CN106187767A - A kind of process for purification and device removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid - Google Patents
A kind of process for purification and device removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid Download PDFInfo
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- CN106187767A CN106187767A CN201610725641.2A CN201610725641A CN106187767A CN 106187767 A CN106187767 A CN 106187767A CN 201610725641 A CN201610725641 A CN 201610725641A CN 106187767 A CN106187767 A CN 106187767A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The present invention relates to a kind of ethyl acetate waste liquid dehydration reclaimed for packages printing industry VOC retracting device and remove the process for purification of alcohol, step is as follows: the ethyl acetate waste liquid from packages printing industry VOC retracting device puts in reactor, add a certain amount of organic acid and catalyst reacting by heating, the mode using rectification carries out initial gross separation to ethyl acetate, and the thick ester of ethyl acetate, water and unreacted ethanol composition steams from rectification capital；Reflux in condensed rear section, in part extraction to transfer tank.Thick ester in transfer tank is sent into Pervaporation membrane separator and is carried out the isolated thick ester of dehydration, continues to react away remaining ethanol in being back to reactor after being dehydrated the condensation of thick ester, and whole for ethyl acetate extraction acquisition ethyl acetate is refined finished product.Ethyl acetate yield of the present invention reaches as high as 100%, and technical process is simple, is suitable for alcohol water content scope big, and equipment takes up an area little, and operation energy consumption is low, is particularly suitable for the refined needs of small lot ethyl acetate.
Description
Technical field
The present invention relates to a kind of process for purification removing alcohol for the dehydration of ethyl acetate waste liquid, particularly relate to a kind of esterification
Be combined waste liquid with pervaporation method and be dehydrated the method removing alcohol purified acetic acid ethyl ester, belong to infiltrating and vaporizing membrane application.
Background technology
Ethyl acetate is a kind of important Organic Chemicals, can be used for manufacturing acetamide, acetoacetic ester, methyl heptenyl
Ketone etc., and extensively apply in industries such as essence and flavoring agent, paint, medicine, senior ink, pyroxylin, nitrocellulose, dyestuffs.As
Binding agent, for printing-ink, the production of olivet；As extractant, for the production of the products such as medicine, organic acid；Make
For perfume base, for fruit essence and the primary raw materials of the spice such as whiskey, butter such as Fructus Ananadis comosi, Fructus Musae, Fructus Fragariae Ananssaes.Printing packaging
The ink that industry uses contains the ethyl acetate of 30～40%, and glue contains a certain amount of ethanol.After being completed for printing, empty by heat
Solvent is evaporated by gas, then is reclaimed the ethyl acetate waste liquid obtained containing ethanol Yu water by VOC retracting device.
Ethyl acetate is removed in the traditional handicraft of ethanol and water, (the second when ethanol is relatively low with the content of water in ethyl acetate
Acetoacetic ester purity >=95～98%), generally use the rectifying column rectification of single set, by cut out ethyl acetate, alcohol and water ternary or
The front-end volatiles of binary azeotrope composition reach the purpose of purified acetic acid ethyl ester, although this technique is simple, but actually used in only
Being limited to the situation that alcohol in ester is relatively low with water content, if alcohol is higher with the content of water, then the ethyl acetate yield of distillation process is very
Low.Additionally, ethyl acetate content about 60 ~ 80% in the front-end volatiles that cut out of rectification, this portion of ethyl acetate reclaim exist certain tired
Difficult.So, when in ethyl acetate, ethanol is higher with the content of water, the mode that simple rectification cuts out front-end volatiles is the most applicable, logical
Normal mode is to use extracting rectifying, and the difference of dissolubility when utilizing extractant to dissolve ethyl acetate, ethanol water, in extraction tower
Ethyl acetate being steamed as light component from tower top, second alcohol and water enters back into recovery with extractant after extraction tower tower reactor is discharged
Tower, steams second alcohol and water, reclaims extractant for recycled.Some processes such as Chinese patent, authorizes publication No.
Narration in " method of salting, compounding, extracting, rectifying separating ethyl acetate-ethanol-water mixed liquid " that CN100575332C authorizes
Use sodium acetate and organic composite extractant carry out extractive distillation with salt to ethyl acetate.Application publication number CN103467286A
" a kind of method of separating ethyl acetate-ethanol mixture " announced describes use ionic liquid or ionic liquid with organic
The composite extractant of solvent composition carries out extracting rectifying to ethyl acetate.But it is higher that this processing disadvantages is operation energy consumption, rectifying column
Bottom temperature is higher, and required steam quality requires height, and the content of the second alcohol and water simultaneously contained in ethyl acetate need to be the most fixing,
If fluctuation is big, then needs to adjust operating parameter, even need change equipment.Extraction rectification technique is mainly directed towards the body that treating capacity is bigger
System, if ethyl acetate waste liquid amount less (≤1000t/a), uses the problem that extraction rectification technique will face frequent start-stop car.And
And, use extracting rectifying to typically require at least two set rectifying columns, if refined ethanol, a set of rectifying column, a whole set of acetic acid need to be further added by
Ethyl ester reclaims process for refining equipment and takes up an area big.
Summary of the invention
It is an object of the invention to propose a kind of process for purification removing alcohol for the dehydration of ethyl acetate waste liquid.The method has
Technical process is simple, and occupation area of equipment is little, and safety coefficient is high, and energy consumption is low, and ethyl acetate yield is high, is suitable for alcohol water content scope
Greatly, alcohol water ratio does not limits, simple to operate, the feature of cleanliness without any pollution.
Technical scheme:
A kind of process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid, comprises the steps:
1st step, in the ethyl acetate waste liquid containing ethanol and water in printing packaging industry, adds organic acid and catalyst,
React；
2nd step, the steam that reaction produces is after rectifying column separates, and the light component of rectifying tower top is through condensation, condensed fluid part
Being back to rectifying column, part is sent in infiltrating and vaporizing membrane and is dehydrated；
3rd step, the ester obtained after infiltrating and vaporizing membrane dehydration, return to reactor reacts；
4th step, after ethanol and water content meet the requirements in infiltrating and vaporizing membrane retains the thick ester of dehydration of side, will be dehydrated thick ester whole
Extraction obtains ethyl acetate and refines finished product.
Wherein, the ethyl acetate waste liquid containing ethanol Yu water in described printing packaging industry refers to printing packaging industry
After packaging is carried out heat treatment, the waste liquid that the steam obtained is obtained through VOC retracting device.
The organic acid of the described addition in the 1st step can be acetic acid, maleic anhydride, citric acid, oxalic acid, caproic acid, lactic acid,
Optimum is acetic acid.
The described addition in the 1st step organic acid mole inventory is ethanol mole in ethyl acetate waste liquid 1～
1.5 times, optimum is 1.2 times.
The catalyst of the described addition in the 1st step can be concentrated sulphuric acid, acidic catalyst resin, and optimum is concentrated sulphuric acid.
In the 1st described step, the operating reflux ratio of rectifying column is 0.1～1.5.
In the 2nd step, after the condensed fluid carrying out being dehydrated in feeding infiltrating and vaporizing membrane needs first to vaporize with vaporizer heating,
It is re-fed into infiltration evaporation membrance separation；As preferably, the temperature of the steam obtained after heating vaporization is 70～160 DEG C.
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,
Per-meate side absolute pressure is 100～4000 Pa.
The film that described Pervaporation membrane separator uses is preferential water permeable membrane, can be molecular screen membrane, amorphous dioxy
SiClx film, PVA film, optimum is molecular screen membrane.
Infiltration evaporation membrane separator group is to be connected by 1～200 Pervaporation membrane separator series, parallel or series-parallel connection, with
Reach different process requirements and production capacity.
A kind of refining plant removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid, includes: reactor, reaction
The top of still arranges rectifying column, and the top of rectifying column is provided with capital condenser, and the condensate outlet of capital condenser leads to successively
Crossing transfer tank, vaporizer and separate unit connection with infiltration evaporation, it is cold that the per-meate side of infiltration evaporation separation unit is provided with penetrating fluid
Condenser, vacuum pump；The side connection that retains of infiltration evaporation separation unit has dehydration finished product condenser, the condensation of dehydration finished product condenser
Liquid outlet is connected with reactor.
The condensate outlet of described capital condenser is also connected with the capital of rectifying column.
VOC retracting device it is also associated with on described reactor.
Described VOC retracting device can use activated carbon adsorption retracting device, membrance separation retracting device, condensation to reclaim dress
Put.
Beneficial effect
Compared with the process for purification that alcohol is removed in the most conventional ethyl ester waste liquid dehydration, the method for the present invention has a characteristic that
1. the present invention uses infiltration evaporation membrane separator group to be dehydrated, and is not limited by azeotropic, and technical process is simple, and safety coefficient is high,；
Infiltration evaporation membrane separator group automaticity the most of the present invention is high, and easy and simple to handle, occupation area of equipment is few；
3. the present invention uses the mode of esterification to go alcohol, ethyl acetate yield to reach as high as more than 100%, good separating effect, with
Time the dehydration of infiltration evaporation membrane separator group may advantageously facilitate reaction and carry out；
4. the process for purification of alcohol is removed in the ethyl acetate waste liquid dehydration that the present invention provides, and reclaims ethyl acetate purity and reaches as high as
More than 99.7%, and reclaim ethyl acetate purity improve will not significantly improve investment；
5. the ethyl acetate waste liquid dehydration that the present invention provides removes the process for purification flexibility of alcohol greatly, alcohol in the ethyl acetate being suitable for
Water content may be up to 30%, and alcohol water ratio does not limits, and is not required to change device parameter, can process the acetic acid of different alcohol water content
Ethyl ester waste liquid.
6. the process for purification of alcohol is removed in the ethyl acetate waste liquid dehydration that the present invention provides, and the organic acid of input is completely used for instead
Should, unreacted organic acid can be used for lower batch of liquid waste processing.
Accompanying drawing explanation
Fig. 1 is the refining plant figure that alcohol is removed in the dehydration of ethyl acetate waste liquid；
Wherein, 1, reactor；2, rectifying column；3, capital condenser；4, transfer tank；5, vaporizer；6, infiltration evaporation separation unit；
7, vacuum pump；8, penetrating fluid condenser；9, dehydration finished product condenser.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail.But those skilled in the art will manage
Solving, 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, according to the technology described by the document in this area or condition or carried out according to product description.Examination used
Agent or instrument unreceipted production firm person, be can by city available from conventional products.
The value expressed using range format should be interpreted as in a flexible way not only including clearly listing as scope
The numerical value of limit value, but also include containing all single numerical value within the range or subinterval, just as each numerical value and Zi Qu
Between be expressly recited out.Such as, the concentration range of " about 0.1% to about 5% " should be understood to not only to include clearly to list
The concentration of about 0.1% to about 5%, also includes the single concentration (e.g., 1%, 2%, 3% and 4%) in the range of indication and subinterval (example
As, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Heretofore described percentage ratio without special instruction in the case of,
Refer to percentage by weight.
" embodiment ", " another embodiment ", " embodiment " addressed in this manual etc., refer to
In conjunction with this embodiment describe specific features, structure or be included in the application generality describe at least one embodiment in.
The most multiple local appearance statement of the same race is not necessarily to refer to same embodiment.Furthermore, it is understood that combine arbitrary
When embodiment describes a specific features, structure or feature, to be advocated is to combine other embodiments to realize this spy
Levy, structure or feature also fall in the application scope of the claimed.
It is an object of the invention to go the subtractive process of alcohol for the dehydration of ethyl acetate waste liquid, ethyl acetate containing alcohol waste liquid puts into
In reactor, and add a certain amount of organic acid and catalyst reacting by heating, rectifying column uses the mode of rectification to reactor
In ethyl acetate carry out initial gross separation, prevent organic acid to be distilled out of with catalyst, ethyl acetate, water and do not reacted away
Ethanol composition thick ester steam from rectification capital；Through capital condenser condensation rear section backflow, in part extraction to transfer tank.
Thick ester in transfer tank is sent into Pervaporation membrane separator and is carried out the isolated thick ester of dehydration, is back to anti-after being dehydrated the condensation of thick ester
Continue to react remaining ethanol in answering still, until ethanol meets the requirements with the content of water in ethyl acetate, ethyl acetate is whole
Extraction obtains ethyl acetate and refines finished product.
In the present invention, the ethyl acetate waste liquid containing ethanol Yu water in described printing packaging industry refers to printing packaging
After industry carries out heat treatment to packaging, the waste liquid that the steam obtained is obtained through VOC retracting device；Have in the middle of these waste liquids
From the ethyl acetate in ink and water, the second alcohol and water come from glue, it addition, some other in ink and glue can
Volatile ingredient also can reside in the middle of waste liquid, such as: the volatile material such as hydro carbons, benzene class, ethers, acrylic compounds, isocyanates.
Feed liquid or VOC recovered liquid are processed by the pretreatment mode that can also use other, to reduce other impurity therein
Point, such as adsorb, absorption etc..
Can be reclaimed by the steam during VOC retracting device packaging produces, to obtain VOCs therein, used
VOC retracting device is not particularly limited, and activated carbon adsorption retracting device, membrance separation retracting device, condensation can be used to reclaim dress
Put.
One according to the present invention preferred embodiment, uses acetic acid as organic acid, have relative to other during reaction
Machine acid, such as: acetic acid, maleic anhydride, citric acid, oxalic acid, caproic acid and lactic acid, acetic acid and ethanol synthesis produce ethyl acetate, no
New impurity can be produced, and separation process is remarkably improved the yield of ethyl acetate.
One according to the present invention preferred embodiment, and the organic acid mole inventory added before reaction is ethyl acetate
In waste liquid 1～1.5 times of ethanol mole, optimum is 1.2 times, and this inventory both can ensure that ethanol is fully reacted, and also will not
Cause organic acid excess too many.
According to another embodiment improved of the present invention, for the thick ester of rectifying column extraction condensed after, preferably
After the heating vaporization of thick ester vaporizer, the thicker ester steam steamed by vaporizer sends into infiltration evaporation membrane separator component
From.As preferably, the temperature of thick ester steam is 70～160 DEG C.
One according to the present invention preferred embodiment, and the infiltrating and vaporizing membrane of employing is molecular screen membrane, relative to other
Similar membrane material, such as: amorphous silica film, PVA film, molecular screen membrane obtain being dehydrated a yield of thick ester after separating
High and membrane flux of in separation process is bigger.
The refining plant that the present invention provides, its structure is as it is shown in figure 1, include: reactor 1, and the top of reactor 1 is arranged
Rectifying column 2, the top of rectifying column 2 is provided with capital condenser 3, and the condensate outlet of capital condenser 3 passes sequentially through transfer tank
4, vaporizer 5 separates unit 6 and connects with infiltration evaporation, and the per-meate side of infiltration evaporation separation unit 6 is provided with penetrating fluid condenser
8, vacuum pump 7；The side connection that retains of infiltration evaporation separation unit 6 has dehydration finished product condenser 9, is dehydrated the cold of finished product condenser 9
Condensate outlet is connected with reactor 1；The condensate outlet of described capital condenser 3 also capital with rectifying column 2 is connected；Separately
Outward, described reactor 1 is also associated with VOC retracting device, for the steam in packaging operation is carried out VOC recovery, described
VOC retracting device can use activated carbon adsorption retracting device, membrance separation retracting device, condensate recycling device etc..
Embodiment 1
The process for purification of alcohol is removed in the dehydration of ethyl acetate waste liquid, and the device of employing is as it is shown in figure 1, operating process comprises the following steps:
3000 kg ethyl acetate containing alcohol waste liquids (main component is: 53% water, 24% ethyl acetate, 18% ethanol, 3% hydro carbons) put into reaction
In still 1, and according to 1.5 times of addition organic acid of ethanol mole, and 10kg concentrated sulphuric acid reacting by heating, rectifying column 2 uses essence
The mode evaporated carries out initial gross separation to the ethyl acetate in reactor, prevents organic acid to be distilled out of, ethyl acetate, water, Yi Jiwei
The thick ester of the ethanol composition reacted away steams from rectification capital；Condense rear section through capital condenser 3 and be back to rectifying column 3,
Part extraction is to transfer tank 4.Thick ester feeding vaporizer 5 in transfer tank 4 is heated to 110 DEG C and enters in vapour form by 8
(every grade of membrane module area is 1 m for individual molecular screen membrane, silicon dioxide film, PVA film assembly2) infiltration evaporation membrance separation in series
Device 6 carries out dehydration and separates.Feed liquid lateral pressure is 0.2 MPa(gauge pressure), osmotic lateral pressure controls at 1000 Pa.Feed liquid side solution
In water and a small amount of ethyl acetate obtain penetrating fluid through infiltrating and vaporizing membrane in vapour form, per-meate side is taken out vacuum pump 7
Under suction, the penetrating fluid obtained condenses through penetrating fluid condenser 8.Coating materials liquid side feed liquid water content passes through infiltration evaporation membrane separator meeting
Reduce significantly, obtain being dehydrated thick ester, be dehydrated in thick ester is back to reactor 1 after dehydration finished product condenser 9 condensation and continue instead
Answering remaining ethanol, until ethyl acetate terminating during ethanol content≤0.5wt.% run, whole for ethyl acetate extraction being obtained
Ethyl acetate refines finished product.
When using different membrane material, the data such as the thick ester of dehydration of gained, penetrating fluid, flux are as shown in table 1.Average water
Flux is converted according to the average flux processing 10 batches of waste liquids with penetrating fluid water content.
Table 1
As can be seen from the table, molecular screen membrane is particularly suitable for the processed during alcohol is removed in the dehydration of ethyl acetate waste liquid, institute
Penetrating fluid water content, water flux be better than the membrane material of other kind, simultaneously because dehydrating effect is more preferable, the reaction to ethanol
Facilitation effect becomes apparent from, and reaches to process equally when requiring, operation hours is shorter.
Embodiment 2
The process for purification of alcohol is removed in the dehydration of ethyl acetate waste liquid, and the device of employing is as it is shown in figure 1, operating process comprises the following steps:
3000 kg ethyl acetate containing alcohol waste liquids (main component is: 45% water, 31% ethyl acetate, 20% ethanol, 1% ether solvent) put into
In reactor 1, and respectively according to 1,1.2,1.5 times of addition acetic acid of ethanol mole, and 10kg concentrated sulphuric acid reacting by heating, rectification
The mode using rectification in post 2 carries out initial gross separation to the ethyl acetate in reactor, prevents organic acid to be distilled out of, acetic acid second
The thick ester that ester, water and the ethanol not reacted away form steams from rectification capital；Press respectively after capital condenser 3 condenses
Carrying out being partly refluxed to rectifying column 3 according to reflux ratio, part extraction is to transfer tank 4.Thick ester in transfer tank 4 sends into vaporizer 5 quilt
It is heated to 110 DEG C and enters into by 8 molecular screen membranes that (every grade of membrane module area is 1 m in vapour form2) infiltration in series
Vaporization membrane separator 6 carries out dehydration and separates.Feed liquid lateral pressure is 0.2 MPa(gauge pressure), osmotic lateral pressure controls at 500 Pa.Material
Water and a small amount of ethyl acetate in the solution of liquid side obtain penetrating fluid through infiltrating and vaporizing membrane in vapour form, and per-meate side is in vacuum
Under the suction of pump 7, the penetrating fluid obtained condenses through penetrating fluid condenser 8.Coating materials liquid side feed liquid water content passes through infiltrating and vaporizing membrane
Seperator can reduce significantly, obtains being dehydrated thick ester, is dehydrated thick ester and is back to reactor 1 after dehydration finished product condenser 9 condensation
Interior continuation reacts remaining ethanol, until terminating during ethanol content≤0.1wt.% in ethyl acetate running, ethyl acetate is whole
Extraction obtains ethyl acetate and refines finished product.
The data such as the thick ester of dehydration of gained, penetrating fluid, flux are as shown in table 2.Distillate pH value is according to processing 10 batches of waste liquids
Distillate pH value testing result convert.
Table 2
As can be seen from the table, before reaction, acetic acid molar feed ratio is the biggest, and in ethyl acetate, ethanol removal is the fastest, but puts into
Many acetic acid, can cause the pH of rectifying column distillate to decline, thus affect the life-span of molecular screen membrane longtime running.
Embodiment 3
The process for purification of alcohol is removed in the dehydration of ethyl acetate waste liquid, and the device of employing is as it is shown in figure 1, operating process comprises the following steps:
3000 kg ethyl acetate containing alcohol waste liquids (main component is: 32% water, 37% ethyl acetate, 23% ethanol, 5% hydro carbons) put into reaction
In still 1, and respectively according to 1.2 times of additions acetic acid, maleic anhydride, citric acid, caproic acids of ethanol mole, and 10kg concentrated sulphuric acid adds
Thermal response, uses the mode of rectification that the ethyl acetate in reactor is carried out initial gross separation, prevents organic acid from being steamed in rectifying column 2
Going out, the thick ester that ethyl acetate, water and the ethanol not reacted away form steams from rectification capital；Condense through capital condenser 3
Rear carrying out being partly refluxed to rectifying column 3 according to reflux ratio respectively, part extraction is to transfer tank 4.Thick ester in transfer tank 4 is sent into and is steamed
Send out device 5 to be heated to 120 DEG C and enter into by 8 molecular screen membranes that (every grade of membrane module area is 1 m in vapour form2) in series
Pervaporation membrane separator 6 carry out dehydration separate.Feed liquid lateral pressure is 0.25 MPa(gauge pressure), osmotic lateral pressure controls
700 Pa.Water and a small amount of ethyl acetate in the solution of feed liquid side obtain penetrating fluid through infiltrating and vaporizing membrane in vapour form, ooze
Side is under the suction of vacuum pump 7 thoroughly, and the penetrating fluid obtained condenses through penetrating fluid condenser 8.Coating materials liquid side feed liquid water content passes through
Infiltration evaporation membrane separator can reduce significantly, obtains being dehydrated thick ester, is dehydrated thick ester and returns after dehydration finished product condenser 9 condensation
Continue to react remaining ethanol, until ethyl acetate terminating during ethanol content≤0.3wt.% run, by second to reactor 1
The whole extraction of acetoacetic ester obtains ethyl acetate and refines finished product.
The ethyl acetate yield of gained, ethanol content are down to the 2wt.% operation time, ethanol content is down to 0.3wt.% and is run
At the end of time and reaction, reactor component is as shown in table 3.Equipment average operating time is according to the operation processing 10 batches of waste liquids
Time converts.
Table 3
As can be seen from the table, when using maleic anhydride to participate in reaction as organic acid, it is the fastest that reaction is carried out, the reaction of acetic acid
Time is placed in the middle, but for ethyl acetate system, uses acetic acid to be remarkably improved yield, reduces waste liquid and by-product produces.
Embodiment 4
The process for purification of alcohol is removed in the dehydration of ethyl acetate waste liquid, and the device of employing is as it is shown in figure 1, operating process comprises the following steps:
3000 kg ethyl acetate containing alcohol waste liquids (main component is: 51% water, 35% ethyl acetate, 12% ethanol, 1% propylene glycol monomethyl ether) are thrown
Enter in reactor 1, and respectively according to 1.5 times of addition acetic acid of ethanol mole, and 10kg concentrated sulphuric acid reacting by heating, rectifying column 2
The mode of middle employing rectification carries out initial gross separation to the ethyl acetate in reactor, prevents organic acid to be distilled out of, ethyl acetate,
The thick ester that water and the ethanol not reacted away form steams from rectification capital；Respectively according to returning after capital condenser 3 condenses
Flow ratio carries out being partly refluxed to rectifying column 3, and part extraction is to transfer tank 4.Thick ester in transfer tank 4 is sent into vaporizer 5 and is heated
Enter into by 10 molecular screen membranes to 130 DEG C that (every grade of membrane module area is 1 m in vapour form2) infiltration evaporation in series
Membrane separator 6 carries out dehydration and separates.Feed liquid lateral pressure is respectively 0.05,0.1,0.15,0.2,0.25 MPa(gauge pressure), per-meate side
Stress control is at 900 Pa.Water and a small amount of ethyl acetate in the solution of feed liquid side obtain through infiltrating and vaporizing membrane in vapour form
Penetrating fluid, per-meate side is under the suction of vacuum pump 7, and the penetrating fluid obtained condenses through penetrating fluid condenser 8.Coating materials liquid side feed liquid water
Content can be reduced significantly by infiltration evaporation membrane separator, obtains being dehydrated thick ester, is dehydrated thick ester cold through dehydration finished product condenser 9
Continue to react remaining ethanol in being back to reactor 1 after Ning, until ethyl acetate terminates during ethanol content≤0.1wt.% fortune
OK, whole for ethyl acetate extraction acquisition ethyl acetate is refined finished product.
The data such as the thick ester of dehydration of gained, penetrating fluid, flux are as shown in table 4.Distillate pH value is according to processing 10 batches of waste liquids
Distillate pH value testing result convert.
Table 4
Embodiment 5
The process for purification of alcohol is removed in the dehydration of ethyl acetate waste liquid, and the device of employing is as it is shown in figure 1, operating process comprises the following steps:
3000 kg ethyl acetate containing alcohol waste liquids (main component is: 51% water, 35% ethyl acetate, 12% ethanol, 1% propylene glycol monomethyl ether) are thrown
Enter in reactor 1, and respectively according to 1.5 times of addition acetic acid of ethanol mole, and 10kg concentrated sulphuric acid reacting by heating, rectifying column 2
The mode of middle employing rectification carries out initial gross separation to the ethyl acetate in reactor, prevents organic acid to be distilled out of, ethyl acetate,
The thick ester that water and the ethanol not reacted away form steams from rectification capital；Respectively according to returning after capital condenser 3 condenses
Flow ratio carries out being partly refluxed to rectifying column 3, and part extraction is to transfer tank 4.Thick ester in transfer tank 4 processes through activated carbon adsorption
After, feed liquid feeding vaporizer 5 is heated to 130 DEG C and enters in vapour form by 10 molecular screen membranes (every grade of membrane module area
It is 1 m2) Pervaporation membrane separator 6 in series carry out dehydration separate.Feed liquid lateral pressure is respectively 0.05,0.1,0.15,
0.2,0.25 MPa(gauge pressure), osmotic lateral pressure controls at 900 Pa.Water in the solution of feed liquid side and a small amount of ethyl acetate with
Vapor form obtains penetrating fluid through infiltrating and vaporizing membrane, and per-meate side is under the suction of vacuum pump 7, and the penetrating fluid obtained is through penetrating fluid
Condenser 8 condenses.Coating materials liquid side feed liquid water content can be reduced significantly by infiltration evaporation membrane separator, obtains being dehydrated thick ester,
It is dehydrated in thick ester is back to reactor 1 after dehydration finished product condenser 9 condensation and continues to react remaining ethanol, until ethyl acetate
Terminate during middle ethanol content≤0.1wt.% running, whole for ethyl acetate extraction acquisition ethyl acetate is refined finished product.
The data such as the thick ester of dehydration of gained, penetrating fluid, flux are as shown in table 5.Distillate pH value is according to processing 10 batches of waste liquids
Distillate pH value testing result convert.
Table 5
Embodiment 6
The process for purification of alcohol is removed in the dehydration of ethyl acetate waste liquid, and the device of employing is as it is shown in figure 1, operating process comprises the following steps:
3000 kg ethyl acetate containing alcohol waste liquids (main component is: 45% water, 35% ethyl acetate, 16% ethanol, 1% propylene glycol monomethyl ether) are thrown
Enter in reactor 1, and respectively according to 1.3 times of addition acetic acid of ethanol mole, and 8kg concentrated sulphuric acid reacting by heating, in rectifying column 2
Use rectification mode the ethyl acetate in reactor is carried out initial gross separation, prevent organic acid to be distilled out of, ethyl acetate, water,
And the thick ester of the ethanol composition not reacted away steams from rectification capital；Respectively according to backflow after capital condenser 3 condenses
Ratio carries out being partly refluxed to rectifying column 3, and part extraction is to transfer tank 4.Thick ester in transfer tank 4 is sent into vaporizer 5 and is heated to
140 DEG C enter in vapour form by 8 molecular screen membranes that (every grade of membrane module area is 1 m2) infiltrating and vaporizing membrane in series
Separator 6 carries out dehydration and separates.Feed liquid lateral pressure is respectively 0.1MPa(gauge pressure), osmotic lateral pressure controls at 300-1000 Pa.
Water and a small amount of ethyl acetate in the solution of feed liquid side obtain penetrating fluid through infiltrating and vaporizing membrane in vapour form, and per-meate side is very
Under the suction of empty pump 7, the penetrating fluid obtained condenses through penetrating fluid condenser 8.Coating materials liquid side feed liquid water content passes through infiltration evaporation
Membrance separation chance reduces significantly, obtains being dehydrated thick ester, is dehydrated thick ester and is back to reactor after dehydration finished product condenser 9 condensation
Continue in 1 to react remaining ethanol, until ethyl acetate terminating during ethanol content≤0.1wt.% run, ethyl acetate is complete
Portion's extraction obtains ethyl acetate and refines finished product.
The data such as the thick ester of dehydration of gained, penetrating fluid, flux are as shown in table 6.Distillate pH value is according to processing 10 batches of waste liquids
Distillate pH value testing result convert.
Table 6
Claims (10)
1. the process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid, it is characterised in that include as follows
Step: the 1st step, in the ethyl acetate waste liquid containing ethanol and water in printing packaging industry, adds organic acid and catalyst,
React；2nd step, the steam that reaction produces is after rectifying column separates, and the light component of rectifying tower top is through condensation, condensed fluid
Being partly refluxed to rectifying column, part is sent in infiltrating and vaporizing membrane and is dehydrated；3rd step, the ester obtained after infiltrating and vaporizing membrane dehydration,
Return to reactor reacts；4th step, in infiltrating and vaporizing membrane retains the thick ester of dehydration of side, ethanol meets the requirements with water content
After, thick for dehydration ester whole extraction acquisition ethyl acetate is refined finished product.
The process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 1, it is special
Levying and be, the ethyl acetate waste liquid containing ethanol Yu water in described printing packaging industry refers to that printing packaging industry is to packaging
After carrying out heat treatment, the waste liquid that the steam obtained is obtained through VOC retracting device.
The process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 1, it is special
Levying and be, the organic acid of the described addition in the 1st step can be acetic acid, maleic anhydride, citric acid, oxalic acid, caproic acid, lactic acid,
Optimum is acetic acid.
The process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 1, it is special
Levy and be, the described addition in the 1st step organic acid mole inventory is ethanol mole in ethyl acetate waste liquid 1～
1.5 times, optimum is 1.2 times.
The process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 1, it is special
Levying and be, the catalyst of the described addition in the 1st step can be concentrated sulphuric acid, acidic catalyst resin, and optimum is concentrated sulphuric acid.
The process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 1, it is special
Levying and be, in the 1st described step, the operating reflux ratio of rectifying column is 0.1～1.5.
The process for purification removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 1, it is special
Levy and be, in the 2nd step, after the condensed fluid carrying out being dehydrated in feeding infiltrating and vaporizing membrane needs first to vaporize with vaporizer heating,
It is re-fed into infiltration evaporation membrance separation；As preferably, the temperature of the steam obtained after heating vaporization is 70～160 DEG C；In the 2nd step
In, the gauge pressure of the feed liquid side of infiltrating and vaporizing membrane is 0～0.6 MPa；Per-meate side is connected with vacuum system, and per-meate side absolute pressure is 100
～10000 Pa；The film that described Pervaporation membrane separator uses is preferential water permeable membrane, can be molecular screen membrane, amorphous two
Silicon oxide film, PVA film, optimum is molecular screen membrane；Infiltration evaporation membrane separator group is by 1～200 Pervaporation membrane separator
Series, parallel or series-parallel connection connect.
8. the refining plant removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid, it is characterised in that include: anti-
Answering still (1), the top of reactor (1) to arrange rectifying column (2), the top of rectifying column (2) is provided with capital condenser (3), capital
The condensate outlet of condenser (3) passes sequentially through transfer tank (4), vaporizer (5) separates unit (6) and connects with infiltration evaporation, oozes
The per-meate side of vaporization separation unit (6) is provided with penetrating fluid condenser (8), vacuum pump (7) thoroughly；Infiltration evaporation separation unit (6)
Retain side connect have dehydration finished product condenser (9), dehydration finished product condenser (9) condensate outlet be connected with reactor (1).
The refining plant removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 8, it is special
Levying and be, the condensate outlet of described capital condenser (3) also capital with rectifying column (2) is connected；Described reactor (1)
On be also associated with VOC retracting device；Described VOC retracting device can use activated carbon adsorption retracting device, membrance separation to reclaim
Device, condensate recycling device etc..
The refining plant removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid the most according to claim 8, it is special
Levying and be, the film that described infiltration evaporation separation unit (6) uses is preferential water permeable membrane, can be molecular screen membrane, amorphous two
Silicon oxide film, PVA film, optimum is molecular screen membrane；Infiltration evaporation separation unit (6) is by 1～200 Pervaporation membrane separator
Series, parallel or series-parallel connection connect.
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| CN106587475A (en) * | 2016-12-21 | 2017-04-26 | 苏州市晶协高新电子材料有限公司 | Apparatus and method for recycling ethyl acetate in waste liquid by using super-gravity bed combining membrane separation technology |
| CN111229134A (en) * | 2020-03-24 | 2020-06-05 | 安徽立兴化工有限公司 | Chemical production equipment and use method |
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