CN206033625U - A refining plant that is used for package printing trade ethyl acetate waste liquid dehydration to remove mellow wine - Google Patents
A refining plant that is used for package printing trade ethyl acetate waste liquid dehydration to remove mellow wine Download PDFInfo
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- CN206033625U CN206033625U CN201620940262.0U CN201620940262U CN206033625U CN 206033625 U CN206033625 U CN 206033625U CN 201620940262 U CN201620940262 U CN 201620940262U CN 206033625 U CN206033625 U CN 206033625U
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- ethyl acetate
- condenser
- waste liquid
- dehydrated
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 329
- 239000007788 liquid Substances 0.000 title claims abstract description 83
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 230000018044 dehydration Effects 0.000 title claims abstract description 47
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 47
- 238000007639 printing Methods 0.000 title claims abstract description 20
- 238000007670 refining Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000001764 infiltration Methods 0.000 claims abstract description 28
- 230000008595 infiltration Effects 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 230000008016 vaporization Effects 0.000 claims abstract description 22
- 239000012466 permeate Substances 0.000 claims abstract description 12
- 238000009834 vaporization Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 195
- 239000012528 membrane Substances 0.000 claims description 59
- 239000012530 fluid Substances 0.000 claims description 31
- 230000000149 penetrating effect Effects 0.000 claims description 29
- 238000001704 evaporation Methods 0.000 claims description 23
- 230000008020 evaporation Effects 0.000 claims description 23
- 239000006200 vaporizer Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000005373 pervaporation Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 35
- 239000003507 refrigerant Substances 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 description 85
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 59
- 150000002148 esters Chemical class 0.000 description 46
- 208000005156 Dehydration Diseases 0.000 description 42
- 150000007524 organic acids Chemical class 0.000 description 19
- 238000000605 extraction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000012855 volatile organic compound Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000000746 purification Methods 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003204 osmotic effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000686 essence Substances 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 229940079938 nitrocellulose Drugs 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 1
- FMYHFHVAPZDDPJ-UHFFFAOYSA-N ethanol;ethyl acetate;hydrate Chemical compound O.CCO.CCOC(C)=O FMYHFHVAPZDDPJ-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- HDKLIZDXVUCLHQ-UHFFFAOYSA-N non-3-en-2-one Chemical compound CCCCCC=CC(C)=O HDKLIZDXVUCLHQ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model relates to a refining plant that is used for package printing trade ethyl acetate waste liquid dehydration to remove mellow wine, including: reation kettle (1), the upper portion of reation kettle (1) sets up rectifying column (2), and the top of rectifying column (2) is provided with capital condenser (3), and the cold refrigerant outlet of capital condenser (3) loops through transfer jar (4), evaporimeter (5) and permeates vaporization separation unit (6) and be connected, and infiltration vaporization separation unit's (6) infiltration side is provided with penetrant condenser (8), vacuum pump (7), infiltration vaporization separation unit's (6) the side of holding back is connected with dehydration finished product condenser (9), and the cold refrigerant outlet of dehydration finished product condenser (9) is connected with reation kettle (1). The utility model discloses it is simple that the ethyl acetate yield reaches as high as 100%, process, and it is big to be suitable for pure water content scope, and equipment takes up an area of for a short time, and operating power consumption is low, and the volume of being particularly suitable for small batch ethyl acetate is refined to be needed.
Description
Technical field
This utility model is related to a kind of refining plant for removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid, and category oozes
Vaporize thoroughly film application.
Background technology
Ethyl acetate is a kind of important Organic Chemicals, can be used to manufacture acetamide, acetoacetic ester, methyl heptenyl
Ketone etc., and extensively apply in industries such as essence and flavoring agent, paint, medical, 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 the primary raw material of the spice such as the fruit essences such as Fructus Ananadis comosi, Fructus Musae, Fructus Fragariae Ananssae and whiskey, butter.Printing packaging
Industry using ink contain 30～40% ethyl acetate, glue contains a certain amount of ethanol.After being completed for printing, with hot sky
Solvent is evaporated by gas, then obtains the ethyl acetate waste liquid containing ethanol Yu water by the recovery of VOC retracting devices.
Ethyl acetate is removed in the traditional handicraft of ethanol and water, when in ethyl acetate, ethanol is relatively low with the content of water（Second
Acetoacetic ester purity >=95～98%）, generally using 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 are reaching the purpose of purified acetic acid ethyl ester, although the technique is simple, it is actually used in only
It is limited to alcohol and the relatively low situation of water content in ester, if alcohol is higher with the content of water, the ethyl acetate yield of distillation process is very
It is low.Additionally, ethyl acetate content about 60 ~ 80% in the front-end volatiles that cut out of rectification, this portion of ethyl acetate reclaim exists it is certain tired
It is difficult.So, when in ethyl acetate, ethanol is higher with the content of water, simple rectification cuts out the mode of front-end volatiles and is no longer suitable for, and leads to
Normal mode is to adopt extracting rectifying, and the difference of dissolubility when dissolving ethyl acetate, ethanol water using extractant, in extraction tower
Steam ethyl acetate as light component from tower top, second alcohol and water enters back into recovery with extractant from after the discharge of extraction tower tower reactor
Tower, steams second alcohol and water, and reclaiming extractant is used for recycled.Some processes such as Chinese patent, authorizes publication No.
What CN100575332C was authorized《The method of salting, compounding, extracting, rectifying separating ethyl acetate-ethanol-water mixed liquid》Middle narration
Extractive distillation with salt is carried out to ethyl acetate using sodium acetate and organic composite extractant.Application publication number CN103467286A
Announce《A kind of method of separating ethyl acetate-ethanol mixture》In describe using ionic liquid or ionic liquid with it is organic
The composite extractant of solvent composition carries out extracting rectifying to ethyl acetate.But the processing disadvantages are that operation energy consumption is higher, rectifying column
Bottom temperature is higher, and required steam quality has high demands, while the content of the second alcohol and water contained in ethyl acetate more need to be fixed,
If fluctuation is big, needs to adjust operating parameter, or even need change equipment.Extraction rectification technique is mainly directed towards the larger body for the treatment of capacity
System, if ethyl acetate waste liquid amount is less（≤1000t/a）, the problem of frequent driving and parking will be faced using extraction rectification technique.And
And, at least two sets rectifying columns are generally needed using extracting rectifying, if refined ethanol, need to be further added by a set of rectifying column, a whole set of acetic acid
Ethyl ester reclaims process for refining equipment and takes up an area greatly.
The content of the invention
The purpose of this utility model is to propose a kind of refining plant for removing alcohol for the dehydration of ethyl acetate waste liquid.The method
Simple with technical process, occupation area of equipment is little, and safety coefficient is high, and energy consumption is low, ethyl acetate high income, is suitable for alcohol water content
Scope is big, and alcohol water ratio is not limited, simple to operate, the characteristics of cleanliness without any pollution.
Technical scheme：
A kind of process for purification for 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 with water in printing packaging industry, adds organic acid and catalysis
Agent, is reacted；
2nd step, reacts the steam for producing after rectifying column separation, and rectifying tower top light component is through condensation, condensed fluid
Rectifying column is partly refluxed to, part is dehydrated in sending into infiltrating and vaporizing membrane；
3rd step, the ester obtained after infiltrating and vaporizing membrane dehydration, is reacted in returning to reactor；
4th step, after ethanol is met the requirements with water content in infiltrating and vaporizing membrane retains the thick ester of dehydration of side, will be dehydrated thick ester
All extraction obtains the refined finished product of ethyl acetate.
Wherein, the ethyl acetate waste liquid containing ethanol with water in described printing packaging industry refers to printing packaging industry
Packaging is carried out after heat treatment, the waste liquid that the steam for obtaining is obtained through VOC retracting devices.
The organic acid of the addition in the 1st described step can be acetic acid, maleic anhydride, citric acid, oxalic acid, caproic acid, lactic acid,
Optimum is acetic acid.
The organic acid mole inventory of the addition in the 1st described step be ethyl acetate waste liquid in ethanol mole 1～
1.5 times, optimum is 1.2 times.
The catalyst of the addition in the 1st described 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 being dehydrated in sending into infiltrating and vaporizing membrane needs first to be vaporized with vaporizer heating,
It is re-fed into infiltration evaporation membrance separation；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 is adopted is preferential water permeable membrane, can be molecular screen membrane, amorphous dioxy
SiClx film, PVA film, optimum are molecular screen membranes.
Infiltration evaporation membrane separator group is connected by 1～200 Pervaporation membrane separator series, parallel or series-parallel connection, with
Reach different processing requirements and production capacity.
A kind of refining plant for removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid, includes：Reactor, reaction
The top of kettle arranges rectifying column, is provided with capital condenser at the top of rectifying column, and the condensate outlet of capital condenser leads to successively
Cross transfer tank, vaporizer and separate unit connection with infiltration evaporation, infiltration evaporation separates the per-meate side of unit, and to be provided with penetrating fluid cold
Condenser, vacuum pump；Infiltration evaporation separates the retention side of unit and is connected with dehydration finished product condenser, is dehydrated the condensation of 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 devices are also associated with described reactor.
Described VOC retracting devices can reclaim dress using activated carbon adsorption retracting device, membrance separation retracting device, condensation
Put.
Beneficial effect
Compared with the process for purification of alcohol is removed in ethyl ester waste liquid dehydration conventional at present, method of the present utility model has following special
Point：
1. this utility model is dehydrated using infiltration evaporation membrane separator group, is not limited by azeotropic, and technical process is simple, safety
Coefficient is high,；
2. this utility model infiltration evaporation membrane separator group high degree of automation, easy to operate, and occupation area of equipment is few；
3. this utility model goes alcohol, ethyl acetate yield to reach as high as more than 100% by the way of esterification, separates
Effect is good, while 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 this utility model is provided, and reclaims ethyl acetate purity highest
Up to more than 99.7%, and the ethyl acetate purity for reclaiming is improved and will not significantly improve investment；
5. big, the applicable acetic acid of the process for purification flexibility of alcohol is removed in the ethyl acetate waste liquid dehydration that this utility model is provided
In ethyl ester, alcohol water content is may be up to 30%, and alcohol water ratio is not limited, and is not required to change device parameter, can be processed different alcohol water and contain
The ethyl acetate waste liquid of amount.
6. the ethyl acetate waste liquid dehydration that this utility model is provided goes the process for purification of alcohol, the organic acid of input to be completely used for
Reaction, unreacted organic acid can be used for lower batch of liquid waste processing.
Description of the drawings
Fig. 1 is the refining plant figure that alcohol is removed in the dehydration of ethyl acetate waste liquid；
Wherein, 1, reactor；2nd, rectifying column；3rd, capital condenser；4th, transfer tank；5th, vaporizer；6th, infiltration evaporation is separated
Unit；7th, vacuum pump；8th, penetrating fluid condenser；9th, it is dehydrated finished product condenser.
Specific embodiment
This utility model is described in further detail below by specific embodiment.But those skilled in the art will
Understand, the following example is merely to illustrate this utility model, and should not be regarded as limiting scope of the present utility model.In embodiment not
Dated particular technique or condition person, enter according to the technology or condition described by document in the art or according to product description
OK.Agents useful for same or the unreceipted production firm person of instrument, be can by city available from conventional products.
Using range format expression value should be interpreted as in a flexible way not only include clearly include as scope
The numerical value of limit value, but also including all single numbers or subinterval for covering within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood to not only include what is clearly included
The concentration of about 0.1% to about 5%, also including the single concentration in the range of alluding to（Such as, 1%, 2%, 3% and 4%）And subinterval（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.Percentage ratio described in this utility model is in the situation without special instruction
Under, refer to percentage by weight.
It is addressed in this manual to " one embodiment ", " another embodiment ", " embodiment " etc., refer to
Specific features, structure with reference to embodiment description are included at least one embodiment of the application generality description.
It is not necessarily to refer to same embodiment that statement of the same race occur in multiple places in the description.Furthermore, it is understood that combining arbitrary
When embodiment describes specific features, structure or a feature, to be advocated is realizing this spy with reference to other embodiment
Levy, structure or feature also fall in the application scope of the claimed.
The purpose of this utility model is to be dehydrated the subtractive process for removing alcohol, ethyl acetate containing alcohol waste liquid for ethyl acetate waste liquid
In input reactor, and a certain amount of organic acid and catalyst reacting by heating is added, to anti-by the way of rectification in rectifying column
Answer the ethyl acetate in kettle to carry out initial gross separation, prevent organic acid to be distilled out of with catalyst, ethyl acetate, water and not anti-
The thick ester of the ethanol composition that should fall is steamed from rectification capital；The partial reflux Jing after the condensation of capital condenser, partly produces to transfer
In tank.Thick ester in transfer tank is sent into Pervaporation membrane separator and carries out the thick ester of isolated dehydration, returns after being dehydrated thick ester condensation
It is back in reactor and continues the remaining ethanol of reaction, until ethanol is met the requirements with the content of water in ethyl acetate, by acetic acid second
All extraction obtains the refined finished product of ethyl acetate to ester.
In this utility model, the ethyl acetate waste liquid containing ethanol with water in described printing packaging industry refers to printing
Packaging industry is carried out after heat treatment to packaging, the waste liquid that the steam for obtaining is obtained through VOC retracting devices；In the middle of these waste liquids
There are the ethyl acetate come from ink and water, the second alcohol and water come from glue, in addition, other in ink and glue one
A little volatilizable compositions can also be resided in the middle of waste liquid, for example：The volatility such as hydro carbons, benzene class, ethers, acrylic compounds, isocyanates
Material.Feed liquid or VOC recovered liquids can also be processed using other pretreatment modes, to reduce, therein other are miscellaneous
Matter composition, such as absorption, absorption etc..
The steam in production can be packed by VOC retracting devices to be reclaimed, it is to obtain VOCs therein, used
VOC retracting devices are not particularly limited, and can reclaim dress using activated carbon adsorption retracting device, membrance separation retracting device, condensation
Put.
According to one of the present utility model preferred embodiment, acetic acid is adopted during reaction as organic acid, relative to which
His organic acid, for example：Acetic acid, maleic anhydride, citric acid, oxalic acid, caproic acid and lactic acid, acetic acid and ethanol synthesis produce acetic acid second
Ester, will not produce new impurity, and separation process is remarkably improved the yield of ethyl acetate.
According to one of the present utility model preferred embodiment, the organic acid mole inventory added before reacting is acetic acid
1～1.5 times of ethanol mole in ethyl ester waste liquid, optimum is 1.2 times, and the inventory can both ensure that ethanol was fully reacted,
It is not result in that organic excessive acid is too many.
According to another improved embodiment of the present utility model, it is condensed for the thick ester of rectifying column extraction after, most
Be well by the heating vaporization of thick ester vaporizer after, then the thick ester steam that vaporizer is steamed sends into infiltration evaporation membrane separator group
Separate.Preferably, the temperature of thick ester steam is 70～160 DEG C.
According to one of the present utility model preferred embodiment, the infiltrating and vaporizing membrane of employing is molecular screen membrane, relative to
Other similar membrane materials, for example：Amorphous silica film, PVA film, molecular screen membrane obtain being dehydrated thick ester once after separating
Membrane flux in high income and separation process is larger.
The refining plant that this utility model is provided, its structure is as shown in figure 1, include：Reactor 1, the top of reactor 1
Rectifying column 2 is set, and the top of rectifying column 2 is provided with capital condenser 3, during the condensate outlet of capital condenser 3 is passed sequentially through
Turn tank 4, vaporizer 5 and separate unit 6 with infiltration evaporation to connect, infiltration evaporation separates the per-meate side of unit 6, and to be provided with penetrating fluid cold
Condenser 8, vacuum pump 7；Infiltration evaporation separates the retention side of unit 6 and is connected with dehydration finished product condenser 9, dehydration finished product condenser 9
Condensate outlet be connected with reactor 1；The condensate outlet of described capital condenser 3 is also connected with the capital of rectifying column 2；
In addition, VOC retracting devices are also associated with described reactor 1, for the steam in packaging operation is carried out VOC recovery, institute
The VOC retracting devices stated can be using 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 shown in figure 1, operating process includes following step
Suddenly：3000 kg ethyl acetate containing alcohol waste liquids（Main component is：53% water, 24% ethyl acetate, 18% ethanol, 3% hydro carbons）Input is anti-
Answer in kettle 1, and 1.5 times according to ethanol mole add organic acid, and 10kg concentrated sulphuric acid reacting by heating, adopt in rectifying column 2
The mode of rectification carries out initial gross separation to the ethyl acetate in reactor, prevents organic acid to be distilled out of, ethyl acetate, water and
The thick ester of the ethanol composition not reacted away is steamed from rectification capital；Rectifying column is partly refluxed to Jing after capital condenser 3 is condensed
3, partly produce to transfer tank 4.Thick ester in transfer tank 4 send into vaporizer 5 be heated to 110 DEG C enter in vapour form by
8 molecular screen membranes, silicon dioxide film, PVA film components（Every grade of membrane module area is 1 m2）Infiltrating and vaporizing membrane in series point
Dehydration separation is carried out from device 6.Feed liquid lateral pressure is 0.2 MPa（Gauge pressure）, osmotic lateral pressure control is in 1000 Pa.Feed liquid side is molten
Water and a small amount of ethyl acetate in liquid obtains penetrating fluid through infiltrating and vaporizing membrane in vapour form, and per-meate side is in vacuum pump 7
Under suction, the penetrating fluid Jing penetrating fluids condenser 8 for obtaining is condensed.Coating materials liquid side feed liquid water content passes through infiltration evaporation membrane separator
Can significantly reduce, obtain being dehydrated thick ester, be dehydrated thick ester and be back in reactor 1 Jing after dehydration finished product condenser 9 is condensed and continue
Remaining ethanol is reacted, until terminating operation in ethyl acetate during ethanol content≤0.5wt.%, all extraction is obtained by ethyl acetate
Obtain the refined finished product of ethyl acetate.
When using different membrane materials, 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 for 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 at the dehydration during alcohol is removed in the dehydration of ethyl acetate waste liquid
Reason, the membrane material of the penetrating fluid water content of gained, water flux better than other species, simultaneously because dehydrating effect is more preferably, to ethanol
Reaction facilitation effect become apparent from, when reaching same processing requirement, 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 shown in figure 1, operating process includes following step
Suddenly：3000 kg ethyl acetate containing alcohol waste liquids（Main component is：45% water, 31% ethyl acetate, 20% ethanol, 1% ether solvent）Throw
Enter in reactor 1, and acetic acid, and 10kg concentrated sulphuric acid reacting by heating, essence is added according to the 1 of ethanol mole, 1.2,1.5 times respectively
Initial gross separation is carried out to the ethyl acetate in reactor by the way of rectification in fractional distillation column 2, prevents organic acid to be distilled out of, acetic acid second
The thick ester of ester, water and the ethanol composition not reacted away is steamed from rectification capital；Pressed Jing after capital condenser 3 is condensed respectively
Carry out being partly refluxed to rectifying column 3 according to reflux ratio, partly produce to transfer tank 4.Thick ester in transfer tank 4 sends into 5 quilt of vaporizer
It is heated to 110 DEG C to be entered into by 8 molecular screen membranes in vapour form（Every grade of membrane module area is 1 m2）Infiltration in series
Vaporization membrane separator 6 carries out dehydration separation.Feed liquid lateral pressure is 0.2 MPa（Gauge pressure）, osmotic lateral pressure control is in 500 Pa.Material
Water and a small amount of ethyl acetate in the solution of liquid side obtains 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 Jing penetrating fluids condenser 8 for obtaining is condensed.Coating materials liquid side feed liquid water content passes through infiltrating and vaporizing membrane
Seperator significantly can be reduced, and obtain being dehydrated thick ester, be dehydrated thick ester and be back to reactor 1 Jing after dehydration finished product condenser 9 is condensed
It is interior to continue the remaining ethanol of reaction, until in ethyl acetate, during ethanol content≤0.1wt.%, terminate operation, by ethyl acetate whole
Extraction obtains the refined finished product of ethyl acetate.
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 10 batches of waste liquids of process
Distillate pH value testing result converted.
Table 2
As can be seen from the table, before reacting, acetic acid molar feed ratio is bigger, and in ethyl acetate, ethanol removal is faster, but throws
Enter excessive acetic acid, the pH of rectifying column distillate can be caused to decline, so as to 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 shown in figure 1, operating process includes following step
Suddenly：3000 kg ethyl acetate containing alcohol waste liquids（Main component is：32% water, 37% ethyl acetate, 23% ethanol, 5% hydro carbons）Input is anti-
Answer in kettle 1, and acetic acid, maleic anhydride, citric acid, caproic acid, and 10kg concentrated sulphuric acids is added according to 1.2 times of ethanol mole respectively
Reacting by heating, carries out initial gross separation to the ethyl acetate in reactor in rectifying column 2 by the way of rectification, prevents organic acid quilt
Steam, the thick ester of ethyl acetate, water and the ethanol composition not reacted away is steamed from rectification capital；Jing capitals condenser 3 is cold
Carry out being partly refluxed to rectifying column 3 according to reflux ratio after solidifying respectively, partly produce to transfer tank 4.Thick ester in transfer tank 4 is sent into
Vaporizer 5 is heated to 120 DEG C and is entered into by 8 molecular screen membranes in vapour form（Every grade of membrane module area is 1 m2）Series connection structure
Into Pervaporation membrane separator 6 carry out dehydration separation.Feed liquid lateral pressure is 0.25 MPa（Gauge pressure）, osmotic lateral pressure control exist
700 Pa.Water and a small amount of ethyl acetate in the solution of feed liquid side obtains penetrating fluid through infiltrating and vaporizing membrane in vapour form, oozes
Under the suction of vacuum pump 7, the penetrating fluid Jing penetrating fluids condenser 8 for obtaining is condensed for saturating side.Coating materials liquid side feed liquid water content passes through
Infiltration evaporation membrane separator significantly can be reduced, and obtain being dehydrated thick ester, be dehydrated thick ester and return Jing after dehydration finished product condenser 9 is condensed
Continue the remaining ethanol of reaction to reactor 1, until in ethyl acetate, during ethanol content≤0.3wt.%, terminate operation, by second
All extraction obtains the refined finished product of ethyl acetate to acetoacetic ester.
The ethyl acetate yield of gained, ethanol content are down to 2wt.% run times, ethanol content and are down to 0.3wt.% operations
At the end of time and reaction, reactor component is as shown in table 3.Equipment average operating time is according to the operation for processing 10 batches of waste liquids
Time is converted.
Table 3
As can be seen from the table, when participating in reacting as organic acid using maleic anhydride, it is most fast that reaction is carried out, acetic acid
Response time is placed in the middle, but for ethyl acetate system, is remarkably improved yield using acetic acid, reduces waste liquid and by-product produce
It is raw.
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 shown in figure 1, operating process includes following step
Suddenly：3000 kg ethyl acetate containing alcohol waste liquids（Main component is：51% water, 35% ethyl acetate, 12% ethanol, 1% propylene glycol monomethyl ether）
In input reactor 1, and acetic acid, and 10kg concentrated sulphuric acid reacting by heating, rectifying column is added according to 1.5 times of ethanol mole respectively
Initial gross separation is carried out to the ethyl acetate in reactor by the way of rectification in 2, prevents organic acid to be distilled out of, ethyl acetate,
The thick ester of water and the ethanol composition not reacted away is steamed from rectification capital；Jing capital condenser 3 condense after respectively according to return
Flow ratio carries out being partly refluxed to rectifying column 3, partly produces to transfer tank 4.Thick ester in transfer tank 4 is sent into vaporizer 5 and is heated
Entered into by 10 molecular screen membranes in vapour form to 130 DEG C（Every grade of membrane module area is 1 m2）Infiltration evaporation in series
Membrane separator 6 carries out dehydration separation.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 in 900 Pa.Water and a small amount of ethyl acetate in the solution of feed liquid side is obtained through infiltrating and vaporizing membrane in vapour form
Penetrating fluid, under the suction of vacuum pump 7, the penetrating fluid Jing penetrating fluids condenser 8 for obtaining is condensed per-meate side.Coating materials liquid side feed liquid water
Content significantly can be reduced by infiltration evaporation membrane separator, obtain being dehydrated thick ester, be dehydrated thick ester Jing dehydrations finished product condenser 9 cold
It is back to after solidifying in reactor 1 and continues the remaining ethanol of reaction, until terminates fortune in ethyl acetate during ethanol content≤0.1wt.%
OK, by ethyl acetate, all extraction obtains the refined finished product of ethyl acetate.
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 10 batches of waste liquids of process
Distillate pH value testing result converted.
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 shown in figure 1, operating process includes following step
Suddenly：3000 kg ethyl acetate containing alcohol waste liquids（Main component is：51% water, 35% ethyl acetate, 12% ethanol, 1% propylene glycol monomethyl ether）
In input reactor 1, and acetic acid, and 10kg concentrated sulphuric acid reacting by heating, rectifying column is added according to 1.5 times of ethanol mole respectively
Initial gross separation is carried out to the ethyl acetate in reactor by the way of rectification in 2, prevents organic acid to be distilled out of, ethyl acetate,
The thick ester of water and the ethanol composition not reacted away is steamed from rectification capital；Jing capital condenser 3 condense after respectively according to return
Flow ratio carries out being partly refluxed to rectifying column 3, partly produces to transfer tank 4.Thick ester in transfer tank 4 is processed through activated carbon adsorption
Afterwards, feed liquid feeding vaporizer 5 is heated to 130 DEG C and is entered into by 10 molecular screen membranes in vapour form（Every grade of membrane module area
For 1 m2）Pervaporation membrane separator 6 in series carries out dehydration separation.Feed liquid lateral pressure be respectively 0.05,0.1,0.15,
0.2、0.25 MPa（Gauge pressure）, osmotic lateral pressure control is in 900 Pa.Water and a small amount of ethyl acetate in the solution of feed liquid side with
Vapor form obtains penetrating fluid through infiltrating and vaporizing membrane, per-meate side under the suction of vacuum pump 7, the penetrating fluid Jing penetrating fluids for obtaining
Condenser 8 is condensed.Coating materials liquid side feed liquid water content significantly can be reduced by infiltration evaporation membrane separator, obtain being dehydrated thick ester,
It is dehydrated thick ester and is back in reactor 1 Jing after dehydration finished product condenser 9 is condensed and continue the remaining ethanol of reaction, until ethyl acetate
Terminate operation during middle ethanol content≤0.1wt.%, all extraction obtains the refined finished product of ethyl acetate by ethyl acetate.
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 10 batches of waste liquids of process
Distillate pH value testing result converted.
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 shown in figure 1, operating process includes following step
Suddenly：3000 kg ethyl acetate containing alcohol waste liquids（Main component is：45% water, 35% ethyl acetate, 16% ethanol, 1% propylene glycol monomethyl ether）
In input reactor 1, and acetic acid, and 8kg concentrated sulphuric acid reacting by heating, rectifying column 2 is added according to 1.3 times of ethanol mole respectively
It is middle that initial gross separation is carried out to the ethyl acetate in reactor by the way of rectification, prevent organic acid to be distilled out of, ethyl acetate,
The thick ester of water and the ethanol composition not reacted away is steamed from rectification capital；Jing capital condenser 3 condense after respectively according to return
Flow ratio carries out being partly refluxed to rectifying column 3, partly produces to transfer tank 4.Thick ester in transfer tank 4 is sent into vaporizer 5 and is heated
Entered into by 8 molecular screen membranes in vapour form to 140 DEG C（Every grade of membrane module area is 1 m2）Infiltration evaporation in series
Membrane separator 6 carries out dehydration separation.Feed liquid lateral pressure is respectively 0.1MPa（Gauge pressure）, osmotic lateral pressure control is in 300-1000
Pa.Water and a small amount of ethyl acetate in the solution of feed liquid side obtains penetrating fluid, per-meate side through infiltrating and vaporizing membrane in vapour form
Under the suction of vacuum pump 7, the penetrating fluid Jing penetrating fluids condenser 8 for obtaining is condensed.Coating materials liquid side feed liquid water content is by infiltration
Vaporization membrane separator significantly can be reduced, and obtain being dehydrated thick ester, be dehydrated thick ester and be back to instead Jing after dehydration finished product condenser 9 is condensed
Answer, until in ethyl acetate, during ethanol content≤0.1wt.%, terminate operation, by acetic acid second
All extraction obtains the refined finished product of ethyl acetate to ester.
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 10 batches of waste liquids of process
Distillate pH value testing result converted.
Table 6
Claims (7)
1. it is a kind of to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, it is characterised in that to include：Instead
Answer kettle（1）, reactor（1）Top arrange rectifying column（2）, rectifying column（2）Top be provided with capital condenser（3）, capital
Condenser（3）Condensate outlet pass sequentially through transfer tank（4）, vaporizer（5）Unit is separated with infiltration evaporation（6）Connection, oozes
Vaporization separates unit thoroughly（6）Per-meate side be provided with penetrating fluid condenser（8）, vacuum pump（7）；Infiltration evaporation separates unit（6）
Retention side be connected with dehydration finished product condenser（9）, it is dehydrated finished product condenser（9）Condensate outlet and reactor（1）Connection.
2. according to claim 1 to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, which is special
Levy and be, described capital condenser（3）Condensate outlet also with rectifying column（2）Capital connection.
3. according to claim 1 to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, which is special
Levy and be, described reactor（1）On be also associated with VOC retracting devices.
4. according to claim 3 to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, which is special
Levy and be, described VOC retracting devices reclaim dress selected from activated carbon adsorption retracting device, membrance separation retracting device or condensation
Put.
5. according to claim 1 to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, which is special
Levy and be, described infiltration evaporation separates unit（6）The middle film for adopting is for preferential water permeable membrane.
6. according to claim 5 to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, which is special
Levy and be, preferential water permeable membrane is selected from molecular screen membrane, amorphous silica film or PVA film.
7. according to claim 1 to be dehydrated the refining plant for removing alcohol for packages printing industry ethyl acetate waste liquid, which is special
Levy and be, infiltration evaporation separates unit（6）It is to be connected by 1～200 Pervaporation membrane separator series, parallel or series-parallel connection.
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