equipment such as high-pressure pump 1, interchanger 2, preheater 3, reactor I4, reactor II5, water cooler 6, separator 7, recycle pump 8.Fatty acid methyl ester A is preheated to 200 ~ 202 DEG C successively after high-pressure pump 1 is pressurizeed after interchanger 2 and preheater 3, then reactor I and the reactor II of hydrogen atmosphere is passed into hydrogen-oil ratio 5800 ~ 6500, new hydrogen B2 is passed between reactor I and reactor II, maintain the density of hydrogen of reactor II, hydrogenated mixture is back to interchanger 2 by bottom reactor II, with recycle hydrogen B1 and the new fatty acid methyl ester A heat exchange dropped into, save energy consumption.Hydrogenated mixture after heat exchange enters water cooler 6 through interchanger 2 top, enters separator 7 after cooling, and the hydrogen having neither part nor lot in reaction refluxes through recycle pump 8, and hydrogenated products mixture C enters distillation system by flowing out bottom separator 7.Fatty acid methyl ester hydrogenation reactor assembly is readjusted, altering reactor aspect ratio, reactor I aspect ratio is adjusted to 12.44 by 16.33, when device maximum load is produced, reactor I empty tower gas velocity is kept to 0.058m/s by 0.071m/s, material is increased retention in reactor I, is beneficial to and plays reactor I inner catalyst maximum utility.By the point control of two-stage series connection reactor top temperature in reactor I middle and lower part, the middle part occurring in reactor I is concentrated in reaction.Reactor II aspect ratio is adjusted to 14.74 by 16.33, useful volume reduces 33.33% simultaneously, during corresponding maximum production load, reactor II empty tower gas velocity is promoted to 0.087m/s by 0.071m/s, reactor II empty tower gas velocity improves to be beneficial to takes reaction heat out of system fast, avoids the generation of side reaction.Although cut down useful volume (the about 4m of reactor
3), save the input amount (about 6t) of per production cycle Cu-Zn catalyzer, but still can ensure identical or higher production capacity, reduce the growing amount of fatty alkane impurity, hydrogenated products RH value drops to 0.67 ~ 0.88% by 0.79 ~ 1.0%, thus improves the quality of hydrogenated products and ultimately increase the yield of fatty alcohol.
The contrast of table 1Henkel technique and present invention process correlation parameter
Henkel technique | Convert methanol technics | The present invention | |
Reactor mass space velocity | 0.32~0.35/h | 0.34~0.37/h | 0.41~0.45/h |
Catalytic bed top temperature point | 232℃ | 225℃ | 220℃ |
Reactant preheating is consumed energy | Low | High (methanol content is high) | Low |
Hydrogenated products separation costs | Low | High (methanol content is high) | Low |
Hydrogenated products RH | 0.79~1.0% | 0.8~1.0% | 0.67~0.88% |
Hydrogenated products SV | 0.5~0.8 | 0.5~1.0 | 0.3~0.6 |
Hydrogenated products ester content | 0.02~0.06 | 0.04~0.1 | 0.01~0.05 |
As seen from the above table, compared with traditional method, after adopting method of the present invention, not only save pre-thermal energy consumption, reduced hydrogenation products separation costs, and improve the quality of hydrogenated products.
Claims (1)
1. a production method for natural fatty alcohol, comprises purified lipase fatty acid glyceride; After alcoholysis by the fatty acid methyl ester of generation by the hydrogenator I and the hydrogenator II that enter two-stage series connection after carbon chain lengths fractionation successively; Hydrogenation products is passed into vaporizer separating methanol; Eventually pass rectification under vacuum and obtain finished product, it is characterized in that: the feed hydrogen oil ratio of described hydrogenator I is 5800 ~ 6500, reaction pressure 24.5 ~ 25.5MPa, feed preheat temperature is 200 ~ 202 DEG C, the empty tower gas velocity of hydrogenator I is 0.055 ~ 0.061m/s, the upper temp of hydrogenator I 203 ~ 205 DEG C, middle portion temperature 215 ~ 220 DEG C, temperature of lower is at 216 ~ 225 DEG C; Reaction pressure 24.5 ~ the 25.5MPa of hydrogenator II, empty tower gas velocity is 0.079 ~ 0.092m/s, the upper temp of hydrogenator II 205 ~ 210 DEG C, middle portion temperature 208 ~ 215 DEG C, temperature of lower is at 210 ~ 220 DEG C; The aspect ratio of hydrogenator I is 12 ~ 13; The aspect ratio of hydrogenator II is 14 ~ 15, and hydrogenator I is 1.3 ~ 1.5 with the useful volume ratio of hydrogenator II.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US5043485A (en) * | 1987-07-22 | 1991-08-27 | Henkel Kommanditgesellschaft Auf Aktien | Process for the hydrogenation of fatty acid methyl ester mixtures |
CN1223169A (en) * | 1997-11-28 | 1999-07-21 | 阿莫尼·卡萨尔公司 | Method for in-situ modernization of heterogeneous exothermic synthesis reactor |
CN101633602A (en) * | 2008-07-24 | 2010-01-27 | 上海中远化工有限公司 | Method for preparing fatty alcohol through fixed bed hydrogenation by using fatty acid methyl ester |
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DE19810440C1 (en) * | 1998-03-11 | 1999-09-23 | Dhw Deutsche Hydrierwerke Gmbh | Process for the production of unsaturated fatty alcohols from lauric oils |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US5043485A (en) * | 1987-07-22 | 1991-08-27 | Henkel Kommanditgesellschaft Auf Aktien | Process for the hydrogenation of fatty acid methyl ester mixtures |
CN1223169A (en) * | 1997-11-28 | 1999-07-21 | 阿莫尼·卡萨尔公司 | Method for in-situ modernization of heterogeneous exothermic synthesis reactor |
CN101633602A (en) * | 2008-07-24 | 2010-01-27 | 上海中远化工有限公司 | Method for preparing fatty alcohol through fixed bed hydrogenation by using fatty acid methyl ester |
Non-Patent Citations (1)
Title |
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加氢制脂肪醇工艺中消除热点的措施;石荣荣;《科技信息》;20090405(第10期);第81页 * |
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