CN106925191A - A kind of continuous alkoxylation device and technique - Google Patents
A kind of continuous alkoxylation device and technique Download PDFInfo
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- CN106925191A CN106925191A CN201511016863.9A CN201511016863A CN106925191A CN 106925191 A CN106925191 A CN 106925191A CN 201511016863 A CN201511016863 A CN 201511016863A CN 106925191 A CN106925191 A CN 106925191A
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- conversion zone
- return circuit
- epoxyalkane
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- stripping section
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/007—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/146—Multiple effect distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of continuous alkoxylation device and technique.Described device includes a destilling tower, and the destilling tower includes：Conversion zone and the stripping section below the conversion zone；The conversion zone is used to be reacted for initiator and epoxyalkane, and the conversion zone is provided with an initiator charging aperture and at least one epoxyalkane charging aperture, wherein the initiator charging aperture is located at the top of at least one epoxyalkane charging aperture；The stripping section is used to product and unconverted reactants separate.Continuous alkoxylation device of the invention, the high selectivity of low boiling ethoxylated product is improve in terms of engineering, by in destilling tower, multiple epoxyalkane charging apertures are set, ensure that uniform concentration distribution of the epoxyalkane in conversion zone, reduce the generation of higher boiling ethoxylated product, it is ensured that the selectivity of low boiling ethoxylation target product as high as possible.
Description
Technical field
The present invention relates to continuous alkoxylation device, specially one kind can simultaneously realize continuous alkoxy
Change the reaction unit and method of catalytic reaction and product separated.
Background technology
Oxirane is the important derivatives of ethene, and it occurs with many organic compounds containing active hydrogen
Ethoxylation, wherein the compound containing active hydrogen is referred to as initiator or initiator, including alkyl phenol,
Natural alcohol, synthol, primary amine, diamines, aliphatic acid, ethylene glycol and polyethylene glycol etc..Using different
Initiator can obtain thousands of kinds of important fine chemicals by ethoxylation, mainly have ethylene glycol,
Glycol ether, APEO, polyethylene glycol, monoethanolamine etc., these ethoxylates are modern industries
In very important chemical intermediate and fine chemical product.
By taking the reaction of alcohol (being represented with ROH) and oxirane (EO) as an example, ethoxylation can be represented
For：
ROH+EO→RO(EO)1H
RO(EO)1H+EO→RO(EO)2H
RO(EO)2H+EO→RO(EO)3H
…………
__________________
ROH+nEO→RO(EO)nH
Above ethoxylation is typically characterised by：(1) is irreversible parallel-consecutive reaction, reaction
A series of ethoxylated homologs of different ethoxymer distributions will be generated；(2) reactions are strongly exothermic, often rub
Your oxirane open loop thermal discharge is about 92kJ；(3) boiling-point difference of ethoxylated products is big, general feelings
Per one oxirane of addition under condition, the boiling point of product increases about 40 DEG C.
Industrially, the target product for generally requiring be with lower boiling some or several addition products,
Other addition products then turn into accessory substance or poorly efficient component, therefore, how to improve low boiling target product
Key that is selective, making full use of reaction heat to turn into various ethoxylation process exploitations and improvement needs consideration
Problem.
At present, wide variety of ethoxylation technique includes intermittent reaction technique and successive reaction work both at home and abroad
Skill, batch technology include traditional batch tank ethoxylation technique, Press circulation atomizing technique and
Buss loops reaction process, these techniques be widely used in production Determination of Polyoxyethylene Non-ionic Surfactants and
The contour molecular weight ethoxylated product of polyethylene glycol.The low-molecular-weight such as monoethanolamine and glycol ether, it is low plus
Into in the industrialized production of ethoxylated products, continuous pipe type reaction process is used mostly.
Chinese patent 92108847.7 discloses a kind of method for producing EGME, methyl alcohol and epoxy second
Alkane prepares EGME by ethoxylation, and the reactor system for using is by a can-like reactor
Followed by it is made up of a tubular reactor.United States Patent (USP) US3935279 discloses a kind of production second
The pipeline continuous reaction process flow of glycol ethers, is mainly synthesized and separated group structure by two sections of glycol ethers
Into wherein first paragraph is adiabatic reaction and the separation of product, and second segment is the steaming of isothermal reactor and product
Evaporate.Although these techniques cut both ways, using first reaction, rear separation, unconverted reactant circulation
Traditional route, all have that low boiling ethoxylated product is selectively low, reaction heat can not obtain direct profit
It is excessive (generally higher than 6) with, the proportioning of raw material initiator and oxirane, homogeneous catalyst etching apparatus,
The problems such as separation difficulty and dead catalyst pollute.
Reaction distillation is a kind of emerging chemical process reinforcement technique for growing up the eighties in last century.The skill
PROCESS COUPLING the most key in the two field of chemical engineering will be reacted and separated to art in same unit
In, a representative art as innovation traditional unit operations, it is considered to be the pioneer of process intensification.
Analog study that peace dimension is medium to report catalytic distillation process synthesizing glycol monomethyl ether [《Chemical Reaction Engineering with
Technique》, in April, 2008, volume 24, the 2nd phase], the structure of the catalytic distillation tower that the document is introduced
For：Whole tower is divided into the conversion zone of the structured packing equipped with supported catalyst and equipped with common structured packing
Stripping section, in its top feed of conversion zone, in the bottom feed of conversion zone, tower returns oxirane methyl alcohol entirely
Stream operation, tower reactor discharging.The process has a novelty, but in terms of the engineer applied for still have perhaps
More indeterminable problem.First, when oxirane is from a throat-fed, entering in tower
Local concentration is high at material, and this will cause the generation of more ethoxylation side reactions and the production of more accessory substances；
Secondly, the method ethylene oxide reaches 100% in the conversion per pass of conversion zone, and this is a kind of reason
Think situation, in fact there is the reasons such as catalyst deactivation, the conversion per pass of oxirane can not reach 100%
When, now oxirane and then will influence tower normal operating by the accumulation of the top of tower；Again, due to
The boiling-point difference of reactant and product is big, and big along tower temperature span in reactive distillation column, bottom temperature is far above
Conversion zone temperature, causes heating media operation temperature high, and greatly, system energy consumption is high for load.
The content of the invention
A primary object of the present invention is at least one defect for overcoming above-mentioned prior art, there is provided one
Continuous alkoxylation device, including a destilling tower are planted, the destilling tower includes conversion zone and stripping section；
Conversion zone is used to be reacted for initiator and epoxyalkane, and the conversion zone is provided with an initiator to be entered
Material mouth and at least one epoxyalkane charging aperture, wherein the initiator charging aperture is located at described at least one
The top of epoxyalkane charging aperture；Stripping section be located at the conversion zone lower section, be used to by product with
Unconverted reactants separate.
According to an embodiment of the present invention, the first current return circuit is additionally provided with above the conversion zone,
So that unconverted reactant reenters the conversion zone and participates in reaction.
Another implementation method of the invention, second liquid phase import is provided with the conversion zone, described
Second liquid phase import is connected with first current return circuit.
Another implementation method of the invention, the destilling tower include be sequentially communicated from top to bottom tower top,
The conversion zone, the stripping section and bottom of towe；Gaseous phase outlet is provided with the top of the tower top, in institute
State and backflow import is provided with the side wall of tower top, the gaseous phase outlet is connected to be formed with the backflow import
First current return circuit；The second liquid phase import is arranged at the 1/3~2/3 of the conversion zone height.
Another implementation method of the invention, the second current return circuit is provided with the stripping section, in institute
State and having heaters is set on the second current return circuit.
Another implementation method of the invention, second current return circuit is arranged at the profit reduction and reserving section highly
1/3~2/3 at.
Another implementation method of the invention, is provided with the 3rd current return circuit below the stripping section,
Reboiler is provided with the 3rd current return circuit.
Another implementation method of the invention, the destilling tower is plate column.
Invention further provides a kind of continuous alkoxylation technique, the alkoxylation exists
Carried out in one destilling tower, the destilling tower includes conversion zone and the stripping section below the conversion zone,
The technique includes：
Initiator is set to carry out alkoxylation in the conversion zone with epoxyalkane, wherein the alkylene oxide
Hydrocarbon enters the conversion zone by least one import；And
Gained product carries out separating-purifying from the conversion zone into the stripping section.
According to an embodiment of the present invention, the conversion zone is provided with catalyst, the initiator with
Epoxyalkane reacts in the catalyst counter current contacting.
Another implementation method of the invention, is provided with the first current return circuit above the conversion zone,
The unconverted reactant in part reenters the reaction by first current return circuit in the conversion zone
Section participates in reaction, and remaining unconverted reactant together enters the stripping section with the product.
Another implementation method of the invention, second liquid phase import is provided with the conversion zone, described
Second liquid phase import is connected with first current return circuit.
Another implementation method of the invention, the second current return circuit is provided with the stripping section, in institute
State and be provided with below stripping section the 3rd current return circuit, the unconverted reactant in the stripping section passes through
Second current return circuit or the 3rd current return circuit reenter the conversion zone and participate in reaction.
Continuous alkoxylation device of the invention and technique, improve low boiling ethoxy in terms of engineering
The high selectivity of base product, sets multiple epoxyalkane charging apertures, it is ensured that epoxy by destilling tower
Uniform concentration distribution of the alkane in conversion zone, reduces the generation of higher boiling ethoxylated product, it is ensured that
The selectivity of low boiling ethoxylation target product as high as possible.
The continuous alkoxylation device of an embodiment of the present invention, is set by the middle part of conversion zone
One tower top material second liquid phase import, it is ensured that the conversion ratio of epoxyalkane.Another embodiment party of the present invention
The continuous alkoxylation device of formula, an intermediate heater is set by the middle part of stripping section, is made
The energy consumption of the tower bottom reboiler of reactive distillation column is reduced.
Brief description of the drawings
It is of the invention each by being considered in conjunction with the accompanying following the following detailed description of the embodiment of the present invention
Target, feature and advantage is planted to will become apparent.Accompanying drawing is only exemplary diagram of the invention,
It is not necessarily drawn to scale.In the accompanying drawings, same reference represents same or similar all the time
Part.Wherein：
Fig. 1 is the structural representation of the continuous alkoxylation device of an embodiment of the present invention.
Specific embodiment
Embodying feature of present invention will describe in detail in the following description with the exemplary embodiment of advantage.Should
What is understood is that the present invention can have various changes in different implementation methods, and it does not all depart from this hair
Bright scope, and explanation therein and diagram are treated as purposes of discussion in itself, and it is not used to limitation originally
Invention.
As shown in figure 1, the continuous alkoxylation device of an embodiment of the present invention, including reaction is steamed
Tower 10 is evaporated, reactive distillation column 10 includes conversion zone I and stripping section II.Conversion zone I is used to supply initiator
Reacted with epoxyalkane, while also the heavy constituent of generation can be made to leave reaction zone by distillation,
Conversion zone I is provided with the epoxyalkane charging aperture 12 of initiator charging aperture 11 and at least one, wherein rising
Beginning agent charging aperture 11 is located at the top of epoxyalkane charging aperture 12；Stripping section, be used to by product with
Unconverted reactants separate.Wherein, product heavy constituent can be produced by bottom of towe, and initiator passes through
Distillation comes back to conversion zone I and continues to react.
Invention further provides a kind of continuous alkoxylation technique carried out using said apparatus,
The alkoxylation is carried out in reactive distillation column 10, wherein the technique includes：Make initiator and ring
Oxygen alkane carries out alkoxylation in conversion zone I, and epoxyalkane enters distillation by least one import
Tower 10；Gained product autoreaction section I carries out separating-purifying into stripping section II.
The ring-opening reaction of epoxyalkane and similar reaction can be anti-in continuous alkoxylate of the invention
Answer and carry out in device, epoxyalkane for example can be oxirane, expoxy propane or oxirane with
The mixture of expoxy propane.Below by taking the reaction of oxirane as an example, to continuous alkoxylate of the invention
Reaction unit and technique are described in detail.Continuous alkoxylation device of the invention and technique can
For the production of low addition ethoxylated product, such as production of glycol monoether product.
Reactive distillation column of the invention 10 can be packed tower, or plate column.In oxirane
In reaction, preferably plate column, liquid phase thing in the placement and intermediate heater 61 in order to catalyst 21
The extraction of material, tower plate structure can be cross-current type column plate, reverse-flow column plate or injecting type column plate, preferably
Injecting type column plate.The catalyst 21 for being used can be solid porous catalyst, and catalyst 21 can be placed
On the column plate of conversion zone I, and modes of emplacement is unrestricted.
According to function, the inside of reactive distillation column 10 can be divided into tower top 101, conversion zone I, stripping
Section II and bottom of towe 102, four are set gradually and are connected from top to bottom, and the solid for catalytic reaction is urged
Agent is arranged at conversion zone I so that initiator can be reacted herein with oxirane, conversion zone with
The preferred ratio of the height of stripping section is 2:1.Conversion zone I is located at the top of stripping section II, in conversion zone
Initiator charging aperture 11 and epoxyalkane charging aperture 12, epoxyalkane charging aperture can be opened up on I side wall
12 number can be one, or multiple, such as four, multiple epoxyalkane charging apertures 12
Can be uniformly arranged along the short transverse of reactive distillation column 10.Initiator charging aperture 11 enters positioned at epoxyalkane
The top of material mouth 12, catalyst 21 is met in order to initiator with oxirane from bottom to top, and
Reacted in the presence of catalyst 21.Such as initiator charging aperture 11 can be located at close to tower top 101
Position.
Initiator charging aperture 11 can be by the phase of feed pipe 31 with initial agent feeding device (not shown)
Connection, in the presence of feed pump 32, initiator can enter reactive distillation column 10 by feed pipe 31.
Can be the small organic compound containing active hydrogen of molecular weight, such as first with the initiator of reacting ethylene oxide
Alcohol, ethanol, propyl alcohol, butanol, propenyl or butenol.
Epoxyalkane charging aperture 12 can be by feed pipe with oxirane feedway (not shown)
41 are connected, and in the presence of feed pump 42, oxirane can enter reaction distillation by feed pipe 41
Tower 10.The presence of multiple epoxyalkane charging apertures 12, can be such that oxirane is protected in the concentration of conversion zone I
Hold uniform, it is to avoid the local concentration of the neighbouring oxirane of charging aperture is too high in reactive distillation column 10, reduces
The generation of accessory substance.
Gaseous phase outlet 13 and overhead condensation liquid liquid phase can be set in the top of the conversion zone I of reactive distillation column 10
Backflow import 14, gaseous phase outlet 13 can for example be opened in the top of tower top 101, in order to gas phase
The effusion of material.Backflow import 14 can be opened on the topmost side wall of tower top 101, and can be higher than starting
Agent charging aperture 11.Gaseous phase outlet 13 can be by being arranged on outside reactive distillation column 10 with backflow import 14
Pipeline be connected, formed the first current return circuit 50.Further, can be on the first current return circuit 50
Set gradually condenser 51, return tank 52 and reflux pump 53.
During operation, boiling point initiator high can be in the presence of feed pump 32 from the starting close to tower top 101
Agent charging aperture 11 enters the conversion zone I of reactive distillation column 10, and the oxirane of low boiling point can be in feed pump
Enter reaction distillation from multiple epoxyalkane charging apertures 12 after distributing flow via control valve in the presence of 42
The conversion zone I of tower 10.The charging molar flow ratio of initiator and oxirane can be such as (1~2):1.
Two kinds of raw materials reactive distillation column 10 the counter current contacting of conversion zone I, in the presence of solid catalyst 21
Generation ethoxylation, reaction temperature can be 80~160 DEG C, preferably 100~140 DEG C, the behaviour of tower
It can be 0.1~1.0MPa in terms of absolute pressure to make pressure.
The raw material of (having neither part nor lot in reaction) portion of non-converted in conversion zone I is in the form of a vapor from gaseous phase outlet 13
Into the first current return circuit 50, return tank 52 is entered after the circulating water condensation of condensed device 51, and
In the presence of reflux pump 53, reactive distillation column 10 is entered as the liquid-phase reflux of tower from backflow import 14.
Further, second liquid phase import 15, second liquid phase import 15 can be also opened up on the side wall of conversion zone I
The lower section of initiator charging aperture 11 is can be located at, for example it can be located at the 1/3~2/3 of the height h of conversion zone I
Place, at preferably 1/2, i.e., the position of second liquid phase import 15 can be with the distance of the lower end of conversion zone I
1/2h.Specifically, such as second liquid phase import 15 can be located at the 3rd~5 from bottom to top of conversion zone I bottoms
Between block column plate, preferably conversion zone I bottoms the 3rd piece of column plate top from bottom to top.
Second liquid phase import 15 can be connected by pipeline with the first current return circuit 50 so that the first backflow
The backflow material of path 50 can enter reactive distillation column 10 by the import 14 that flows back, second liquid phase import 15,
The oxirane not converted completely in overhead condensation liquid can be made to continue back at conversion zone I reacted, to adjust
Save the conversion ratio of oxirane.Further, backflow import 14, second liquid phase can be entered by controlling valve
The ratio between inlet amount of mouth 15 is adjusted to such as 1:(0.2~0.5).Regulation without second liquid phase import 15 is made
Used time, can be turned off, only provide the liquid-phase reflux of tower by flowing back import 14.
The product and the unconverted raw material initiator of another part of generation are with the shape of liquid in conversion zone I
Formula autoreaction section I flow to stripping section II, and most of initiator is anti-by being reentered after the separation of stripping section II
Section I is answered to participate in reaction, product leaves reactive distillation column 10 by discharging opening 16, discharge nozzle 80.
Said process can be carried out continuously, oxirane and initiator continuous feed, and tower top does not discharge, oxirane
Converted completely in tower, bottom of towe extraction ethoxylated product and a small amount of initiator.
Second current return circuit 60 is arranged at the outside of reactive distillation column 10, and it can be located at the outer of stripping section II
Portion, for example its can be located at the 1/3~2/3 of the height of stripping section II.Specifically, can be in the stage casing of stripping section II
Liquid-phase outlet 17, gas phase import 18 are opened up on neighbouring side wall, gas phase import 18 is located at liquid-phase outlet 17
Top.Liquid-phase outlet 17 can be by being arranged at the pipeline outside reactive distillation column 10 and gas phase import 18
It is connected, forms the second current return circuit 60, heater 61 also can be set on the second current return circuit 60.
Unconverted liquid phase feed enters the second current return circuit 60 by liquid-phase outlet 17, and heated device 61 is heated
After vaporization, phase feed is formed, and enter reactive distillation column 10 from gas phase import 18, further passed through
Stripping section II reenters conversion zone I and participates in reaction.Specifically, liquid-phase outlet 17 can be opened in bottom of towe
On more than 102 the 3rd block of column plate, gas phase import 18 can be opened in the 4th block of column plate of bottom of towe more than 102
On, heater 61 can be located at reactive distillation column 10 it is outer, from the 3rd~5 block of column plate of bottom of towe more than 102
Place.
Further, the second gas phase import 19, the second gas phase import can be opened up on the side wall of bottom of towe 102
19 can be connected by being arranged at the pipeline outside reactive distillation column 10 with discharging opening 16, be formed the 3rd time
Logical circulation road 70, can be set reboiler 71 on the 3rd current return circuit 70.Unconverted liquid phase feed can be entered
One step enters the 3rd current return circuit 70 by discharging opening 16, after the heating vaporization of reboiler 71, formation gas
Phase raw material, and reactive distillation column 10 is reentered from gas phase backflow import 19, further by stripping section
II reenters conversion zone I participates in reaction.Discharging opening 16 can for example be arranged at the bottom of bottom of towe 102,
In order to the collection of product.
The continuous alkoxylation device and technique of an embodiment of the present invention, using the mistake of reaction distillation
Journey reinforcement technique, can simultaneously realize ethoxylation catalytic reaction and product distillation in a reactive distillation column
Separate, solve the reaction that prior art needs just be carried out using multitower or multiple reactors and multi-step
And separation problem, existing process flow is enormously simplify, reduce production cost.
The continuous alkoxylation device and technique of another implementation method of the present invention, improve in terms of engineering
The high selectivity of low boiling ethoxylated product.Dynamics data shows, each step of ethoxylation
Addition speed is essentially identical, if the local concentration of conversion zone oxirane is too high, the generation of accessory substance
Amount is big.Multiple epoxyalkane charging apertures are set by destilling tower, it is ensured that epoxyalkane is in conversion zone
Uniform concentration distribution, reduce higher boiling ethoxylated product generation, it is ensured that low boiling as high as possible
The selectivity of point ethoxylation target product.
The continuous alkoxylation device and technique of another implementation method of the present invention, improve in terms of engineering
The conversion ratio of oxirane.It is well known that oxirane is a kind of high-risk chemical, it is easily so explosive to have
Poison, typically requires that oxirane is converted completely as far as possible in tower in engineering.Using another implementation of the invention
The device and technique of mode, even if the oxirane of charging is not converted completely in conversion zone, it is also possible to from
Second liquid phase import 15 enters conversion zone I and continues to react, it is ensured that oxirane forms in tower and circulates and turn
Change completely, occur without low boiling oxirane in top of tower accumulation problem.
The continuous alkoxylation device and technique of another implementation method of the present invention, ethoxy in conversion zone I
A large amount of reaction heat that glycosylation reaction is produced can be completely used for the vaporization of liquid in tower, it is not necessary to from reaction distillation
Reaction heat is removed in tower, the maximum for realizing reaction heat is directly utilized.
The continuous alkoxylation device and technique of another implementation method of the present invention, reduce in terms of engineering
The operating cost of destilling tower tower, for the boiling-point difference ratio of reactant and ethoxylated product in destilling tower 10
The larger, problem that big along tower temperature span, column bottom temperature is far above conversion zone temperature, by stripping section
II set heater 61, using the lower heating medium of temperature, it is possible to decrease high-grade reboiler 71 plus
The consumption of thermal medium, and then the energy consumption of reboiler 71 is reduced, save the operating cost of system.
Specifically, the heating-up temperature of heater 61 can be 120~160 DEG C, the heating temperature of reboiler 71
Degree can be 160~220 DEG C, because temperature in the corresponding tower in position set by heater 61 can be than boiling again
The temperature of the corresponding bottom of towe in position of device 71 is low 40~80 DEG C, corresponding to be supplied to the outer of intermediate heater
The potential temperature and grade of portion's heating medium are also corresponding low, and the load of heater 61 can be reboiler 71
0.1~0.5, such as 0.2, the consumption that tower bottom reboiler high-grade heats medium can be reduced according to this, so as to reach
To the purpose of energy-conservation.Temperature can be than the position of reboiler 71 in the corresponding tower in position set by heater 61
The temperature of corresponding bottom of towe is low 40~80 DEG C.
The continuous alkoxylation device and technique of another implementation method of the present invention are logical by the second backflow
The molar flow ratio of the liquid phase feed on road 60 and the liquid phase feed for passing through the 3rd current return circuit 70 can be
1:(3~5).The load of heater 61 can be the 0.1~0.5 of reboiler 71, such as 0.2.Second time
The presence of the current return circuit 70 of logical circulation road 60 and the 3rd can make raw material that reaction is backed within distillation
Section I continues to react, so that it is guaranteed that it has conversion ratio high.
The continuous alkoxylation device and technique of another implementation method of the present invention, reduce in terms of engineering
The operating cost of destilling tower tower, for the boiling-point difference ratio of reactant and ethoxylated product in destilling tower 10
The larger, problem that big along tower temperature span, column bottom temperature is far above conversion zone temperature, by stripping section
II the second current return circuit 60 sets heater 61, using the lower heating medium of temperature, it is possible to decrease high
Grade reboiler 71 heating medium consumption, this by reduce system operating cost, while improve being
The thermodynamic efficiency of system.
Hereinafter, in conjunction with the drawings and the specific embodiments to continuous alkoxylation device of the invention and technique
It is described further.
Embodiment 1
With oxirane and methyl alcohol as raw material, synthesizing glycol monomethyl ether
The equipment and structural parameters of reactive distillation column used 10 is：The internal diameter of reactive distillation column 10 is 0.5m,
Total number of plates is 16 pieces of column plates (sorting from top to bottom, not including condenser and reboiler).Wherein conversion zone
I includes 11 blocks of column plates, and stripping section II includes 5 blocks of column plates, and initiator charging aperture 11 is arranged at the 1st piece
Column plate top, four epoxyalkane charging apertures 12 are respectively arranged on the 3rd, 5,9,11 blocks of column plates,
Backflow import 14 is arranged at the 1st column plate top, and second liquid phase import 15 is arranged at the 7th piece of column plate top,
Liquid-phase outlet 17 is arranged on the 15th block of column plate, and gas phase import 18 is arranged on the 14th block of column plate.
The operating condition and operating mode of tower be：Methanol feed stream amount is 4.5kmol/h, total stream of oxirane
It is 4.5kmol/h to measure, and point flows such as four strands enter conversion zone I, the charging mole of methyl alcohol and oxirane
Flow-rate ratio is 1:1.The operating pressure of tower is 0.4MPa (with absolute manometer), and the temperature of tower top 101 is
104 DEG C, the mean temperature of conversion zone I is 118 DEG C, and the temperature of bottom of towe 102 is 162 DEG C；Condenser duty
It is 1.78GJ/h, reboiler 71 boils than being 5.0 again, and thermic load is 1.24GJ/h, and heater 61 is adopted
Go out fluid flow for 12.0kmol/h, thermic load is 0.35GJ/h, and overhead vapours is cooled with circulating water, tower
Bottom heating-up temperature is 190 DEG C, and the heating-up temperature of heater 61 is 150 DEG C；Return tank of top of the tower 52 is to backflow
The fluid flow mol ratio of import 14 and the distribution of second liquid phase import 15 is 1:0.2.
Operation 1.5 hours, tower stable operation, each point for measuring temperature temperature reading stabilization in tower, from bottom of towe discharge
Product in take out sample, it is constituted with chromatogram after cooling and is analyzed.
Analyzing testing result is：Bottom product mole is constituted：It is not detected by oxirane, methyl alcohol 3.80%,
Glycol monoethyl ether 93.30%, diethylene glycol monomethyl ether 2.90%, be not detected by triethylene glycol monomethyl ether and
The ethoxylated product of adduct number higher.It is computed, oxirane conversion ratio 100%, methyl alcohol conversion
Rate 96.20% (mole meter), glycol monoethyl ether is 93.30% to the selectivity of oxirane.
Embodiment 2
With oxirane and absolute ethyl alcohol as raw material, synthesizing glycol list ether
The device structure parameter of destilling tower is same as Example 1.
The operating condition and operating mode of tower be：Absolute ethyl alcohol feed rate is 0.50kmol/h, oxirane
Total flow is 0.50kmol/h, the assignment of traffic such as four bursts of chargings, the raw materials components mole ratio of ethanol and oxirane
It is 1:1.The operating pressure of tower is 0.25MPa (with absolute manometer), and the temperature of tower top 101 is 101 DEG C,
The mean temperature of conversion zone I is 110 DEG C, and the temperature of bottom of towe 102 is 160 DEG C, and condenser duty is
2.35GJ/h, reboiler 71 is boiled than being 7.0 again, thermic load is 2.273GJ/h, and heater 61 is adopted
Go out fluid flow for 12.0kmol/h, thermic load is 0.35GJ/h, and overhead vapours is cooled with circulating water, then
Boiling device 71 190 DEG C of heat-conducting oil heatings, heater 61 140 DEG C of heat-conducting oil heatings, return tank of top of the tower
52 do not produce product, and the mol ratio of backflow import 14 and the fluid flow of second liquid phase import 15 is 1:0.2.
Operation 1.5 hours, tower stable operation, each temperature reading stabilization of point for measuring temperature in tower, from bottom of towe discharge
Product in take out sample, it is constituted with chromatogram after cooling and is analyzed.
Analyzing testing result is：Bottom product mole is constituted：Oxirane 0% is not detected by, it is anhydrous
Ethanol 4.20%, ethylene glycol monoethyl ether 92.80%, diethylene glycol monoethyl ether 3.00% is not detected by three second
The ethoxylated product of 2-ethoxyethanol and adduct number higher.It is computed, oxirane conversion ratio 100%,
Ethanol conversion 95.8% (mole meter), ethylene glycol monoethyl ether to the selectivity 92.80% of oxirane (mole
Meter).
Embodiment 3
With oxirane and n-butanol as raw material, synthesizing glycol monobutyl ether
The device parameter of tower is identical with example.
The operating condition of tower is：N-butanol feed rate is 8.0kmol/h, and the total flow of oxirane is
The assignment of traffic such as 8.0kmol/h, four bursts of chargings, the raw materials components mole ratio of n-butanol and oxirane is 1:1.
The operating pressure of tower is 0.25MPa (with absolute manometer), and the temperature of tower top 101 is 130 DEG C, reaction
Section mean temperature is 140 DEG C, and the temperature of bottom of towe 102 is 200 DEG C, and condenser duty is 3.22GJ/h,
Reboiler 71 boils than being 6.0 again, and thermic load is 2.87GJ/h, the extraction fluid flow of heater 61
It is 15.0kmol/h, thermic load is 0.60GJ/h, and overhead vapours is cooled with circulating water, reboiler 71 adds
Thermal recovery uses 160 DEG C of conduction oils, return tank of top of the tower 52 not to produce product with 220 DEG C of conduction oils, heater 61
The mol ratio of product, backflow import 14 and the fluid flow of second liquid phase import 15 is 1:0.2.
Operation 1.5 hours, tower stable operation, each temperature reading stabilization of point for measuring temperature in tower, from bottom of towe discharge
Product in take out sample, it is constituted with chromatogram after cooling and is analyzed.
Analyzing testing result is：Bottom product mole is constituted：It is not detected by oxirane, n-butanol
5.79%, ethylene glycol monobutyl ether 90.40%, diethylene glycol monobutyl ether 3.81% is not detected by triethylene glycol
The ethoxylated product of monobutyl ether and adduct number higher.It is computed, oxirane conversion ratio 100%,
The conversion ratio 94.21% of n-butanol, selectivity 90.40% of the ethylene glycol monobutyl ether to oxirane.
Present invention utilizes the process intensification means of reaction distillation, epoxyalkane can be made to consume completely, low boiling
The selectivity of point ethoxylated products reaches more than 90%, low, small to equipment and corrosive pipeline with energy consumption
With the advantage of high financial profit.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Implementation method described in the invention is not used to limit guarantor of the invention merely for exemplary purpose
Shield scope, those skilled in the art can be made within the scope of the invention various other replacements, change and change
Enter, thus, the invention is not restricted to above-mentioned implementation method, and only it is defined by the claims.
Claims (10)
1. a kind of continuous alkoxylation device, an including destilling tower, the destilling tower includes：
Conversion zone, for being reacted for initiator and epoxyalkane, a starting is provided with the conversion zone
Agent charging aperture and at least one epoxyalkane charging aperture, wherein the initiator charging aperture is located at described at least one
The top of individual epoxyalkane charging aperture；And
Stripping section, positioned at the lower section of the conversion zone, is used to product and unconverted reactants separate.
2. device according to claim 1, wherein being additionally provided with first above the conversion zone
Current return circuit, so that unconverted reactant reenters the conversion zone and participates in reaction.
3. device according to claim 2, wherein the conversion zone is provided with second liquid phase import,
The second liquid phase import is connected with first current return circuit.
4. device according to claim 3, wherein the destilling tower includes being sequentially communicated from top to bottom
Tower top, the conversion zone, the stripping section and bottom of towe；Gaseous phase outlet is provided with the top of the tower top,
It is provided with backflow import on the side wall of the tower top, the gaseous phase outlet is connected shape with the backflow import
Into first current return circuit；The second liquid phase import is arranged at the 1/3~2/3 of the conversion zone height
Place.
5. device according to claim 1, wherein the stripping section is provided with the second current return circuit,
Having heaters is set on second current return circuit.
6. a kind of continuous alkoxylation technique, the alkoxylation is carried out in a destilling tower,
The destilling tower includes conversion zone and the stripping section below the conversion zone, and the technique includes：
Initiator is set to carry out alkoxylation in the conversion zone with epoxyalkane, wherein the epoxyalkane
The conversion zone is entered by least one import；And
Gained product carries out separating-purifying from the conversion zone into the stripping section.
7. technique according to claim 6, wherein the conversion zone is provided with catalyst, it is described
Initiator and epoxyalkane react in the catalyst counter current contacting.
8. technique according to claim 6, wherein being provided with the first backflow above the conversion zone
Path, the unconverted reactant in part is reentered described by first current return circuit in the conversion zone
Conversion zone participates in reaction, and remaining unconverted reactant together enters the stripping section with the product.
9. technique according to claim 8, wherein the conversion zone is provided with second liquid phase import,
The second liquid phase import is connected with first current return circuit.
10. technique according to claim 6, wherein the stripping section is provided with the second current return circuit,
The 3rd current return circuit is provided with below the stripping section, the unconverted reactant in the stripping section leads to
Cross second current return circuit or the 3rd current return circuit reenters the conversion zone and participates in reaction.
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| CN108479100A (en) * | 2018-04-19 | 2018-09-04 | 福州大学 | The catalytic distillation device of lipase resolving chiral 1- benzyl carbinols and the method for producing chirality 1- benzyl carbinols |
| CN112973161A (en) * | 2019-12-12 | 2021-06-18 | 江苏民生特种设备集团有限公司 | Internal packing device of distillation tower |
| CN115253341A (en) * | 2022-08-15 | 2022-11-01 | 惠州市红墙化学有限公司 | Method and device for removing and converting alkylene oxide |
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| CN204589032U (en) * | 2015-04-24 | 2015-08-26 | 天津普莱化工技术有限公司 | A kind of device of reactive distillation synthesizing glycol monobutyl ether |
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| CN1657514A (en) * | 2004-02-18 | 2005-08-24 | 中国石油化工股份有限公司 | Method of preparing ethylene glycol |
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| CN112973161A (en) * | 2019-12-12 | 2021-06-18 | 江苏民生特种设备集团有限公司 | Internal packing device of distillation tower |
| CN115253341A (en) * | 2022-08-15 | 2022-11-01 | 惠州市红墙化学有限公司 | Method and device for removing and converting alkylene oxide |
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