CN1249739A - Method for extracting (meth) acrylic acid - Google Patents
Method for extracting (meth) acrylic acid Download PDFInfo
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- CN1249739A CN1249739A CN98803154A CN98803154A CN1249739A CN 1249739 A CN1249739 A CN 1249739A CN 98803154 A CN98803154 A CN 98803154A CN 98803154 A CN98803154 A CN 98803154A CN 1249739 A CN1249739 A CN 1249739A
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- methyl
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- extraction agent
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- acrylic acid
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000000605 extraction Methods 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 239000012074 organic phase Substances 0.000 claims abstract description 13
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical group CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 55
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 230000002411 adverse Effects 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 20
- 239000007789 gas Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- -1 alkanol Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical group CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a method for extracting an aqueous solution containing (meth)acrylic acid. Said solution is brought into contact with a solution containing at least one extracting agent which can be converted into (meth)acrylic acid and forms a miscibility gap with the aqueous solution to produce an organic phase containing (meth)acrylic acid and extraction agent and an aqueous phase.
Description
The present invention relates to contain the extracting process of (methyl) acrylic acid aqueous solution, this method is that this aqueous solution is contacted with the solution that contains at least a extraction agent, this extraction agent can one step or multistep change into (methyl) but vinylformic acid and form the compatibility zone with this aqueous solution.
Term " (methyl) vinylformic acid " used among the application not only is meant vinylformic acid but also be meant methacrylic acid.
Because the high reactivity list ethene formula unsaturated link(age) and the acid function of methacrylic acid so methacrylic acid is the effective monomer of preparation polymkeric substance, for example, are used to prepare the aqueous polymers dispersion liquid that is suitable as tackiness agent.This also is applicable to vinylformic acid.
Except method for distinguishing, can be in the presence of catalyzer, for example contain the molybdenum of oxidised form and the poly-metal deoxide of vanadium,, obtain methacrylic acid with oxygen or oxygen-containing gas gaseous oxidation 1-butylene, iso-butylene, isobutyric aldehyde, isopropylformic acid, iso-butylene, MTBE and/or methacrylaldehyde.Oxidation is to carry out at elevated temperatures, because suitable heat is emitted in reaction, so preferably use rare gas element such as N
2, CO
2And/or hydrocarbon and/or steam diluting reaction thing.Yet, these methods can not obtain pure methacrylic acid, except containing methacrylic acid, reaction gas mixtures also contains for example unconverted methacrylaldehyde of raw material, steam, rare gas element (for example nitrogen) and by product (for example carbon oxides), low grade aldehyde is formaldehyde for example, and higher-boiling compound is citraconic acid for example, and the spy is acetate in addition, must from reaction gas mixtures, isolate methacrylic acid (reference, for example EP-A253409 and DE-A1962431) subsequently.Yet other possible initial compounds are those compounds, form actual C as intermediate at first by these compounds in gas phase oxidation
4Initial compounds is as methacrylaldehyde.The methyl ether (MTBE) that example is the trimethyl carbinol.
In order to prepare methacrylaldehyde, can also make formaldehyde and propionic aldehyde carry out condensation reaction, obtain methacrylaldehyde through distillation then.This method is described among the EP-B58927.Available then ordinary method changes into methacrylic acid by catalytic vapor phase oxidation reaction with the methacrylaldehyde that so obtains.This class reaction especially is described among the EP-A297445.
Use similar method, by corresponding C
3Compound, particularly propylene and/or propenal obtain vinylformic acid.
If plan to isolate (methyl) vinylformic acid by extracting process from the reaction gas mixtures that generates, reaction gas mixtures should at first pass through condensation step so, extracts then.Therefore, EP-B345083 has described a kind of like this method, and this method comprises the methacrylic acid extraction step, and wherein the stable hydrocarbon with 6-9 carbon atom extracts methacrylic acid.
According to EP-A710643, in the method for purifying methacrylic acid, by adding organic solvent, the aliphatic hydrocrbon of preferred 5-9 carbon atom, aromatic hydrocarbons, ester or its mixture extract the moisture methacrylic acid solution that obtains by cooling and condensation reaction gas from aqueous solution.
Japanese Patent JP57095938 has described by extracting vinylformic acid with oxo solvent and tertiary amine extraction from the dilution aqueous solution.The example of solvent is trioctylamine and 2, the 6-2,6-dimethyl-4-heptanol.
Yet, all these methods all are imperfect, promptly all to make used additives extraction (methyl) vinylformic acid in each case, on the one hand, this auxiliary agent will have extra charge just can obtain, in addition, need additional step in order to isolate this auxiliary agent once more in the method, this just needs extra charge and additional energy consumption.
The none method has been described with no compounding agent solution extraction (methyl) acrylic acid possibility in the existing method.So far used extraction agent only is to change into (methyl) acrylic acid auxiliary agent.
Therefore, the purpose of this invention is to provide the method that extraction contains (methyl) acrylic acid aqueous solution, this method can be carried out under the situation that does not make used additives, in addition, can use conventional equipment to carry out, and have low relatively energy consumption.
We have found that this purpose can realize with method of the present invention.
Therefore, the present invention relates to contain the extracting process of (methyl) acrylic acid aqueous solution, this method is, this aqueous solution is contacted with the solution that contains at least a extraction agent, this extraction agent can change into (methyl) but vinylformic acid and form miscibility gap with this aqueous solution, wherein organic phase contains (methyl) vinylformic acid and extraction agent, and has obtained containing water.
As defined in claims particularly, term " extraction agent " comprise can a step or multistep change into (methyl) vinylformic acid and simultaneously with contain (methyl) but acrylic acid aqueous solution forms all compounds of miscibility gap.
Special example is paraffinic hydrocarbons, alkanol, alkene or chain olefine aldehydr or its 2 or a plurality of mixtures of 3-4 carbon atom, and these compounds can change into (methyl) vinylformic acid and form miscibility gap with above-mentioned aqueous solution.
The compound that is applicable to this purpose is the methyl ether (MTBE) of (methyl) propenal, iso-butylene, propylene, propane, butane, isobutyric aldehyde, the trimethyl carbinol or their 2 or a plurality of mixtures preferably.What especially preferably use is (methyl) propenal.
Contain the solution of the acrylic acid extraction agent of at least a changing into (methyl) or form by this extraction agent fully, or with other materials for example water and/mixture of acetate.This solution also can contain the impurity that generates in the preparation process of component, so this extraction agent needn't purifying before extraction.
Also can add the additive that improves effect of extracting in this solution.Its example is a foam preventer, the polyvalent alcohol of tallow fatty alcohol and other for example, and emulsion splitter, the material of alkali metal chloride and tensio-active agent and expansion miscibility gap for example, higher alkane hydrocarbon for example, particularly those contain the paraffinic hydrocarbons of 4-14 carbon atom.
To being included in this solution and can changing into the concentration of (methyl) acrylic acid extraction agent, in principle without limits, but the concentration of this extraction agent is preferably about 50-100 in solution, and especially preferably about 70-is about 99.9, particularly about 90-97% (weight).
Under any circumstance, above-mentioned solution must with contain (methyl) acrylic acid aqueous solution and have miscibility gap.
Particularly, if this novel method is incorporated into a kind of preparation (methyl) acrylic acid, perhaps with this method combine operations, so preferably, being used for extraction (methyl) vinylformic acid and containing the acrylic acid extraction agent of at least a changing into (methyl) is the solution that can be used as (methyl) vinylformic acid synthesis material, and the concentration of preferred extraction agent is 50-100% (weight).Particularly preferably be the solution that contains (methyl) propenal.
Oxidation C in first step
3/ C
4That compound obtains, and the reaction gas mixtures that still contains raw material described mixture condensation after, also can be used as be used for extraction (methyl) acrylic acid, contain at least a extraction agent and also can change into (methyl) acrylic acid solution.
Contained and after extraction, exist certain density extraction agent preferably to reclaim containing aqueous phase in solution by the thermal separation method, for example, perhaps reclaim by distillation with discharge gas or its 2 kinds or multiple mixture stripping in steam or rare gas element such as nitrogen, air, carbonic acid gas, the preparation of (methyl) vinylformic acid.If necessary, after delivering in addition (comprehensive process) step, extraction agent in fact changes into gas phase fully, can be used for preparation (methyl) vinylformic acid then.
To (methyl) acrylic acid concentration in the aqueous solution equally without limits.(methyl) acrylic acid content is preferably about 80, especially preferred about 40, about 20% (weight) of about 5-particularly of about 1-of about 0.01-in this solution.Particularly, if this solution is obtained by preparation (methyl) vinylformic acid industrial, this solution is except containing (methyl) vinylformic acid and water so, also can contain a spot of, usually be less than about 3% (weight) be used for preparation (methyl) acrylic acid raw material and a spot of, be less than the acetate of 10% (weight) usually.
As mentioned above, obtained containing the organic phase of (methyl) vinylformic acid and extraction agent in the extraction.The extraction preferably carry out by this way, promptly used (methyl) acrylic acid total amount or total amount substantially be present in this mutually in.Organic phase also contains extraction agent and a spot of water, acetate and higher-boiling compound except containing (methyl) vinylformic acid.What obtain contains water and also can contain a spot of (methyl) vinylformic acid, extraction agent and acetate, but these materials can be removed by thermal separation method major part.
A preferred embodiment according to this novel method, the organic phase that contains (methyl) vinylformic acid and extraction agent is through the thermal separation method, for example with steam or rare gas element for example nitrogen, air, carbonic acid gas, the oxidation raw material forms in the preparation of (methyl) vinylformic acid discharge gas or the mixture stripping of these rare gas elementes, perhaps distillation extraction agent/water mixture.In the method, (methyl) vinylformic acid is isolated from most of extraction agent and water with higher-boiling compound and acetate.
Have no particular limits carrying out the used temperature of this novel method.Unique prerequisite is to want to form organic aqeous two-phase mutually under the pressure of temperature of selecting and selection.Usually, about 150 ℃ at about 0-of this novel methods are carried out under about 80 ℃ of the preferably about 30-, about 70 ℃ of particularly about 50-, and when with (methyl) propenal during as extraction agent, used temperature is higher than about 68 ℃ under superatmospheric pressure.If use other extraction agent, must be according to extraction agent and corresponding change temperature and/or pressure.
The all devices that is generally used for extracting is described in, Ullmanns industrial chemistry encyclopaedia for example, and the 4th edition, the 2nd volume, 546 pages and following or the like, particularly 560 pages and each page (1972) backward, these equipment can be used for carrying out this novel method.Special example is mixing tank-settling vessel device, extraction tower, the tower extraction tower of spray, pulse or non-pulse formula tray column and packing tower and stirring extraction tower or the extraction plant that uses centrifugal force.
Can will contain (methyl) acrylic acid aqueous solution and contain the acrylic acid extraction agent of at least a changing into (methyl) mutual and stream, cross-flow or counter current contact, preferred counter current contact method.
Extraction can be carried out in 1 step or a plurality of step, can also use the blended extraction plant.
The method according to this invention can be carried out continuously or intermittently, preferred continuation method.
A part that also can be used as preparation (methyl) vinylformic acid method is carried out this new extractive process.In the condensation of the reaction mixture that directly obtains in by gaseous oxidation preparation (methyl) vinylformic acid, (methyl) acrylic acid amount that extract is usually corresponding to (methyl) acrylic acid amount of condensation not.
As mentioned above, through the preferred extraction agent that is used to extract that reclaims in extraction back.The particularly suitable method that recovery is dissolved in the extraction agent part that contains aqueous phase is the thermal separation method, for example the discharge gas that forms with steam or rare gas element such as nitrogen, air, carbonic acid gas, in the oxidation that is used for preparing (methyl) acrylic acid raw material or the mixture stripping or the distillation extraction agent/water mixture of these rare gas elementes.
Gas stripping process carries out under following condition usually: temperature is about 100 ℃ of about 30-, and about 80 ℃ of preferably about 50-, pressure are about 1-about 1.5 * 10
5Pa.For other pressure, must correspondingly change temperature.
Without any special restriction, any conventional stripper plant of solution-air contact that makes can use, for example packing tower, sieve-tray tower, bubble-plate column or spray column to the type of used stripper plant.Other wieldy spray equipments are described in EP-A706986, the 3rd hurdle, and in the described absorption tower of prior art of quoting during 11-38 is capable, this patent is incorporated herein by reference fully in the application.
As mentioned above, same by the thermal separation method, preferably make organic phase reclaim (methyl) vinylformic acid contained in the organic phase through (methyl) vinylformic acid condensation step, this step has obtained containing the condenses of the acetate of (methyl) vinylformic acid of the main amount that exists in the organic phase and main amount, and usually in organic phase contained extraction agent change into gaseous state.
For this reason, organic phase is through the thermal separation method, and this method is operated under the temperature that has reached above-mentioned purpose, and (methyl) vinylformic acid that has promptly reached main amount separates with the extraction agent of main amount.
These separation methods are known in the prior art, and are described in, and for example openly apply among DOS4235321 and the DOS3721865 in Germany especially, and these methods are used for the gas reaction mixture that condensation obtains at preparation (methyl) vinylformic acid.
For fear of or reduce the polymerization of (methyl) vinylformic acid and/or extraction agent, also can in present method solutions employed, add stablizer, thiodiphenylamine for example, quinhydrones or derivatives thereof.
From on can find out obviously that the problem of azeotropic (methyl) vinylformic acid/hydrate can overcome in simple mode by adding the novel method can change into (methyl) acrylic acid extraction agent.Can save the highly energy-consuming separating step that comprises the distillatory costliness like this.In addition, avoided owing to handling the pollution problem that auxiliary agent brings.
The following examples have illustrated the present invention.Embodiment 1
In service temperature is to be the aqueous solution that 92% aqueous solution extraction (weight), that contain methacrylaldehyde contains 10.3% (weight) methacrylic acid and 2.2% (weight) acetate by the adverse current method with methacrylaldehyde content in three sections inline mixer-settling vessels of 50 ℃, and 30 minutes the residence time is enough to be separated.
The organic phase that obtains contains to some extent (methyl) vinylformic acid of the total amount that adds, this mutually in its concentration be 17.6% (weight).Extraction obtains 361 gram (methyl) vinylformic acid.Embodiment 2
The aqueous solution that contains 10.3% (weight) methacrylic acid and 2.2% (weight) acetate with organic methacrylaldehyde solution one-step extracting 630 grams of 300 grams, methacrylaldehyde solution contains 7% water, obtains the water that contains that 580 grams contain 1.7% (weight) methacrylic acid and 1.2% (weight) acetate.
In this extraction step, methacrylaldehyde solution contains 14.4% (weight) methacrylic acid and 1.1% (weight) acetate.Embodiment 3
The aqueous solution that contains 1.7% (weight) methacrylic acid and 1.2% (weight) acetate with organic methacrylaldehyde solution one-step extracting 449 grams of 212 grams, methacrylaldehyde solution contains 7% water, obtains the water that contains that 434 grams contain 0.37% (weight) methacrylic acid and 1.2% (weight) acetate.
In this extraction step, methacrylaldehyde solution contains 2.9% (weight) methacrylic acid and 1.1% (weight) acetate.Embodiment 4
The aqueous solution that contains 0.37% (weight) methacrylic acid and 1.2% (weight) acetate with organic methacrylaldehyde solution one-step extracting 328 grams of 156 grams, methacrylaldehyde solution contains 7% water, obtains the water that contains that 325 grams contain 0.06% (weight) methacrylic acid and 0.68% (weight) acetate.
In this extraction step, methacrylaldehyde solution contains 0.65% (weight) methacrylic acid and 0.56% (weight) acetate.Embodiment 5
In 3 sections mixing tanks-settling vessel system, with joining 3.49 kilograms of/hour first aqueous solutions that kilogram/hour first methacrylaldehyde solution counter-current extraction of 1.63 in the 3rd settling vessel contains 10.3% (weight) methacrylic acid and 2.2% (weight) acetate.The first methacrylaldehyde solution contains 7% water.In first extraction section (first settling vessel), first aqueous solution is contacted with the effusive triisobutene aldehyde of second settling vessel solution.
The effusive second methacrylaldehyde solution of effusive second aqueous solution of first settling vessel and the 3rd settling vessel is contacted, in the 3rd section, effusive the 3rd aqueous solution of second settling vessel is contacted with the first methacrylaldehyde solution.
Obtain 3 kilograms/hour the 4th from the 3rd settling vessel and contain water, the 4th aqueous solution contains 0.8% (weight) methacrylic acid and 1.5% (weight) acetate.Obtain 2 kilograms of/hour the 4th methacrylaldehyde solution from first settling vessel, the 4th methacrylaldehyde solution contains 17.6% (weight) methacrylaldehyde and 1.6% (weight) acetate.
In all embodiment, after being less than 3 minutes, finish being separated between aqueous solution and the methacrylaldehyde solution.
All embodiment carry out under 50 ℃ of temperature and normal atmosphere.
Claims (10)
1. extracting process that contains (methyl) acrylic acid aqueous solution, this method is that this aqueous solution is contacted with the solution that contains at least a extraction agent, this extraction agent can change into (methyl) but vinylformic acid and form the compatibility zone with this aqueous solution wherein obtains (methyl) vinylformic acid and organic phase and a kind of water of extraction agent of a kind of containing.
2. according to the process of claim 1 wherein that this solution contains one or more extraction agents that concentration is 50-100% (weight), this extraction agent can change into (methyl) vinylformic acid.
3. according to the method for claim 1 or 2, wherein one or more can change into methyl ether (MTBE) that (methyl) acrylic acid extraction agent is (methyl) propenal, iso-butylene, propylene, propane, butane, isobutyric aldehyde, the trimethyl carbinol or their 2 or a plurality of mixtures.
4. require each method according to aforesaid right, wherein containing contained (methyl) the acrylic acid concentration of (methyl) acrylic acid aqueous solution is 0.01-80% (weight).
5. require each method according to aforesaid right, wherein contain at least a changing into (methyl) but vinylformic acid and with solution that aqueous solution forms the extraction agent in compatibility zone be the solution that in preparation (methyl) vinylformic acid, can be used as raw material.
6. require each method according to aforesaid right, wherein extraction is at mixing tank-settling vessel device, packed extraction tower, the tower extraction tower of spray, pulse-or non-pulse tray column or packing tower, stirring extraction tower or use in the extraction plant of centrifugal force and carry out.
7. require each method according to aforesaid right, wherein extraction is carried out continuously.
8. require each method according to aforesaid right, wherein extraction is that adverse current is carried out.
9. require each method according to aforesaid right, wherein contain water, obtain a kind of gas and a kind of waste water that contains extraction agent through the thermal separation method.
10. require each method according to aforesaid right, the organic phase that wherein contains (methyl) vinylformic acid and extraction agent is contained (methyl) acrylic acid liquid phase and the gas phase that contains extraction agent through the thermal separation method.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19709392A DE19709392A1 (en) | 1997-03-07 | 1997-03-07 | Process for the extraction of (meth) acrylic acid |
| DE19709392.2 | 1997-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1249739A true CN1249739A (en) | 2000-04-05 |
Family
ID=7822581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98803154A Pending CN1249739A (en) | 1997-03-07 | 1998-03-05 | Method for extracting (meth) acrylic acid |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0973718A1 (en) |
| JP (1) | JP2001514643A (en) |
| KR (1) | KR20000075989A (en) |
| CN (1) | CN1249739A (en) |
| AU (1) | AU6827698A (en) |
| BR (1) | BR9808158A (en) |
| CA (1) | CA2282492A1 (en) |
| DE (1) | DE19709392A1 (en) |
| ID (1) | ID22758A (en) |
| TW (1) | TW438760B (en) |
| WO (1) | WO1998040342A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386302C (en) * | 2006-03-29 | 2008-05-07 | 上海华谊丙烯酸有限公司 | Method for extracting (methyl) acrylic acid aqueous solutior |
| CN102186549A (en) * | 2008-10-15 | 2011-09-14 | 阿科玛股份有限公司 | Method of recovering carboxylic acids from dilute aqueous streams |
| CN103796982A (en) * | 2011-09-16 | 2014-05-14 | 赢创罗姆有限公司 | Process for preparation of methacrylic acid and methacrylic acid ester |
| CN103796984A (en) * | 2011-09-16 | 2014-05-14 | 赢创罗姆有限公司 | Process for preparation of methacrylic acid and methacrylic acid esters |
| CN105399620A (en) * | 2015-11-13 | 2016-03-16 | 惠州市长润发涂料有限公司 | Acrylic acid extraction recovery technology |
| CN106748749A (en) * | 2016-11-10 | 2017-05-31 | 万华化学集团股份有限公司 | A kind of method for separating TIB in tert-butyl acrylate reaction solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7803969B2 (en) | 2001-01-12 | 2010-09-28 | Evonik Stockhausen Gmbh | Continuous process for the production and purification of acrylic acid |
| DE10211686A1 (en) | 2002-03-15 | 2003-10-02 | Stockhausen Chem Fab Gmbh | (Meth) acrylic acid crystal and process for the production and purification of aqueous (meth) acrylic acid |
| CN101384539B (en) | 2005-12-26 | 2013-05-08 | 三菱丽阳株式会社 | Method for extracting methacrylic acid |
| JP5100150B2 (en) | 2006-03-02 | 2012-12-19 | 株式会社コガネイ | shock absorber |
| DE102008000787A1 (en) * | 2008-03-20 | 2009-09-24 | Evonik Röhm Gmbh | Process for the purification of methacrylic acid |
| DE102008020688B3 (en) | 2008-04-24 | 2009-11-05 | Evonik Stockhausen Gmbh | Process for the preparation and purification of aqueous phases |
| US9156769B2 (en) | 2008-10-15 | 2015-10-13 | Arkema Inc. | Method of recovering carboxylic acids from dilute aqueous streams |
| WO2013037134A1 (en) * | 2011-09-16 | 2013-03-21 | Evonik Roehm Gmbh | Process for preparation of methacrylic acid and methacrylic acid esters |
| WO2013037133A1 (en) * | 2011-09-16 | 2013-03-21 | Evonik Roehm Gmbh | Process for preparing methacrylic acid and/or alkyl methacrylates |
| JP5959645B2 (en) * | 2011-09-16 | 2016-08-02 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Method for regenerating methacrylic acid from high boiling and aqueous phases |
| EP3122714A4 (en) * | 2014-03-24 | 2017-11-01 | Arkema, Inc. | Method of recovering carboxylic acids from dilute aqueous streams |
| EP3175897B1 (en) | 2015-12-04 | 2018-04-04 | Evonik Degussa GmbH | Improved method for the extraction of aromatic substances from fat-containing and/or aqueous liquid phases |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4839421A (en) * | 1971-09-30 | 1973-06-09 | ||
| DE2161525A1 (en) * | 1971-12-10 | 1973-06-20 | Sumitomo Chemical Co | Extraction of acrylic and/or methacrylic acid - from soln, using a methylethyl ketone/benzene extractant mixture |
| JPH0684326B2 (en) * | 1988-06-03 | 1994-10-26 | 株式会社日本触媒 | Recovery method of methacrolein |
| JPH08134011A (en) * | 1994-11-04 | 1996-05-28 | Mitsui Toatsu Chem Inc | Purification of methacrylic acid |
-
1997
- 1997-03-07 DE DE19709392A patent/DE19709392A1/en not_active Withdrawn
-
1998
- 1998-03-05 EP EP98913652A patent/EP0973718A1/en not_active Withdrawn
- 1998-03-05 JP JP53918298A patent/JP2001514643A/en active Pending
- 1998-03-05 BR BR9808158-6A patent/BR9808158A/en not_active Application Discontinuation
- 1998-03-05 AU AU68276/98A patent/AU6827698A/en not_active Abandoned
- 1998-03-05 CN CN98803154A patent/CN1249739A/en active Pending
- 1998-03-05 WO PCT/EP1998/001256 patent/WO1998040342A1/en not_active Application Discontinuation
- 1998-03-05 ID IDW990963A patent/ID22758A/en unknown
- 1998-03-05 CA CA002282492A patent/CA2282492A1/en not_active Abandoned
- 1998-03-05 KR KR1019997008075A patent/KR20000075989A/en not_active Application Discontinuation
- 1998-03-06 TW TW087103308A patent/TW438760B/en active
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|---|---|---|---|---|
| CN100386302C (en) * | 2006-03-29 | 2008-05-07 | 上海华谊丙烯酸有限公司 | Method for extracting (methyl) acrylic acid aqueous solutior |
| CN102186549A (en) * | 2008-10-15 | 2011-09-14 | 阿科玛股份有限公司 | Method of recovering carboxylic acids from dilute aqueous streams |
| CN105085233B (en) * | 2008-10-15 | 2017-11-07 | 阿科玛股份有限公司 | Method for reclaiming carboxylic acid from dilute aqueous flow |
| CN103796982A (en) * | 2011-09-16 | 2014-05-14 | 赢创罗姆有限公司 | Process for preparation of methacrylic acid and methacrylic acid ester |
| CN103796984A (en) * | 2011-09-16 | 2014-05-14 | 赢创罗姆有限公司 | Process for preparation of methacrylic acid and methacrylic acid esters |
| CN103796982B (en) * | 2011-09-16 | 2015-10-14 | 赢创罗姆有限公司 | The preparation method of methacrylic acid and methacrylic ester |
| CN103796984B (en) * | 2011-09-16 | 2016-03-23 | 赢创罗姆有限公司 | The preparation method of methacrylic acid and methacrylic ester |
| CN105399620A (en) * | 2015-11-13 | 2016-03-16 | 惠州市长润发涂料有限公司 | Acrylic acid extraction recovery technology |
| CN106748749A (en) * | 2016-11-10 | 2017-05-31 | 万华化学集团股份有限公司 | A kind of method for separating TIB in tert-butyl acrylate reaction solution |
| CN106748749B (en) * | 2016-11-10 | 2019-06-18 | 万华化学集团股份有限公司 | A method of triisobutylene in separation tert-butyl acrylate reaction solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2282492A1 (en) | 1998-09-17 |
| JP2001514643A (en) | 2001-09-11 |
| TW438760B (en) | 2001-06-07 |
| DE19709392A1 (en) | 1998-09-10 |
| ID22758A (en) | 1999-12-09 |
| WO1998040342A1 (en) | 1998-09-17 |
| EP0973718A1 (en) | 2000-01-26 |
| BR9808158A (en) | 2000-03-28 |
| KR20000075989A (en) | 2000-12-26 |
| AU6827698A (en) | 1998-09-29 |
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