CN105152860A - Method for refining mixed alcohol by rectification-pervaporation coupling process - Google Patents
Method for refining mixed alcohol by rectification-pervaporation coupling process Download PDFInfo
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- CN105152860A CN105152860A CN201510561566.6A CN201510561566A CN105152860A CN 105152860 A CN105152860 A CN 105152860A CN 201510561566 A CN201510561566 A CN 201510561566A CN 105152860 A CN105152860 A CN 105152860A
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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
Abstract
The invention relates to a method for refining mixed alcohol by a rectification-pervaporation coupling process, which belongs to the technical field of separation. The method includes the following steps: aqueous mixed alcohol is sent into a dehydrating tower and rectified to be dehydrated, most of water is removed from the tower kettle, the mixture of the mixed alcohol and a small amount of water which is obtained from the tower top is sent into a rough separation tower and roughly separated, C1-C3 mixed alcohol and a small amount of water which are obtained from the top of the rough separation tower are condensed and then sent into a pervaporation device for further dehydration, the permeation side is water, and the retention side is the C1-C3 mixed alcohol; after C4-C8 mixed alcohol and a small amount of water which are obtained from the tower kettle of the rough separation tower are layered by a phase separator, the oil phase enters the pervaporation device and is separated, and the water phase returns into the dehydration tower. Compared with the prior art, the method does not need to add a third component in the process of dehydration, thus avoiding environment pollution caused by the addition of the third component and saving the retreatment cost for the third component, the process of azeotropic rectification and extractive rectification is omitted, so that energy consumption is reduced, and product quality is increased.
Description
Technical field
The present invention is specifically related to the waste water alcohol mixture process for purification of a kind of rectifying-pervaporation processes coupling, belongs to separation technology field.
Background technology
Gelatin liquefaction industry is in the ascendant both at home and abroad at present, and F-T synthesis is the core technology of ICL for Indirect Coal Liquefaction.While production high-quality liquid fuel, also can produce the aqueous phase by-product containing oxygen-bearing organic matter, can aqueous phase by-product recycle is the important factor that coal liquifaction project success runs.
Oxygen-bearing organic matter in aqueous phase byproduct from Fischer-Tropsch synthesis is industrial solvent important in the industry such as pharmacy, fine chemistry industry and organic raw material.If by its efficient recovery, be not only conducive to the economic benefit improving gelatin liquefaction, also help environmental protection.
Rectifying separation technology is industrial most widely used liquid mixture lock out operation, is widely used in the departments such as oil, chemical industry, light industry, food, metallurgy.The people such as University of Fuzhou Wang Jun peak are studied coal liquifaction by product alcohol mixture recovery process, the rectification process such as proposition azeotropic distillation, extracting rectifying are separated aqueous phase by-product, its experimental result shows, and the water content after being separated in each alcohol mixture is lower, and experimental program is feasible.But owing to employing corresponding organic solvent at azeotropic distillation to the extracting rectifying stage, and the number that whole sepn process rectifying tower uses is more, and observable index is higher, does not meet the requirement of energy-conserving and environment-protective.Pervaporation technology is the membrane separation technique that a kind of new development is got up, and has unique advantage to the separation of some organic mixture system materials, and development in recent years is very fast, is more and more subject to people's attention.
Summary of the invention
The object of the invention is to, for the deficiencies in the prior art, provide
oneplant the method that rectifying-pervaporation coupling technique refines alcohol mixture.In process aqueous phase byproduct from Fischer-Tropsch synthesis, replace azeotropic distillation and extraction and distillation technology to dewater with rectifying-pervaporation coupling technique, decrease the use of rectifying tower, avoid the use of entrainer and extraction agent simultaneously, reduce energy consumption, protection of the environment.
For achieving the above object, the present invention adopts following technical scheme:
Rectifying-pervaporation coupling technique refines a method for alcohol mixture, comprises the steps:
(1) moisture alcohol mixture is sent into dehydration tower (T1) and carry out rectifying and dewatering, most water removes from tower reactor, and mixture feeding rough segmentation tower (T2) that tower top obtains alcohol mixture and a small amount of water carries out rough segmentation;
(2) rough segmentation tower (T2) tower top obtains C1-C3 alcohol mixture and a small amount of water, and after condensation, send into permeation evaporating device (M1), per-meate side is water, and retaining side is C1-C3 alcohol mixture; Rough segmentation tower (T2) tower reactor obtains C4-C8 alcohol mixture and a small amount of water after phase splitter (V1) layering, and oil phase enters permeation evaporating device (M2) and is separated, and per-meate side is water, and retaining side is C4-C8 alcohol mixture; Aqueous phase is back to dehydration tower (T1).
Described permeation evaporating device (M1) and the middle osmotic evaporation film of permeation evaporating device (M2) are hydrophilic film.
In described rough segmentation tower (T2), tower top, tower reactor respectively arrange a permeation evaporating device.
The material of described rough segmentation tower (T2) tower reactor is after permeation evaporating device process, and the water that its per-meate side obtains after condensation returns dehydration tower (T1) to be continued to be separated.
The refining plant that a kind of rectifying as above-pervaporation coupling technique method of refining alcohol mixture is used, comprise dehydration tower (T1), rough segmentation tower (T2), permeation evaporating device (M1), permeation evaporating device (M2), phase splitter (V1), product receiving tank (V2), product receiving tank (V3), described permeation evaporating device (M1), the per-meate side of permeation evaporating device (M2) is connected on infiltration flow container respectively by a condenser, vacuum pump is connected on condenser, the outlet retaining side is connected to product receiving tank by a product condenser, the tower top of described rough segmentation tower (T2), tower reactor directly connects a permeation evaporating device respectively.
Moisture alcohol mixture is sent into dehydration tower dehydration, most water removes from tower reactor, and overhead product is sent into rough segmentation tower and carried out rough segmentation, and rough segmentation column overhead obtains C1-C3 alcohol mixture and a small amount of water sends into permeation evaporating device after condensation, per-meate side is water, and retaining side is C1-C3 alcohol mixture; Rough segmentation tower tower reactor obtains C4-C8 alcohol mixture and a small amount of water after phase splitter layering, and oil phase enters permeation evaporating device and is separated, and aqueous phase is back to dehydration tower.When adopting above-mentioned technique, the per-meate side that Shuifu County combines in film is removed, and organic molecule is trapped within the feed side of film, obtains the very low alcohol mixture of water content, as product extraction in permeation evaporating device outlet; Membrane permeation side mainly consists of water, wherein containing a small amount of alcohol.
The invention has the advantages that:
(1) as a modification of the present invention mode, the cut of rough segmentation column overhead tower reactor dewaters through osmotic evaporation film, and does not need to re-use extracting rectifying and azeotropy rectification column can reach separation requirement.
(2) organism described in is mixed alcohols.
(3) the rectifying tower overhead product described in enters permeation evaporating device with normal pressure liquid phase and dewaters, and per-meate side is pumped into vacuum, and per-meate side overhead product enters refrigerating unit condensation in vapour form.
(4) separatory membrane adopted in water vapour penetration device refers to mineral membrane water being had to selective penetrated property.
(5) the invention provides the device of the F-T synthesis waste water alcohol mixture process for purification of a kind of rectifying one pervaporation processes coupling, comprise the dehydration tower, the rough segmentation tower that connect successively, phase splitter, permeation evaporating device, receiving tank.The per-meate side of permeation evaporating device is connected on infiltration flow container by condenser, and vacuum pump is connected on condenser, and the outlet retaining side is connected to products pot by product condenser.
beneficial effect is:
1) compared with prior art, without the need to adding three components in dehydration of the present invention, eliminating the interpolation pollution on the environment of three components and the reprocessing expense of three components, eliminating sequence of constant boiling and rectification, extracting rectifying process, reduce energy consumption, improve quality product;
2) do not have the discharge of other wastes in this invention dehydration of organic solvent process in addition to water, resource recovery is high; Do not introduce other solvent, easy to operate, obtain product purity high, energy-conservation, cleanly production and resource utilization recycling can be realized.
Accompanying drawing explanation
Fig. 1 is setting drawing of the present invention;
Number in the figure is as follows: T1-dehydration tower, T2-rough segmentation tower, V1-phase splitter, M1, M2-permeation evaporating device, V2, V3-receiving tank.
Embodiment
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
embodiment 1
Rectifying-pervaporation coupling technique refines the method for alcohol mixture, and its concrete steps are as follows:
1) water content is 93.8wt%, feed rate is the alcohol mixture solution of 15L/h, and dehydration tower reflux ratio is 1, middle part charging, and through dehydration tower T1 rectifying and dewatering, tower reactor distillates material for water, and overhead product composition is as shown in table 1;
2) overhead product enters rough segmentation tower T2, and rough segmentation tower reflux ratio is 3, middle part charging; Overhead product content is as shown in table 2, and tower reactor product content is as shown in table 3; The tower kettle product obtained enters phase splitter V1, and phase splitter temperature is 50 DEG C, and oil-phase product enters permeation evaporating device M2 and dewaters further; Rough segmentation tower overhead directly enters permeation evaporating device M1 and dewaters; The experiment condition of pervaporation is: charging flow velocity is 9.97 × 10
-4m/s, temperature is 58.3 DEG C, and per-meate side vacuum tightness is: 2.0kPa, and this permeation evaporating device forms and is made up of 1 tubular type NaA molecular sieve membrane module, and total fill able membrane area is 0.030144m
2, film pipe range 800mm, external diameter 12mm, internal diameter 8mm, obtain the alcohol mixture product steam of water content lower than 0.15wt% in permeation evaporating device outlet, the steam of M1, M2 enters products pot V2 and V3 respectively after condenser condenses; Record penetrating fluid, water content is 99wt%, returns dehydration tower and continues to be separated.
embodiment 2
The F-T synthesis waste water alcohol mixture process for refining of rectifying-pervaporation processes coupling, its concrete steps are as follows:
1) moisture 93.8wt%, feed rate are the alcohol mixture solution of 15L/h, and dehydration tower reflux ratio is 1, middle part charging, and through dehydration tower T1 rectifying and dewatering, tower reactor distillates material for water, and overhead product composition is as shown in table 1;
2) overhead product enters rough segmentation tower T2, and rough segmentation tower reflux ratio is 3, middle part charging; Overhead product content is as shown in table 2, and tower reactor product content is as shown in table 3; The tower kettle product obtained enters phase splitter V1, and phase splitter temperature is 50 DEG C, and oil-phase product enters permeation evaporating device M2 and dewaters further; Overhead product directly enters permeation evaporating device M1 and dewaters; The experiment condition of pervaporation is: charging flow velocity is 7.91 × 10
-4m/s, temperature is 68.3 DEG C, and per-meate side vacuum tightness is: 2.0kPa, and this permeation evaporating device is made up of 1 tubular type NaA molecular sieve membrane module, and total fill able membrane area is 0.030144m
2, film pipe range 800mm, external diameter 12mm, internal diameter 8mm, export the alcohol mixture product steam obtaining water content and be less than 0.1wt% at permeation evaporating device, the steam of M1, M2 enters products pot V2 and V3 respectively after condenser condenses; Record penetrating fluid, water content is 99wt%, returns dehydration tower and continues to be separated.
Table 1
Table 2
Table 3
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. rectifying-pervaporation coupling technique refines a method for alcohol mixture, it is characterized in that: comprise the steps:
(1) moisture alcohol mixture is sent into dehydration tower (T1) and carry out rectifying and dewatering, most water removes from tower reactor, and mixture feeding rough segmentation tower (T2) that tower top obtains alcohol mixture and a small amount of water carries out rough segmentation;
(2) rough segmentation tower (T2) tower top obtains C1-C3 alcohol mixture and a small amount of water, and after condensation, send into permeation evaporating device (M1), per-meate side is water, and retaining side is C1-C3 alcohol mixture; Rough segmentation tower (T2) tower reactor obtains C4-C8 alcohol mixture and a small amount of water after phase splitter (V1) layering, and oil phase enters permeation evaporating device (M2) and is separated, and per-meate side is water, and retaining side is C4-C8 alcohol mixture; Aqueous phase is back to dehydration tower (T1).
2. rectifying according to claim 1-pervaporation coupling technique refines the method for alcohol mixture, it is characterized in that: described permeation evaporating device (M1) and the middle osmotic evaporation film of permeation evaporating device (M2) are hydrophilic film.
3. rectifying according to claim 1-pervaporation coupling technique refines the method for alcohol mixture, it is characterized in that: in described rough segmentation tower (T2), tower top, tower reactor respectively arrange a permeation evaporating device.
4. rectifying according to claim 1-pervaporation coupling technique refines the method for alcohol mixture, it is characterized in that: the material of described rough segmentation tower (T2) tower reactor is after permeation evaporating device process, and the water that its per-meate side obtains after condensation returns dehydration tower (T1) to be continued to be separated.
5. the refining plant that rectifying as claimed in claim 1-pervaporation coupling technique method of refining alcohol mixture is used, comprise dehydration tower (T1), rough segmentation tower (T2), permeation evaporating device (M1), permeation evaporating device (M2), phase splitter (V1), product receiving tank (V2), product receiving tank (V3), described permeation evaporating device (M1), the per-meate side of permeation evaporating device (M2) is connected on infiltration flow container respectively by a condenser, vacuum pump is connected on condenser, the outlet retaining side is connected to product receiving tank by a product condenser, it is characterized in that: the tower top of described rough segmentation tower (T2), tower reactor directly connects a permeation evaporating device respectively.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041196A (en) * | 2019-05-23 | 2019-07-23 | 南通醋酸纤维有限公司 | The recovery method of esters in waste water |
| CN110180327A (en) * | 2019-05-13 | 2019-08-30 | 天津大学 | A kind of method and system of the tail gas resource utilization containing organic amine |
| CN112707866A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Dewatering method for ionic liquid alcohol solution |
| CN113045386A (en) * | 2021-03-11 | 2021-06-29 | 南京师范大学 | Process method for separating tert-butyl alcohol-tetrahydrofuran-water mixed solvent by rectification-membrane separation integrated process |
| CN113717055A (en) * | 2021-09-02 | 2021-11-30 | 西安近代化学研究所 | Separation and purification method and system of 2-methyl-1, 2-propane diamine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180327A (en) * | 2019-05-13 | 2019-08-30 | 天津大学 | A kind of method and system of the tail gas resource utilization containing organic amine |
| CN110041196A (en) * | 2019-05-23 | 2019-07-23 | 南通醋酸纤维有限公司 | The recovery method of esters in waste water |
| CN112707866A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Dewatering method for ionic liquid alcohol solution |
| CN112707866B (en) * | 2019-10-25 | 2022-11-04 | 中国石油化工股份有限公司 | Dewatering method for ionic liquid alcohol solution |
| CN113045386A (en) * | 2021-03-11 | 2021-06-29 | 南京师范大学 | Process method for separating tert-butyl alcohol-tetrahydrofuran-water mixed solvent by rectification-membrane separation integrated process |
| CN113717055A (en) * | 2021-09-02 | 2021-11-30 | 西安近代化学研究所 | Separation and purification method and system of 2-methyl-1, 2-propane diamine |
| CN113717055B (en) * | 2021-09-02 | 2024-03-26 | 西安近代化学研究所 | Separation and purification method and system for 2-methyl-1, 2-propanediamine |
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