CN107253901A - A kind of separation of high-purity isopropanol and purification method - Google Patents
A kind of separation of high-purity isopropanol and purification method Download PDFInfo
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- CN107253901A CN107253901A CN201710616938.XA CN201710616938A CN107253901A CN 107253901 A CN107253901 A CN 107253901A CN 201710616938 A CN201710616938 A CN 201710616938A CN 107253901 A CN107253901 A CN 107253901A
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The present invention discloses separation and the purification method of a kind of high-purity isopropanol, belong to isopropanol purification techniques field, use weight/mass percentage composition for 20~60% isopropanol water solution as raw material, it is taken up in order of priority and carries out corresponding rectifying, adsorption treatment in first rectifying column, multitower adsorption system and Second distillation column, finally gives the isopropanol product that purity is more than 99.9%.The present invention utilizes the absorption in isopropanol water azeotropic point to have selective absorption moisture and reach and skip azeotropic point, the preliminary stage being separated from water in isopropanol occurs for strengthening process, and realize continuous process easily by multitower operation, the entrainer of sequence of constant boiling and rectification and the extractant of extracting rectifying need not be used, realize energy-saving, obtain purer isopropanol product.
Description
Technical field
The invention belongs to isopropanol purification techniques field, more particularly to a kind of separation of high-purity isopropanol with
Purification method.
Background technology
Isopropanol (IPA) as solvent, intermediate, antifreezing agent, bactericide, insecticide, cleaning agent, disinfection preservative etc.,
It is widely used in the industries such as chemical industry, medicine, agricultural chemicals, weaving, residential care, electronics.Isopropyl alcohol production mainly has propylene hydration (to contain
Indirectly with directly) method and acetone hydrogenation method, wherein, hydration method is to use most processes at present.
The thick isopropanol water solution obtained by hydration method, its concentration is about 20~60% (w/w), it is necessary to further refine
Dehydration obtains the higher isopropanol product of purity.But because isopropanol and water can form azeotropic mixture at ambient pressure, consisting of different
Propanol concentration 87.4%, water is 12.6%;Azeotropic temperature is 80.31 DEG C, and the boiling point of itself is 82.45 DEG C under isopropanol normal pressure,
Water is 100 DEG C, and the azeotropic mixture that isopropanol-water solutions are formed is the binary azeotropic system of minimum boiling point.Therefore, to obtain higher
The isopropanol of purity, general rectifying can not be realized, it is necessary to use special separation method, such as, add nonvariant boiling reagent (benzene etc.)
Perseverance it is (common) boiling rectifying, energy-conservation next door sequence of constant boiling and rectification, add extractant (ethylene glycol etc.) extracting rectifying, saline extraction essence
Evaporate, the special extract rectification such as gap extracting rectifying, absorption distillation, variable-pressure rectification;Such as, membrane distillation, infiltrating and vaporizing membrane, membrane contactor etc.
UF membrane;Such as, the adsorption separating method of temp.-changing adsorption (TSA) etc..But it is high, de- that these methods remain separating energy consumption
The problems such as water depth is inadequate, in particular for production electronics level isopropanol product, these methods are difficult to deep dehydration.
Sequence of constant boiling and rectification refining isopropanol by nonvariant boiling reagent of benzene is to industrialize popular method at present, the benzene of addition with
Water, isopropanol form new binary and ternary azeotrope, expand the relative volatility of isopropyl alcohol and water.Generally use two towers
Flow, wherein, azeotropic mixture is from azeotrope column (I) overhead extraction.Because benzene property miscible with water is small, form non-equal after azeotropic mixture is condensed
Phase mixture, The book of Changes quantizer separates oil reservoir (benzene and isopropanol mixture) and water layer, realizes dehydration.The technics comparing into
Ripe, automaticity is high, and yield is big, but investment is big, high energy consumption, and the benzene for still having about 0.5% or so remains in isopropanol product
In, it can only be used as industrial level isopropanol.
Bulkhead azeotropy rectification method is that a vertical partition plate is set in common rectifying tower, and it is thermodynamically equivalent to one
Petlyuk towers (one kind of hot coupling rectifying) realize two traditional tower functions, i.e., only need a tower to can be obtained by 3 pure components.
The back-mixing of intermediate species in two-tower process can be prevented effectively from simultaneously, the melange effect on rectifying column (I) feedboard is reduced, significantly
Thermodynamic efficiency is improved, energy consumption about 10~15% is saved than conventional two-tower process, investment and operating cost is also reduced.But its
Obtained isopropanol purity is still inadequate, and it also requires the addition of nonvariant boiling reagent, energy consumption reduction limited extent.
Extracting rectifying is conventional another isopropanol deep dehydration and refined industrial method, such as, using second two
Alcohol is extractant, is added from the extractive distillation column (I) in two-tower process, is regenerated in extraction regenerator (II) and circulating makes
With.This technique can not only cause the composition disappearance of isopropanol-water azeotropic point, and glycol concentration can be than relatively low.The method
Advantage is that the extractant boiling point of selection is high, not volatile, from bottom of towe outflow, and energy consumption is low, pollutes small, and easily reclaim.But, due to
Ethylene glycol extractant is added in the extractive distillation column (I) that water content is higher, active principle isopropyl alcohol concentration is relatively low, causes extraction
Agent usage amount is increased, and acts on smaller, cost recovery to the expansion of the relative volatility without the isopropanol-water system under extractant
It is higher.
Extractive distillation with salt is a kind of improvement of conventional extraction rectifying, is the coupling of extracting rectifying and dissolved salt rectifying.It is
It is one kind to extracting rectifying using the shortcoming that extracting rectifying extractant effect is poor is improved the characteristics of dissolved salt extractant effect
Reinforcing, adds the relative volatility of extracting rectifying.But as conventional extraction rectifying, Solvent quantity is than larger, and in extraction
Addition in rectifying column (I) is taken, effect is subject to certain restrictions.
Absorption distillation is a kind of brand-new isopropanol dehydration technique, and it is to couple absorption with distillation, using absorption normal
Still there is special selectivity in the range of the azeotropic mixture composition that the isopropanol-water that rule rectifying column (I) can not be crossed is formed,
The vapor liquid equilibrium limitation that conventional rectification is faced is overcome, is able to allow isopropanol water solution to cross azeotropic point, continues using conventional
Rectifying column (II) separated, so as to obtain isopropanol product in bottom of towe.Such as, foreign study develops a kind of fixed bed
The absorption distillation flow of liquid phase feeding, it is mainly additionally arranged two tower temperature swing adsorption units between two conventional rectification towers;State
Inside also there is the absorption distillation method of the liquid phase feeding of research and development circulation fluidized bed, i.e. use ethylene glycol for solid absorbent carrier fluid, class
Like the extracting rectifying flow that ethylene glycol is extractant.For two methods are compared to azeotropic distillation, extraction rectifying method, although energy
Reduce energy consumption, but product purity is not high, yield is relatively low, adsorbent service life is short, to adsorb with the recovery time be difficult to match, regenerate
Not exclusively, adsorbent carrier fluid (such as ethylene glycol) internal circulating load of circulation fluidized bed is also the shortcomings of comparison is high than larger, energy consumption, it is difficult to work
Industry.
UF membrane is carried out in the method for isopropanol dehydration, and the film that infiltrating and vaporizing membrane has high selectivity infiltration and phase transformation permeates
Feature, is widely used for ethanol and isopropanol dehydration, feeds as liquid phase, and water passes through film by phase transformation, and energy consumption is relatively low, operation letter
It is single.But the circulation of permeable membrane is smaller, for the infiltrating and vaporizing membrane less stable of isopropanol dehydration, investment is high, is not suitable for big
The industrial-scale production of amount, dehydration depth is limited.United States Patent (USP) Appl.863722 uses hollow fiber pervaporation membrane, uses
In the centre of two tower azeotropic distillation flows, for crossing the azeotropic point of isopropanol and water, allowing non-permeate, (isopropanol content is higher than
Azeotropic mixture is constituted) enter conventional rectification tower (II), tower top effluent returns to infiltration vapour by condensation rear portion as backflow
Change membranous system charging, penetrant is the water discharge of enrichment, bottom of towe outflow isopropanol product.The method is with oozing by two tower conventional rectifications
Vaporization UF membrane coupling thoroughly, it will be apparent that shortcoming includes, and treating capacity is smaller, the purity of product isopropanol is relatively low, membrane stability is poor,
Product yield is relatively low.
The content of the invention
The present invention provides separation and the purification method of a kind of high-purity isopropanol, low energy consumption, high-purity, produces in high yield
Isopropanol product (purity >=99.9~99.99%, w/w), overcomes high energy consumption present in existing isopropanol process for purification, product
Purity is low, fluctuation of service, the low shortcoming of yield.
To solve above-mentioned technical problem, the present invention uses following technical scheme:
A kind of separation of high-purity isopropanol and purification method, including following process:
(1) rectification working process, raw material is the isopropanol water solution that weight/mass percentage composition is 20~60%, is 20~60 in temperature
Under conditions of DEG C, isopropanol water solution is sent into rectifying is carried out in first rectifying column, the water of tower reactor outflow and other micro restructuring
Impurity is divided to be back to after being handled through reboiler in first rectifying column, tower top outflow is less than isopropanol azeotrope with water for isopropanol content
The gas phase distillate of thing composition;
(2) absorption process, the gas phase distillate that step (1) is obtained is 75~85 DEG C through temperature, pressure be 0.1~
Adsorbed, adsorbed in the multitower adsorption system of feeding filling adsorbent after vapor liquid equilibrium knockout drum processing under the conditions of 0.6Mpa
Column overhead outflow is higher than the gas phase mixture that isopropanol azeotrope with water thing is constituted for isopropanol content, and the temperature of gas phase mixture is
75~85 DEG C, pressure be 0.1~0.6MPa, bottom of towe outflow by regeneration enrichment water fluid, into first rectifying column carry out
Rectifying;
(3) gas phase mixture that step (2) is obtained directly or after condensation enters Second distillation column progress rectifying, the second rectifying
Column overhead distillate after tower top gas-liquid balancer or condenser, a part of gas with through first rectifying column tower top gas-liquid balancer
Gas mixing afterwards, into multitower adsorption system, a part is back to Second distillation column, and Second distillation column the bottomsstream is pure
Isopropanol product of the degree more than 99.9%.
Preferably, one or more adsorption towers always are in absorption in the multitower adsorption system described in step (2)
Stage, and remaining tower is then standby or in being filled operated institute's structure eventually by equal pressure drop-vacuumize/rinse-pressure rises-along putting-inverse put-
Into the desorption and regeneration stage.
Preferably, in step (3), Second distillation column is extractive distillation column, close to tower top position add ethylene glycol,
Ethylene glycol adds salt mixed liquor, ethylene glycol monomethyl ether, ethyl acetate, benzene, methyl phenyl ethers anisole, first benzene and its derivative, propyl butyrate, isobutyl
One or more in ester, diethylene glycol (DEG), methyl benzoate, n-butyl ether, vinyl n-butyl ether are as extractant, and tower top evaporates
Go out thing by condensation, the isopropanol condensate liquid that purity is less than 99.9% is back in extractive distillation column, and purity is more than 99.9%
Isopropanol condensate liquid is used as output of products;Extractive distillation column the bottomsstream sends into extractant regeneration tower, extractant regeneration tower tower
Top distillates pure water, and the extractant that extractant regeneration tower bottom of towe distillates enrichment makes as the extractant circulation of extractive distillation column
With.
Preferably, the multitower adsorption system described in step (2) is to be loaded in multi-tower variable pressure adsorption system, adsorption tower
Expect for the molecular sieve of activated carbon, the activated carbon of load active component, silica gel, activated alumina, molecular sieve or load active component
One or more.
Preferably, the multitower adsorption system described in step (2) is multitower temperature swing adsorption system, during regeneration, is used
Temperature higher than the vapours or hot nitrogen of operation temperature or from Second distillation column, extract one isopropanol gas out and rushed by stripping section
Wash regeneration or filling adsorption tower regeneration is evacuated;Activated carbon, the activated carbon of load active component, silica gel, work are filled with adsorption tower
Property aluminum oxide, molecular sieve, the one or more of the molecular sieve of load active component.
Preferably, the multitower adsorption system described in step (2) be multitower alternating temperature pressure swing adsorption system, absorption with again
It is outside the pale of civilization by the change of operating pressure during raw circulate operation, while by the change of temperature, the circulation behaviour for carrying out alternating temperature pressure-variable adsorption
Make;During regeneration, using temperature higher than the vapours or hot nitrogen of operation temperature or from Second distillation column stripping section to extract one out different
Propyl alcohol gas is rinsed regeneration or filling adsorption tower regeneration is evacuated;Activated carbon, load active component are filled with adsorption tower
Activated carbon, silica gel, activated alumina, molecular sieve, the one or more of the molecular sieve of load active component.
Preferably, in step (2), carry out alternating temperature pressure swing adsorption cycles operation, during regeneration, required heat part or
It all is from heat-shift or the heat-shift of Second distillation column overhead condenser or first of Second distillation column overhead condenser
The heat-shift of rectifying column tower top condenser.
Preferably, the multitower adsorption system described in step (2) is multitower liquid phase temperature swing adsorption system, is used as raw material
Isopropanol water solution after first rectifying column rectifying, the gas phase distillate condensing of tower top outflow is into condensate liquid, part condensation
Liquid returns to first rectifying column as backflow, and a part of condensate liquid enters the absorption column overhead of multitower temperature swing adsorption system, regeneration
When, using temperature, higher than the vapours or hot nitrogen of operation temperature or from Second distillation column, enriching section extracts one isopropanol liquid out
It is rinsed regeneration or filling adsorption tower regeneration is evacuated, regenerated liquid is mixed from bottom of towe outflow with the raw material of first rectifying column, is carried out
Rectifying.
Preferably, the gas that absorption column overhead comes out in multitower liquid phase temperature swing adsorption system in step (2) passes through gas
Liquid balancer is condensed into condensate liquid, and rectifying is carried out into Second distillation column, obtains the hyperpure isopropyl alcohol that purity is more than 99.99%
Product.
A kind of separation of above-mentioned high-purity isopropanol and purification method, remaining step are constant, by the absorption system of step (2)
System is substituted or used in parallel using one-level or two grades of infiltration evaporation membranous systems, i.e. the gas in vapor liquid equilibrium device, is directly entered
Enter infiltration evaporation membranous system, impermeable side outflow steam is that the enrichment isopropanol for the azeotropic component that concentration is more than isopropanol and water steams
Vapour, enters Second distillation column or the abstraction distillation system being made up of extractive distillation column and extraction regenerator after condensation;Ooze
The liquid of the enrichment water of saturating side outflow, returns to first rectifying column and is used as raw material.
Compared with prior art, the beneficial effects of the invention are as follows:
(1) using in isopropanol-water azeotropic point, absorption reaches with selective absorption moisture and skips azeotropic point, strengthens
The preliminary stage being separated from water in isopropanol occurs for process, and realizes continuous process easily by multitower operation, without using permanent
The entrainer of rectifying and the extractant of extracting rectifying are boiled, realizes energy-saving, purer isopropanol product is obtained;
(2) present invention is to divide isopropanol water solution by vapor liquid equilibrium in the gas that conventional rectification tower (I) tower top is distillated
From multitower PSA system is directly entered after device, PSA cycle operation is carried out at identical temperature and pressure, alternating temperature is greatlyd save
In absorption distillation flow distillate first condense be changed into liquid, the energy consumption that normal temperature absorption regeneration is heated again;Meanwhile, in overall flow
Operation temperature maintain essentially in the range of identical so that energy consumption of the invention is substantially reduced;
(3) present invention takes full advantage of strong adsorbate moisture the characteristics of absorption is with regenerating complete under the conditions of adsorption operations,
Adsorption and desorption circulate operation is easily realized so that adsorbent service life extends, it is to avoid the adsorbent caused by depth absorption
The problem of regeneration is difficult, while further promoting the interval expansion of azeotropic point by transformation, it is ensured that full temperature journey pressure-variable adsorption essence
The Stability and dependability of flow is evaporated, treating capacity is big, is easy to implement industrialization;
(4) original multitower gas phase PSA system can be switched to multitower gas phase temp.-changing adsorption (TSA) or multitower by the present invention
Gas phase alternating temperature pressure-variable adsorption (TPSA) flow substitute, operation is flexible, adapts to different thick isopropanol manufacturing process and concentration
Feedstock, operating flexibility is larger;
(5) regeneration gas that the present invention produces the gas phase PSA system or TSA systems or TPSA systems of multitower is by handling
After return in conventional rectification tower (I), meanwhile, conventional rectification tower (II) overhead or middle extract are returned directly to
In these adsorption systems so that isopropanol product yield is increased substantially;
(6) present invention can introduce extraction rectifying method in conventional rectification tower (II), so than traditional extraction rectifying method
More efficient, extractant circulation consumption is few, and product directly can flow out from extractive distillation column (II) tower top, and very high purity can be made
For electronics level isopropanol product, yield is also high, wherein, micro metal ion and other impurities with the higher water of volatility, from
Extract the outflow of regenerator (III) tower top.The method eliminates the follow-up adding ion crosspoint of electronics level isopropanol product, investment with
Energy consumption is greatly lowered;
(7) multitower gas phase PSA or TSA or the TPSA system in the present invention, also changeable is liquid phase adsorption system, but is adsorbed
The techniques such as agent distribution, loadings, absorption sequential, regeneration need to redesign;
(8) multitower gas phase PSA or TSA or the TPSA system in the present invention, can be replaced with one-level or two grades of infiltrating and vaporizing membranes
In generation, is used in parallel;
(9) present invention in when being related to temp.-changing adsorption distillation operation, its regenerate needed for heat can use whole substantially
The condensation institute liberated heat of individual system is compensated, without outside energy.Because avoiding depth suction in adsorption system
The problem of high energy consumption of the higher regeneration temperature of the attached difficult needs of caused regeneration or regenerated load.
Brief description of the drawings
Fig. 1 is the flow diagram of embodiment 1;
Fig. 2 is the schematic flow sheet of embodiment 2;
Fig. 3 is the schematic flow sheet of embodiment 3;
Fig. 4 is the flow diagram of embodiment 4;
Fig. 5 is the schematic flow sheet of embodiment 5;
Fig. 6 is the schematic flow sheet of embodiment 6.
Embodiment
In order that those skilled in the art more fully understands the present invention, below in conjunction with the accompanying drawing in the embodiment of the present invention
Clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Embodiment 1
As shown in figure 1, separation and the purification method of a kind of high-purity isopropanol, are proceeded as follows successively:
1) rectifying column (I):Isopropanol (IPA) content is the aqueous solution of 50% (mass ratio, w/w is similar below), and temperature is
30 DEG C, pressure is normal pressure, and as raw material, from rectifying column (I) bottom, charging carries out conventional rectification, and tower reactor effluent is arranged as waste material
Go out, its component is that water content is more than 99.6%, isopropanol content and is less than 0.4%, and miscellaneous containing other micro heavy constituents
Matter;Tower top outflow be isopropanol content be slightly below isopropanol azeotrope with water thing composition (under normal pressure be 87.5% isopropanol, 17.5%
Water) gas phase distillate, constitute as isopropanol content 85%, water content 15%, 75~85 DEG C of temperature, 0.1~0.6MPa of pressure,
By vapor liquid equilibrium knockout drum, a small amount of liquid flows back as rectifying column (I), and all gas enter multi-tower variable pressure adsorption (PSA) system
System;
2) multitower PSA system:From rectifying column (I) tower top and by the gas of vapor liquid equilibrium device, from filling composite adsorption
4 tower pressure-variable adsorption (PSA) system bottoms of agent enter, wherein, 1 tower absorption, remaining 3 tower are in the desorption and regeneration of different phase;
Using follow-up rectifying column (II) enriching section lateral line withdrawal function, one material is rinsed for regeneration;The outflow of adsorption tower tower top contains for isopropanol
Amount be slightly above isopropanol azeotrope with water thing composition gas phase mixture, isopropyl alcohol concentration be 90~92%, water content be 8~
10%, 75~85 DEG C of temperature, 0.1~0.6MPa of pressure enter rectifying column after vapor liquid equilibrium device or condenser as raw material
(II) conventional rectification is carried out;The fluid of enrichment water of the adsorption tower bottom of towe outflow by regeneration, consisting of isopropanol content 10~
12%, water content 88~90%, by processing, enters rectifying column (I) as raw material and carries out conventional rectification;
3) rectifying column (II):From multitower PSA system adsorption tower overhead, by vapor liquid equilibrium device or condenser
Afterwards, conventional rectification is carried out into rectifying column (II), rectifying column (II) overhead enters the condenser or gas-liquid of the column overhead
Equilibrium separation tank a, part flows back as rectifying column (II), and a part returns to multi-tower variable pressure adsorption (PSA) system feeding;Bottom of towe
Distillate is product isopropanol, and purity is more than 99.9%.
Embodiment 2
As shown in Fig. 2 separation and the purification method of a kind of high-purity isopropanol, in embodiment 1, by what is be made up of 4 towers
Pressure-variable adsorption (PSA) system, switches to one group of (2 towers are in parallel) absorption and one group of (2 towers are in parallel) desorption that parallel two towers are constituted
Temp.-changing adsorption (TSA) system of regeneration, wherein, silica gel and molecular sieve are filled with adsorption tower.Distillated from rectifying column (I) tower top
Thing, the gas after vapor liquid equilibrium enters, adsorption operations temperature from one group of adsorption tower bottom in temp.-changing adsorption (TSA) system
For 75 DEG C, pressure 0.5MPa;The gas of the enrichment isopropanol of adsorption tower tower top outflow fluid phase, consisting of isopropanol 88~
90%, water content is 10~12%, and rectifying column (II) is entered after condensation and carries out further refining spearation (dehydration);Wait to inhale
After the completion of attached, soon start desorption and regeneration.During regeneration, still using one thing of follow-up rectifying column (II) enriching section lateral line withdrawal function
Material, and carried out with condenser after heat exchange, its temperature rises about 10~20 DEG C and is rinsed;Gas is rinsed after condensation, as
Raw material returns to rectifying column (I) charging.Meanwhile, adjacent one group of adsorption tower is in adsorbed state, is achieved in continuous operation.
Embodiment 3
As shown in figure 3, separation and the purification method of a kind of high-purity isopropanol, in embodiment 1, rectifying column (II) is changed
For extractive distillation column (II), and the auxiliary equipment such as an extraction regenerator (III) and corresponding circulating pump is set up, thus, many
An extracting rectifying workshop section is formd behind tower pressure-variable adsorption (PSA) system.In this workshop section, ethylene glycol is used for extractant,
Enter extractive distillation column (II) from the lower section close to extractive distillation column (II) tower top;From 4 tower pressure-variable adsorption (PSA) system tower tops
Effluent, after condensation, from close to the charging of the top of extractive distillation column (II) bottom of towe, is inversely passed with extractant in tower
Matter.The operation temperature of extractive distillation column (II) is 83~85 DEG C, and operating pressure is normal pressure.Distillated from extractive distillation column (II) tower top
Thing is after condensation, and condensate liquid returns to rectifying column (II) as backflow, and on-condensible gas is that purity is produced more than 99.99% isopropanol
Product are exported;The extract of rich oil fluid, i.e. extractant, water and a small amount of isopropanol is flowed out from extractive distillation column (II) bottom of towe, is passed through
Circulation is pumped into close to extraction regenerator (III) tower top bottom, carries out the regeneration of extractant;From extraction regenerator (III) tower top
Water is distillated, the extractant and a small amount of isopropanol fluid for regenerating are flowed out from bottom of towe, by circulating pump, extractive distillation column is sent into
(II), recycle.
Embodiment 4
As shown in figure 4, separation and the purification method of a kind of high-purity isopropanol, in embodiment 1, by rectifying column (I) tower
Vapor liquid equilibrium device on top is changed to condenser (complete condenser), and rectifying column (I) overhead is after complete condenser, a part of liquid
As rectifying column (I) backflow, a part of liquid is directly entered by one group of (2 towers are in parallel) absorption, one group of (2 towers are in parallel) regeneration institute
Liquid phase temp.-changing adsorption (TSA) system of composition, from absorption column overhead charging, adsorption temp is normal temperature, and pressure is normal pressure;Regeneration
When, using inert hot nitrogen, temperature is 100~160 DEG C, and heat comes from the complete condenser and rectifying column (II) of rectifying column (I) tower top
The heat exchange of the complete condenser of tower top, regeneration liquid waste (water content is more than 96.7%, isopropanol content and is less than 3.3%) discharge battery limit (BL),
Nitrogen circulation is used;Composition from the adsorption tower bottom stream in temp.-changing adsorption (TSA) system is, isopropanol 88~90%,
Water 10~12%, directly carries out conventional rectification through being pumped into rectifying column (II), big from rectifying column (II) bottom of towe outflow purity
In 99.9% isopropanol product, after rectifying column (II) overhead is condensed through complete condenser, a part is used as rectifying column (II)
Backflow, a part returns to temp.-changing adsorption (TSA) system, wherein, the initial stage operated in rectifying column (II), overhead is made
First returned to for raw material in rectifying column (I).
Embodiment 5
As shown in figure 5, separation and the purification method of a kind of high-purity isopropanol, on the basis of embodiment 3 and 4, incite somebody to action both
Coupling, i.e. from the bottom stream of liquid phase temp.-changing adsorption (TSA) system of two groups of adsorption towers (2-2 is in parallel) composition, enrichment it is different
Propanol solution, extractive distillation column (II) middle and lower part is delivered to by pump, is extractant close to extractive distillation column (II) tower top bottom
Ethylene glycol is fed, and the operation temperature of extractive distillation column (II) is 83~85 DEG C, and operating pressure is normal pressure.From extractive distillation column (II)
Overhead is after condensation, and condensate liquid returns to rectifying column (II) as backflow, and on-condensible gas is that purity is more than 99.99%
Isopropanol output of products;The extraction of rich oil fluid, i.e. extractant, water and a small amount of isopropanol is flowed out from extractive distillation column (II) bottom of towe
Liquid, is pumped into close to extraction regenerator (III) tower top bottom by circulation, carries out the regeneration of extractant;From extraction regenerator
(III) tower top distillates water, and the extractant and a small amount of isopropanol fluid for regenerating are flowed out from bottom of towe, by circulating pump, feeding extraction
Rectifying column (II) is taken, is recycled.With embodiment 4 except that, in liquid phase temp.-changing adsorption (TSA) system regeneration, directly
The isopropanol product distillated using extractive distillation column (II) tower top is regenerated, and regeneration temperature is 80~85 DEG C, the regeneration of generation
Liquid returns to rectifying column (I) charging.
Embodiment 6
As shown in fig. 6, separation and the purification method of a kind of high-purity isopropanol, in embodiment 1, can be by gas-phase feed
Multi-tower variable pressure adsorption (PSA) system is changed to one-level infiltration evaporation film separation system, i.e. from rectifying column (I) overhead, group
As isopropanol content 85%, water content 15%, 75~85 DEG C of temperature, 0.1~0.6MPa of pressure, through the gas after vapor liquid equilibrium device
Phase fluid, is directly entered infiltration evaporation film separation system, and the isopropanol air-flow of enrichment is flowed out in impermeable side, and isopropyl alcohol concentration is 92
~95%, water 5~8%, the upper semisection for entering back into rectifying column (II) tower body carries out conventional rectification, from the outflow of rectifying column (II) bottom of towe
Purity is the isopropanol product more than 99.9%;Per-meate side flows out composition for 94~96% water, the enrichment water of 4~6% isopropanols,
Or be expelled directly out, or mixed with the raw material for entering rectifying column (I), continue to reclaim a small amount of isopropanol in enrichment water.Per-meate side is adopted
With condensation is evacuated, for the pressure differential motive force needed for permeable membrane both sides provide infiltration.
It will be apparent that embodiment described above is only the part in the embodiment of the present invention, rather than all.Base
The embodiment recorded in the present invention, other all realities that those skilled in the art obtain without creative efforts
Apply example, or the structure change made under the enlightenment of the present invention, the technical schemes that are same or similar to the present invention,
Fall under the scope of the present invention.
Claims (10)
1. separation and the purification method of a kind of high-purity isopropanol, it is characterised in that including following process:
(1) rectification working process, raw material is the isopropanol water solution that weight/mass percentage composition is 20~60%, is 20~60 DEG C in temperature
Under the conditions of, isopropanol water solution is sent into rectifying is carried out in first rectifying column, the water and other micro heavy constituents of tower reactor outflow are miscellaneous
Matter is back in first rectifying column after being handled through reboiler, and tower top outflow is less than isopropanol azeotrope with water thing group for isopropanol content
Into gas phase distillate;
(2) absorption process, the gas phase distillate that step (1) is obtained is 75~85 DEG C through temperature, pressure is 0.1~0.6Mpa bars
Adsorbed after vapor liquid equilibrium knockout drum processing under part in the multitower adsorption system of feeding filling adsorbent, adsorption tower tower top stream
Go out and be higher than the gas phase mixture that isopropanol azeotrope with water thing is constituted for isopropanol content, the temperature of gas phase mixture is 75~85
DEG C, pressure be 0.1~0.6MPa, bottom of towe outflow by regeneration enrichment water fluid, into first rectifying column carry out rectifying;
(3) gas phase mixture that step (2) is obtained directly or after condensation enters Second distillation column progress rectifying, Second distillation column tower
Push up distillate after tower top gas-liquid balancer or condenser, a part of gas with after first rectifying column tower top gas-liquid balancer
Gas mixing, into multitower adsorption system, a part is back to Second distillation column, and Second distillation column the bottomsstream is that purity is big
In 99.9% isopropanol product.
2. separation and the purification method of a kind of high-purity isopropanol as claimed in claim 1, it is characterised in that:In step (2)
Always have in described multitower adsorption system one or more adsorption towers be in absorption phase, and remaining tower it is then standby or in by
Equal pressure drop-fill operation the constituted desorption and regeneration stage eventually along putting-inverse put-and vacuumize/rinse-pressure rises-.
3. separation and the purification method of a kind of high-purity isopropanol as claimed in claim 1, it is characterised in that:In step (3),
Second distillation column is extractive distillation column, close to tower top position add ethylene glycol, ethylene glycol add salt mixed liquor, ethylene glycol monomethyl ether,
Ethyl acetate, benzene, methyl phenyl ethers anisole, first benzene and its derivative, propyl butyrate, isobutyl ester, diethylene glycol (DEG), methyl benzoate, n-butyl ether,
One or more as extractant in vinyl n-butyl ether, overhead is less than 99.9% by condensation, purity
Isopropanol condensate liquid is back in extractive distillation column, and the isopropanol condensate liquid that purity is more than 99.9% is used as output of products;Extraction
Rectifying column the bottomsstream sends into extractant regeneration tower, and extractant regeneration column overhead distillates pure water, and extractant regeneration tower bottom of towe evaporates
The extractant for going out enrichment is recycled as the extractant of extractive distillation column.
4. separation and the purification method of a kind of high-purity isopropanol as described in claim 1 or 2 or 3, it is characterised in that:Step
(2) the multitower adsorption system described in is multi-tower variable pressure adsorption system, and the built-in filler of adsorption tower is activated carbon, load active component
Activated carbon, silica gel, activated alumina, the one or more of the molecular sieve of molecular sieve or load active component.
5. separation and the purification method of a kind of high-purity isopropanol as described in claim 1 or 2 or 3, it is characterised in that:Step
(2) the multitower adsorption system described in is multitower temperature swing adsorption system, during regeneration, and the vapours of operation temperature is higher than using temperature
Or hot nitrogen or stripping section extracts one isopropanol gas out and is rinsed regeneration or filling adsorption tower light soy sauce again from Second distillation column
It is empty;Activated carbon, the activated carbon of load active component, silica gel, activated alumina, molecular sieve, supported active are filled with adsorption tower
The one or more of the molecular sieve of component.
6. separation and the purification method of a kind of high-purity isopropanol as described in claim 1 or 2 or 3, it is characterised in that:Step
(2) the multitower adsorption system described in is multitower alternating temperature pressure swing adsorption system, is pressed when absorption is operated with regeneration cycle by operating
The change of power is outside the pale of civilization, while by the change of temperature, carrying out the circulate operation of alternating temperature pressure-variable adsorption;During regeneration, it is higher than using temperature
The vapours or hot nitrogen of operation temperature or from Second distillation column stripping section extract out one isopropanol gas be rinsed regeneration or
Adsorption tower regeneration is filled to evacuate;Be filled with adsorption tower activated carbon, the activated carbon of load active component, silica gel, activated alumina,
The one or more of molecular sieve, the molecular sieve of load active component.
7. separation and the purification method of a kind of high-purity isopropanol as claimed in claim 6, it is characterised in that:In step (2),
Alternating temperature pressure swing adsorption cycles operation is carried out, during regeneration, required heat is partially or completely from Second distillation column overhead condenser
Heat-shift or Second distillation column overhead condenser heat-shift or the heat-shift of first rectifying column overhead condenser.
8. separation and the purification method of a kind of high-purity isopropanol as described in claim 1 or 2 or 3, it is characterised in that:Step
(2) the multitower adsorption system described in is multitower liquid phase temperature swing adsorption system, as the isopropanol water solution of raw material through the first essence
Evaporate after tower rectifying, the gas phase distillate condensing of tower top outflow is into condensate liquid, and a part of condensate liquid returns to the first essence as backflow
Tower is evaporated, a part of condensate liquid enters the absorption column overhead of multitower temperature swing adsorption system, during regeneration, operation temperature is higher than using temperature
Vapours hot nitrogen or from Second distillation column enriching section extract out one isopropanol liquid be rinsed regeneration or filling absorption
Tower regeneration is evacuated, and regenerated liquid is mixed from bottom of towe outflow with the raw material of first rectifying column, carries out rectifying.
9. separation and the purification method of a kind of high-purity isopropanol as claimed in claim 8, it is characterised in that:In step (2)
The gas that absorption column overhead comes out in multitower liquid phase temperature swing adsorption system is condensed into condensate liquid by vapor liquid equilibrium device, into second
Rectifying is carried out in rectifying column, the hyperpure isopropyl alcohol product that purity is more than 99.99% is obtained.
10. separation and the purification method of a kind of high-purity isopropanol as claimed in claim 1, it is characterised in that remaining step
It is constant, the adsorption system of step (2) is substituted or used in parallel using one-level or two grades of infiltration evaporation membranous systems, i.e. from gas
Gas in liquid balancer, is directly entered infiltration evaporation membranous system, and impermeable side outflow steam is that concentration is more than isopropanol and water
Azeotropic component enrichment IPA vapor, after condensation enter Second distillation column or by extractive distillation column and extraction regenerator
The abstraction distillation system constituted;The liquid of the enrichment water of per-meate side outflow, returns to first rectifying column and is used as raw material.
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109745725A (en) * | 2019-02-02 | 2019-05-14 | 南京工业大学 | A kind of method of energy-saving rectifying-organic azeotropic system of embrane method integrated separation |
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5868906A (en) * | 1995-05-15 | 1999-02-09 | Athens Corporation | Dehydration and purification of isopropyl alcohol to an ultradry and ultrapure level |
CN1458260A (en) * | 2003-05-13 | 2003-11-26 | 天津大学 | Fusel oil molecular sieve gas phase dewatering method and separating and purifying method |
CN1686986A (en) * | 2005-04-13 | 2005-10-26 | 天津大学 | Method for producting absolute ethyl alcohol |
JP2007275690A (en) * | 2006-04-03 | 2007-10-25 | Ngk Insulators Ltd | Method for separating and recovering organic liquid from organic liquid aqueous solution |
CN101333150A (en) * | 2008-07-31 | 2008-12-31 | 中国石油大学(华东) | Technological process and device for separating isopropanol water solution |
CN102452897A (en) * | 2010-12-06 | 2012-05-16 | 江苏达诺尔半导体超纯科技有限公司 | Production process of ultra-high-purity isopropanol |
CN103449968A (en) * | 2013-09-03 | 2013-12-18 | 天津大学 | Biomass adsorption-distillation coupling device and method for refining isopropanol and application thereof |
CN104507897A (en) * | 2012-09-06 | 2015-04-08 | Lg化学株式会社 | Method and apparatus for preparing isopropyl alcohol |
CN105473538A (en) * | 2013-08-20 | 2016-04-06 | Lg化学株式会社 | Method for purifying isopropyl alcohol |
CN105693468A (en) * | 2016-03-22 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Post treatment device and post treatment method of ethanol and isopropanol produced by isopropyl acetate hydrogenation method |
-
2017
- 2017-07-26 CN CN201710616938.XA patent/CN107253901A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5868906A (en) * | 1995-05-15 | 1999-02-09 | Athens Corporation | Dehydration and purification of isopropyl alcohol to an ultradry and ultrapure level |
CN1458260A (en) * | 2003-05-13 | 2003-11-26 | 天津大学 | Fusel oil molecular sieve gas phase dewatering method and separating and purifying method |
CN1686986A (en) * | 2005-04-13 | 2005-10-26 | 天津大学 | Method for producting absolute ethyl alcohol |
JP2007275690A (en) * | 2006-04-03 | 2007-10-25 | Ngk Insulators Ltd | Method for separating and recovering organic liquid from organic liquid aqueous solution |
CN101333150A (en) * | 2008-07-31 | 2008-12-31 | 中国石油大学(华东) | Technological process and device for separating isopropanol water solution |
CN102452897A (en) * | 2010-12-06 | 2012-05-16 | 江苏达诺尔半导体超纯科技有限公司 | Production process of ultra-high-purity isopropanol |
CN104507897A (en) * | 2012-09-06 | 2015-04-08 | Lg化学株式会社 | Method and apparatus for preparing isopropyl alcohol |
CN105473538A (en) * | 2013-08-20 | 2016-04-06 | Lg化学株式会社 | Method for purifying isopropyl alcohol |
CN103449968A (en) * | 2013-09-03 | 2013-12-18 | 天津大学 | Biomass adsorption-distillation coupling device and method for refining isopropanol and application thereof |
CN105693468A (en) * | 2016-03-22 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Post treatment device and post treatment method of ethanol and isopropanol produced by isopropyl acetate hydrogenation method |
Non-Patent Citations (2)
Title |
---|
宫春美: ""生物质固定床吸附_精馏耦合分离异丙醇_水共沸物研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
杨洪先等: ""3A分子筛在异丙醇脱水中的应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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