CN104193651B - Refining method and device for synthesizing acetonitrile from acetic acid by ammoniation - Google Patents
Refining method and device for synthesizing acetonitrile from acetic acid by ammoniation Download PDFInfo
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Abstract
The invention relates to a refining method and device for synthesizing acetonitrile from acetic acid by ammoniation. The refining method comprises the following steps: feeding a crude product obtained in an acetic acid ammoniation reaction section into an absorption section; absorbing the crude product by using an acid absorbent in two stages so as to obtain an acetonitrile mother liquid and a tail gas; feeding the acetonitrile mother liquid into a concentrating tower, concentrating to obtain an acetonitrile aqueous solution, and feeding the acetonitrile aqueous solution into an intermediate tank; feeding the concentrated acetonitrile aqueous solution as a feed into a pervaporation separation machine set, and separating so as to obtain crude acetonitrile; enabling water and a small amount of acetonitrile in a feed solution to penetrate through a pervaporation membrane in a steam manner so as to obtain a penetrating fluid, condensing the penetrating fluid, feeding the penetrating fluid back to the concentrating tower, and further feeding the product on the top of the tower back to the pervaporation separation machine set; and feeding the crude acetonitrile obtained from the pervaporation separation machine set back to a rectifying tower, thereby obtaining finished acetonitrile. In the recycling process, the refining method is high in recycling rate, simple in process, high in security coefficient, high in energy utilization rate, small in material liquid circulation amount, low in operation energy consumption and free of a third component.
Description
Technical field
The present invention relates to a kind of process for purification and device being combined to acetonitrile for Ammonium Acetate, more particularly, to a kind of infiltration vapour
Change method refines the method and device of acetic acid ammoniation process synthesizing acetonitrile, belongs to infiltrating and vaporizing membrane application.
Background technology
The topmost purposes of acetonitrile is to make solvent, such as extracting butadiene, the extractant of isoprene, synthetic fibers
Spin solvent and the solvent of some oil, phenol and coloring matter；Oil prodution industry is used as extract the molten of fat from vegetable and animals oils
Agent；Pharmaceutically it is being used for reaction medium of recrystallization of steroid class medicine etc..Acetonitrile is also medical (vitamin b1), in spice
Mesosome, is the raw material producing 2- picoline, triazine, ethylamine, two propionitrile, imidazoles, the double acetonitrile of propylidene etc..
In acetic acid ammoniation process synthesis and purification acetonitrile traditional handicraft, put into after first acetic acid being vaporized with ammonia in reactor,
Catalyst action with aluminium sesquioxide as carrier issues raw aminating reaction and obtains acetonitrile.React in the crude product body after terminating and wrap
Containing acetonitrile, water and a small amount of ammonia, sequentially enter concentration tower, negative pressure tower and malleation tower after two-stage absorption tower absorption removal ammonia and obtain
To finished product acetonitrile.
Because acetonitrile can form azeotrope (acetonitrile-water azeotrope water content about 16wt.% under normal pressure) with water, using normal
Rule rectificating method cannot by the acetonitrile mother liquor of absorption section be directly refined into finished product acetonitrile (purified acetonitrile water content generally≤
0.1wt.%).At present, Ammonium Acetate is combined to the method for acetonitrile refining in acetonitrile technique adopt concentration tower, a negative pressure more
Tower and a malleation tower, some processes such as Chinese patent, application number cn200910051838.2 disclosed " acetic acid and ammonia by two steps
In the method for high-purity acetonitrile " disclosed " method of synthesizing acetonitrile through one-step ammoniating method with acetic acid " with cn200910047399.8
In describe after double column pressure swing rectification section again plus a finished product acetonitrile tower.This kind of process steam consumption is big, and equipment takes up an area
Area is big, and technological process is long, and feed liquid circulating load is big, complex operation, and acetonitrile yield is low.
Content of the invention
It is an object of the invention to proposition is a kind of is combined to the method for acetonitrile refining and dress in acetonitrile technique for Ammonium Acetate
Put.The method has technical process simply, and occupation area of equipment is few, and safety coefficient is high, and energy consumption is low, acetonitrile high income, and cleaning is no
The feature of pollution.
Technical scheme:
It is combined to the process for purification of acetonitrile for Ammonium Acetate, comprise the steps:
1st step, the crude acetonitrile obtaining acetic acid aminating reaction workshop section are absorbed using acidic absorbent, obtain acetonitrile female
Liquid；
2nd step, acetonitrile mother liquor is carried out heating concentration, the dense acetonitrile obtaining is sent into infiltration evaporation separation unit and taken off
Water, feed liquid side obtains being dehydrated acetonitrile；
3rd step, dehydration acetonitrile is carried out rectified purified, obtain finished product acetonitrile.
Preferably, the absorption process in the 1st described step is to be absorbed through two-stage using acidic absorbent；After absorption
Water content in acetonitrile mother liquor is in 40～70wt.%.
Preferably, after the heating concentration in the 2nd described step, in acetonitrile solution ethane nitrile content concentration to 70～
84wt.%, optimum is 80wt.%.
As improvement, in the 2nd step, before acetonitrile solution is done with infiltration evaporation separation, first acetonitrile solution is evaporated
After device heating vaporization, then the acetonitrile solution steam that vaporizer is steamed is sent into infiltration evaporation seperator group and is separated.As excellent
Choosing, the temperature of acetonitrile solution steam is 60～160 DEG C.As improvement, the 2nd described step obtains being dehydrated acetonitrile steam without cold
Solidifying, send into the rectifying column of the 4th step with vapor phase, the temperature of dehydration acetonitrile is 50～150 DEG C.
Preferably, it is dehydrated the water content control of acetonitrile in the 2nd described step in 0.03～5wt.%.
Preferably, in the 2nd step, the gauge pressure of the feed liquid side of infiltrating and vaporizing membrane is 0～0.4mpa；Per-meate side and vacuum system
System is connected, and per-meate side absolute pressure is 100～4000pa.
The film that described infiltration evaporation separation unit adopts is preferential water permeable membrane, can be molecular screen membrane, amorphous dioxy
SiClx film, pva film, optimum is molecular screen membrane.Infiltration evaporation separation unit be connected by 1～100 Pervaporation membrane separator,
In parallel or series-parallel connection connects, to reach different processing requirements and production capacity.
As improvement, after the infiltration liquid condensing obtaining in the 2nd step, return concentration tower, overhead product returns again to the 2nd step
Infiltration evaporation membrane separator group.
As improvement, in the 1st step, crude acetonitrile, before acidic absorbent is absorbed, is being passed through load
There is the absorbing column of quick lime.
It is combined to the refining plant of acetonitrile for Ammonium Acetate, include the acid absorption tower being sequentially connected, concentration tower, infiltration
Vaporization separates unit, rectifying column；Wherein, the outlet of concentration tower separates the entrance connection of unit with infiltration evaporation, and infiltration evaporation divides
The per-meate side of group of disembarking is connected with the entrance of rectifying column.
Further, acid absorption tower is two-stage.
Further, the outlet of concentration tower is connected by the entrance that vaporizer separates unit with infiltration evaporation.
Further, the film that infiltration evaporation separation unit adopts is preferential water permeable membrane；Described preferential water permeable membrane is molecular sieve
Film, amorphous silica film, pva film.
Further, the per-meate side of infiltration evaporation separation unit is connected with penetrating fluid condenser and vacuum pump.
Further, it is also associated with alkaline absorption tower before acid absorption tower；In described alkaline absorption tower, filling is raw
Calx.
Beneficial effect
Compared with being combined to acetonitrile with double column pressure swing rectification method purification Ammonium Acetate, the method for the present invention has a characteristic that
1. the present invention adopts infiltration evaporation membrane separator group to be dehydrated, and is not limited by azeotropic, and technical process is simple, safety coefficient
Height,；
2. infiltration evaporation membrane separator group high degree of automation of the present invention, easy and simple to handle, occupation area of equipment is few；
3. this method is by the way of first concentration again infiltration evaporation, does not introduce third component it is ensured that product purity；
4. penetrating fluid is returned to concentration tower recycling by the present invention, decreases the discharge capacity of acetonitrile, improves returning of acetonitrile
Yield；
5. the present invention will be not condensed for infiltration evaporation product, enters rectifying column in vapour form, improves system self-energy
Utilization rate, reduce further the heating load of rectifying column；
6. the present invention adopts infiltration evaporation refined with rectifying column substep, realizes obtaining not by changing rectifying column operating parameter
With the demand of purity acetonitrile product, flexible operation；
7. the acetonitrile refining method that the present invention provides, material liquid circulating load is little, reduces tower quantity and size, runs energy
Consumption reduction by 30～60%.
Brief description
Fig. 1 is the acetonitrile refining process flow chart of acetic acid ammoniation process synthesizing acetonitrile；
Fig. 2 is the membrane flux change curve in subtractive process in embodiment 4 and embodiment 5.
Wherein 1 is ammoniation reactor, and 2 and 3 is acid absorption tower, and 4 is concentration tower, and 5 is pans, and 6 is vaporizer, and 7 are
Infiltration evaporation separation unit, 8 is rectifying column, and 9 is penetrating fluid condenser, and 10 is vacuum pump.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted concrete skill in embodiment
Art or condition person, are carried out according to the technology described by document in the art or condition or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, be can by city available from conventional products.
Approximate language used herein can be used for modifying any quantity statement in entire disclosure and claims, and it can
Permit being changed under conditions of not leading to its related basic function to change.Therefore, repaiied by the term of such as " about "
The value of decorations is not limited to specified exact value.In at least some cases, approximate language can be with the instrument for measuring this value
Precision corresponding.Unless indicated otherwise in context or sentence, otherwise range limit can be combined and/or exchange, and
And this scope is confirmed as and includes all subranges contained herein.Except operation embodiment in or elsewhere
In indicate outside, the numeral of the amount of all expression compositions used in specification and claims, reaction condition etc. or
Expression shall be construed as the modification by word " about " in all cases.
The purpose of the present invention is the acetonitrile refining process being combined in acetonitrile technique for Ammonium Acetate, in acetic acid aminating reaction
Afterwards, the crude product (containing acetonitrile, ammonia, acetic acid, water and other by-product) that reaction produces is absorbed by acidic absorbent
Process, the ammonia in product can be got rid of, operation stability, the end product quality of infiltration evaporation separator can be improved；Acid
Absorbent typically can adopt salt solution, such as hydrochloric acid, sulphuric acid etc., when carrying out absorbing process with acidic sorbent, best
It is to be absorbed by two grades, can further eliminate the alkaline impurities in crude product.After processing through acidic absorbent
Acetonitrile mother liquor carries out concentration by concentration tower again, concentration can by acetonitrile and water carry out preliminary separate, and absorb acid
Agent is stayed in aqueous phase, and the acetonitrile after concentration is dehydrated by infiltrating and vaporizing membrane, the water in the solution of feed liquid side and a small amount of
Acetonitrile obtains penetrating fluid through infiltrating and vaporizing membrane in vapour form, returns concentration tower, overhead product enters back into after infiltration liquid condensing
Infiltration evaporation separation unit, feed liquid side obtains being dehydrated acetonitrile, then is sent to be refined in rectifying column, obtains after imurity-removal
Purified acetonitrile.
In absorption section, the topmost purpose that crude product is carried out with two step absorptions is by the on-condensible gas in crude product
Emptying, excess of ammonia gas will be neutralized into as ammonium salt in reaction simultaneously, be stayed in acetonitrile mother liquor with acetonitrile and water.So on the one hand
On-condensible gas in system and acetonitrile can be separated, the excessive ammonia putting into can also be converted to ammonium salt solution, just in reaction
Removing in subsequent technique.In general, the water content in acetonitrile mother liquor is in 40～70wt.%, more suitable for this work
Skill is in 50wt.%.In addition, if if ammonia is not fully converted to ammonium salt, unconverted ammonia can be led to
Always present in acetonitrile solution, in addition to the life-span that meeting affects infiltrating and vaporizing membrane, the pure of final acetonitrile product also can be affected
Degree.In concentration workshop section, the acetonitrile mother liquor that absorption section is obtained carries out preliminary concentration, and topmost purpose is by acetonitrile mother liquor
In ammonium salt discharge from tower reactor with part water, ammonium salt so can be avoided to enter to the feed liquid side of infiltration evaporation separator, shadow
Ring the life-span of infiltrating and vaporizing membrane and the purity of final acetonitrile product, a part of water can also be removed, infiltrating and vaporizing membrane needed for reduction
Area so as to treating capacity and product water content improve.In this workshop section, if concentration tower overhead extraction water content is too high
Words, can lead to the ammonium salt in tower reactor to be dissolved in water and enter in overhead vapours with the process of rectification, final impact acetonitrile finished product
Purity, if instead if overhead extraction water content is too low, can lead to concentration tower operation energy consumption to increase.Preferably by acetonitrile mother liquor
Concentration, to ethane nitrile content 70～84wt.%, is 80wt.% in optimum embodiment.
According to another improved embodiment of the present invention, for the acetonitrile solution producing from concentration tower rectification,
Be well it is heated with vaporizer after, enter to infiltration evaporation separator in vapour form, this mainly can improve
Infiltration evaporation membrane separation efficiency, preferably 60～160 DEG C of the temperature of steam.For better profiting from waste heat, reduce refined behaviour
Make energy consumption, obtain crude product acetonitrile steam from infiltration evaporation separation unit feed liquid side, preferably without condensation, entered with vapor phase
Enter acetonitrile rectifying column, preferably 50～150 DEG C of the temperature of crude product acetonitrile steam.
One according to the present invention preferred embodiment, and the infiltrating and vaporizing membrane of employing is molecular screen membrane, with respect to other
Similar membrane material, for example: amorphous silica film, pva film, molecular screen membrane obtain a yield of crude product acetonitrile after separating
High and the membrane flux in separation process is larger.
According to an improved embodiment of the present invention, return after the infiltration liquid condensing that infiltration evaporation seperator group is isolated
Return concentration tower, distillate the acetonitrile containing certain water yield, return again to infiltration evaporation separation unit, this mainly can fully reclaim and ooze
A small amount of acetonitrile in transparent liquid, improves the total recovery of acetonitrile product, reduces the content of acetonitrile in waste water simultaneously.
Based on above method, a kind of refining plant that can adopt as shown in figure 1, ammoniation reactor 1 discharging opening according to
Secondary be connected with the acid absorption tower 2,3 of two-stage, be sulfuric acid solution in absorption tower, being connected with the import of concentration tower 4 again of absorption tower,
The tower top outlet of concentration tower 4 passes sequentially through pans 5 and vaporizer 6 separates the import connection of unit 7 with infiltration evaporation, permeates vapour
Another section of import with rectifying column 8 changing the feed liquid side separating unit 7 is connected, and per-meate side is connected with penetrating fluid condenser 9 He
Vacuum pump 10, then be connected with the entrance of concentration tower 4.
Embodiment 1
Ammonium Acetate is combined to the process for purification of acetonitrile, and the device of employing is as shown in figure 1, operating process comprises the following steps:
The crude product that will obtain from Ammonium Acetate reactor, the acid absorption tower sequentially entering two-stage is absorbed, in absorption tower all
For dilution heat of sulfuric acid, in the collection of absorbing tower bottom, from the emptying of absorption tower tower top, in tower, leftover materials are on-condensible gas acetonitrile mother liquor
Acetonitrile mother liquor (water content 50wt.% about), be re-fed into concentration tower concentration, and after concentration, ethane nitrile content improves to 80wt.%,
The acetonitrile solution obtaining is delivered to pans, and ammonium salt is discharged from bottom of towe with part water.By the aqueous acetonitrile hydraulic control in pans
Flow processed is respectively 1000,600,400kg/h be transported in vaporizer heating, acetonitrile solution is heated to 110 DEG C with steam
Form enters into that (every grade of membrane module area is 10m by 15 molecular screen membranes, silicon dioxide film, pva membrane module2) in series
Infiltration evaporation separation unit carries out dehydration and separates.Feed liquid lateral pressure is 0.2mpa (gauge pressure), and osmotic lateral pressure controls in 1000pa.
Coating materials liquid side feed liquid water content can significantly be reduced by infiltration evaporation membrane separator, obtains crude product acetonitrile, and it is not condensed straight
Connect and rectifying column is entered with vapor phase, under the suction of vacuum pump, the penetrating fluid obtaining condenses through penetrating fluid condenser per-meate side
Afterwards, it is back to concentration tower and process the wherein a small amount of acetonitrile of recovery.Rectification after crude product acetonitrile steam enters rectifying column obtains water content
The finished product acetonitrile of≤0.1wt.%.
When using different membrane material, the data such as the purification acetonitrile of gained, penetrating fluid, flux is as shown in table 1.Water flux
Converted according to running the average flux in 100 hours.
Table 1
| Film type | Naa molecular screen membrane | Silicon dioxide film | Pva film |
| Water flux kg/m2·h | 1.34 | 0.82 | 0.51 |
| Crude product acetonitrile water content wt.% | 0.50 | 0.61 | 0.69 |
| Infiltration liquid water content | 96.02 | 91.31 | 85.28 |
As can be seen from the table, molecular screen membrane is particularly suitable for the processed during purified acetonitrile, the process of gained
Amount, permeation flux are better than the membrane material of other species, and the water content of penetrating fluid is also superior to other several membrane materials.
Embodiment 2
Ammonium Acetate is combined to the process for purification of acetonitrile, and the device of employing is as shown in figure 1, operating process comprises the following steps:
The crude product that will obtain from Ammonium Acetate reactor, the acid absorption tower sequentially entering two-stage is absorbed, in absorption tower all
For dilution heat of sulfuric acid, in the collection of absorbing tower bottom, on-condensible gas is from the emptying of absorption tower tower top for acetonitrile mother liquor.Acetonitrile mother liquor is (aqueous
Amount 60wt.%) send into concentration tower concentration, after concentration ethane nitrile content be respectively increased to 70,75,80,84wt.%, obtain
To acetonitrile solution be delivered to pans, ammonium salt is discharged from bottom of towe with part water.Feed liquid in pans is controlled flow to divide
Not Wei 1145,1070,1000,952kg/h be transported in vaporizer heating, acetonitrile solution is heated to 110 DEG C with steam shape
Formula enters into that (every grade of membrane module area is 10m by several molecular screen membranes2) infiltration evaporation separation unit in series carries out
It is 808kg/h that dehydration separates to the crude product acetonitrile of water content 1wt.%.Feed liquid lateral pressure is 0.2mpa (gauge pressure), osmotic lateral pressure
Control in 2000pa.Coating materials liquid side feed liquid water content can significantly be reduced by infiltration evaporation membrane separator, obtains crude product acetonitrile,
Its not condensed direct entrance rectifying column in vapour form, under the suction of vacuum pump, the penetrating fluid obtaining is through infiltration for per-meate side
After the condensation of liquid condensing device, it is back to concentration tower and processes the wherein a small amount of acetonitrile of recovery.Crude product acetonitrile steam enters essence after rectifying column
Evaporate the finished product acetonitrile obtaining water content≤0.05wt.%.
When the acetonitrile solution using different moisture content is as the charging of membrance separation unit, the membrane module number of gained,
The data such as penetrating fluid water content, flux are as shown in table 2.Water flux is converted according to running the average flux in 100 hours.
Table 2
| Acetonitrile solution ethane nitrile content wt.% | 70 | 75 | 80 | 84 |
| Water flux kg/m2·h | 2.37 | 1.98 | 1.60 | 1.21 |
| Required membrane separator number | 14 | 13 | 12 | 12 |
| Penetrating fluid water content wt.% | 98.95 | 96.73 | 96.02 | 93.84 |
| Steam consumption t/t (crude product acetonitrile) | 1.56 | 1.50 | 1.44 | 1.65 |
As can be seen from the table, by the acetonitrile solution water content control of concentration tower in suitable scope, can be effective
Reduce the operation energy consumption of whole equipment and required membrane area.
Embodiment 3
Ammonium Acetate is combined to the process for purification of acetonitrile, and the device of employing is as shown in figure 1, operating process comprises the following steps:
The crude product that will obtain from Ammonium Acetate reactor, the acid absorption tower sequentially entering two-stage is absorbed, and acetonitrile mother liquor exists
Absorbing tower bottom is collected, and on-condensible gas is vented from absorption tower tower top.Acetonitrile mother liquor (water content 45wt.% about) send into concentration tower
Concentration, after concentration, ethane nitrile content improves to 80wt.%, and the acetonitrile solution obtaining is delivered to pans, ammonium salt and part
Water is discharged from bottom of towe.Acetonitrile solution in pans is controlled flow to be transported to heating, acetonitrile in vaporizer for 1600kg/h
Aqueous solution is heated to 110 DEG C and enters into that (every grade of membrane module area is 10m by several molecular screen membranes in vapour form2) series connection
The infiltration evaporation separation unit constituting carries out dehydration and separates.Feed liquid lateral pressure is 0.2mpa (gauge pressure), and osmotic lateral pressure is controlled respectively
System is 4000,2000,1000,500pa.Coating materials liquid side feed liquid water content can significantly be reduced by infiltration evaporation membrane separator,
Obtain crude product acetonitrile, its not condensed direct entrance rectifying column in vapour form, per-meate side, under the suction of vacuum pump, obtains
Penetrating fluid, after the condensation of penetrating fluid condenser, is back to concentration tower and processes the wherein a small amount of acetonitrile of recovery.Crude product acetonitrile enters essence
After evaporating tower, rectification obtains the finished product acetonitrile of water content≤0.03wt.%.Water flux enters according to running the average flux in 100 hours
Row conversion.
Table 3
| Crude product acetonitrile water content wt.% | 3 | 1 | 0.5 | 0.1 |
| Water flux kg/m2·h | 1.82 | 1.60 | 1.34 | 0.95 |
| Required membrane separator number | 15 | 19 | 23 | 32 |
| Infiltration liquid water content wt.% | 97.55 | 96.02 | 95.02 | 92.18 |
| Operating cost unit/t (finished product acetonitrile) | 559 | 475 | 496 | 542 |
As can be seen from the table, can in suitable scope by finished product (crude product acetonitrile) water content control of membrance separation unit
Obtain the operating cost of whole equipment and the optimization of required membrane area with effective.
Embodiment 4
Ammonium Acetate is combined to the process for purification of acetonitrile, and the device of employing is as shown in figure 1, operating process comprises the following steps:
The crude product that will obtain from Ammonium Acetate reactor, the acid absorption tower sequentially entering two-stage is absorbed, in absorption tower all
For dilution heat of sulfuric acid, in the collection of absorbing tower bottom, from the emptying of absorption tower tower top, in tower, leftover materials are on-condensible gas acetonitrile mother liquor
Acetonitrile mother liquor (water content 50wt.% about), be re-fed into concentration tower concentration, and after concentration, ethane nitrile content improves to 80wt.%,
The acetonitrile solution obtaining is delivered to pans, and ammonium salt is discharged from bottom of towe with part water.By the aqueous acetonitrile hydraulic control in pans
Flow processed is transported in vaporizer heating for 1000kg/h, acetonitrile solution be heated to 130 DEG C enter in vapour form by
(every grade of membrane module area is 8m to 15 molecular screen membrane membrane modules2) infiltration evaporation separation unit 7 in series carry out dehydration point
From.Feed liquid lateral pressure is 0.3mpa (gauge pressure), and osmotic lateral pressure controls in 1000pa.Coating materials liquid side feed liquid water content passes through infiltration
Vaporization membrance separation chance significantly reduces, and obtains crude product acetonitrile, and it is not condensed directly to enter rectifying column, infiltration with vapor phase
Under the suction of vacuum pump, the penetrating fluid obtaining, after the condensation of penetrating fluid condenser, is back to concentration tower and processes recovery wherein for side
A small amount of acetonitrile.After crude product acetonitrile steam entrance rectifying column, rectification obtains the finished product acetonitrile of water content 0.1wt.%.Run 200 little
When water flux as shown in Figure 2.Its water flux is by 1.85kg/ (m2H) drop to 1.47kg/ (m2·h).
Embodiment 5
Ammonium Acetate is combined to the process for purification of acetonitrile, and operating process comprises the following steps: from Ammonium Acetate reactor 1
The crude product obtaining, the acid absorption tower sequentially enter absorbing column (being filled with quick lime), sequentially entering two-stage is absorbed, and inhales
Receiving in tower is all dilution heat of sulfuric acid, and acetonitrile mother liquor is collected at absorbing tower bottom, and on-condensible gas is vented from absorption tower tower top, surplus in tower
Excess material is acetonitrile mother liquor (water content 50wt.% about), is re-fed into concentration tower concentration, after concentration ethane nitrile content improve to
80wt.% about, the acetonitrile solution obtaining is delivered to pans, and ammonium salt is discharged from bottom of towe with part water.By in pans
Acetonitrile solution controls flow to be transported to heating in vaporizer for 1000kg/h, and acetonitrile solution is heated to 130 DEG C with steam
Form enters into that (every grade of membrane module area is 8m by 15 molecular screen membrane membrane modules2) infiltration evaporation separation unit in series
Carry out dehydration to separate.Feed liquid lateral pressure is 0.3mpa (gauge pressure), and osmotic lateral pressure controls in 1000pa.Coating materials liquid side feed liquid water contains
Amount can significantly reduce by infiltration evaporation membrane separator, obtains crude product acetonitrile, its not condensed directly with vapor phase entrance
Rectifying column, under the suction of vacuum pump, the penetrating fluid obtaining, after the condensation of penetrating fluid condenser, is back at concentration tower per-meate side
Reason reclaims wherein a small amount of acetonitrile.After crude product acetonitrile steam entrance rectifying column, rectification obtains the finished product second of water content 0.1wt.%
Nitrile.The operation water flux of 200 hours is as shown in Figure 2.Its water flux is by 1.87kg/ (m2H) drop to 1.67kg/ (m2·h).
By embodiment 4 and embodiment 5 contrast as can be seen that water flux in embodiment 4 after continuous operation compared with initial flux,
Have dropped about 20.5%, and embodiment 5 is after the pretreatment of quick lime, continuously postrun water flux only about declines
10.7%.
Claims (6)
1. for Ammonium Acetate be combined to acetonitrile process for purification it is characterised in that comprise the steps: the 1st step, by acetic acid ammonification
The crude acetonitrile that reaction workshop section obtains is absorbed using acidic absorbent, obtains acetonitrile mother liquor；2nd step, acetonitrile mother liquor is carried out
Heating concentration, the dense acetonitrile obtaining is sent into infiltration evaporation separation unit and is dehydrated, and feed liquid side obtains being dehydrated acetonitrile；3rd step, general
Dehydration acetonitrile carries out rectified purified, obtains finished product acetonitrile；After heating concentration in the 2nd described step, acetonitrile in acetonitrile solution
Content concentration is to 80 wt.%.
2. according to claim 1 for Ammonium Acetate be combined to acetonitrile process for purification it is characterised in that: described the 1st
In step, acidic absorbent is to be absorbed by two-stage；The water content in acetonitrile mother liquor after absorption is in 40～70 wt.%.
3. according to claim 1 for Ammonium Acetate be combined to acetonitrile process for purification it is characterised in that: in the 2nd step,
When acetonitrile solution is done with infiltration evaporation separation, after first acetonitrile solution being vaporized with vaporizer heating, then vaporizer is steamed
The acetonitrile solution steam going out is sent into infiltration evaporation seperator group and is separated；The 2nd described step obtains being dehydrated acetonitrile steam without cold
Solidifying, send into the rectifying column of the 3rd step with vapor phase, the temperature of dehydration acetonitrile is 50～150 DEG C.
4. according to claim 1 for Ammonium Acetate be combined to acetonitrile process for purification it is characterised in that: described the 2nd
It is dehydrated the water content control of acetonitrile in 0.03～5 wt.% in step；In the 2nd step, the gauge pressure of the feed liquid side of infiltrating and vaporizing membrane is 0
～0.4 mpa；Per-meate side is connected with vacuum system, and per-meate side absolute pressure is 100～4000 pa.
5. according to claim 1 for Ammonium Acetate be combined to acetonitrile process for purification it is characterised in that: described infiltration
The film that vaporization separates unit employing is preferential water permeable membrane, and described preferential water permeable membrane is molecular screen membrane, amorphous silica film
Or pva film；Infiltration evaporation membrane separator group is to be connected by 1～100 infiltration evaporation separation unit series, parallel or series-parallel connection.
6. according to claim 1 for Ammonium Acetate be combined to acetonitrile process for purification it is characterised in that: in the 2nd step
Concentration tower is returned, overhead product returns again to the infiltration evaporation membrane separator group to the 2nd step after the infiltration liquid condensing arriving.
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| CN104447403B (en) * | 2014-12-23 | 2017-01-04 | 山东汇海医药化工有限公司 | The separation method of the acetonitrile crude product that a kind of synthetic method produces |
| CN104926690B (en) * | 2015-06-11 | 2017-07-14 | 江苏九天高科技股份有限公司 | The recovery process for purification and device of acetonitrile in a kind of synthesis for Ceftriaxone Sodium |
| CN106674043B (en) * | 2016-12-21 | 2019-08-06 | 南京九思高科技有限公司 | A kind of acetic acid ammonification prepares the device and method of acetonitrile of high purity |
| CN106631890B (en) * | 2016-12-27 | 2019-08-06 | 南京九思高科技有限公司 | A kind of technique and device of purified acetonitrile |
| CN116120210A (en) * | 2022-12-29 | 2023-05-16 | 南通立洋化学有限公司 | Purification method for preparing acetonitrile by acetic acid ammoniation method and application thereof |
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| CN101830829B (en) * | 2009-03-11 | 2013-08-14 | 于景东 | Method for synthesizing acetonitrile through one-step ammoniating method with acetic acid |
| CN101891648B (en) * | 2009-05-22 | 2014-01-08 | 于景东 | Method for preparing high-purity acetonitrile from acetic acid and ammonia by two steps |
| WO2013146609A1 (en) * | 2012-03-26 | 2013-10-03 | 旭化成ケミカルズ株式会社 | Method for purifying acetonitrile |
| CN104603101B (en) * | 2012-08-31 | 2017-03-01 | 旭化成株式会社 | The purification process of acetonitrile |
| CN103224456B (en) * | 2013-04-08 | 2015-04-22 | 江苏九天高科技股份有限公司 | Process and device for refining acetonitrile with a pervaporation method |
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