CN103796984A - Process for preparation of methacrylic acid and methacrylic acid esters - Google Patents

Process for preparation of methacrylic acid and methacrylic acid esters Download PDF

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CN103796984A
CN103796984A CN201180073461.6A CN201180073461A CN103796984A CN 103796984 A CN103796984 A CN 103796984A CN 201180073461 A CN201180073461 A CN 201180073461A CN 103796984 A CN103796984 A CN 103796984A
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water
methacrylic acid
extraction
component
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CN103796984B (en
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J·A·琼斯
T·巴尔多夫
H·舍费尔
H·西格特
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Evonik Roehm GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0426—Counter-current multistage extraction towers in a vertical or sloping position
    • B01D11/043—Counter-current multistage extraction towers in a vertical or sloping position with stationary contacting elements, sieve plates or loose contacting elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a process for preparation of at least one of methacrylic acid and a methacrylic acid ester, and a process for treatment of an aqueous phase comprising at least one organic compound. The methods comprise process steps: a1) gas phase oxidation of at least one C4 compound to obtain a reaction phase comprising methacrylic acid; a2) quenching of the reaction phase to obtain a crude aqueous phase comprising the methacrylic acid; a3) extraction of at least a part of the methacrylic acid from the crude aqueous phase comprising methacrylic acid into an organic solvent to obtain a crude organic phase comprising the methacrylic acid and a first aqueous phase, wherein the first aqueous phase comprises components i at least 65 wt%, preferably 65-99.9 wt%, more preferably 70-99.8 wt% of water, yet more preferably 75-99 wt%, more preferably 76-98.5 wt%, more preferably 77-98 wt%, even more preferably 78-97.5 wt%, even more preferably 79-95 wt%, yet more preferably 80-90 wt% of water, based on the total weight of the first aqueous phase, and ii not more than 35 wt%, preferably 0.1-35 wt%, preferably 0.2-30 wt%, more preferably 1-25 wt%, yet more preferably 1.5-24 wt%, more preferably 2-23 wt%, even more preferably 2.5-22 wt%, even more preferably 5-21 wt%, yet more preferably 10-20 wt% of at least one organic compound other than the organic solvent used as extraction agent in process step a3), based on the total weight of the first aqueous phase, wherein the sum of the weight amounts of i and ii is 100 wt%; a4) separation and optionally purification of at least a part of the methacrylic acid from the crude organic phase obtained in process step a3); a5) optionally, esterification of at least a part of the methacrylic acid obtained in step a4); b) extraction of at least a part of, preferably all of the first aqueous phase obtained in step a3) with an extraction agent to form an extraction phase comprising component ii and a second aqueous phase, the second aqueous phase being depleted in component ii compared to the first aqueous phase; c) at least partial separation of the second aqueous phase obtained in step b) from the extraction phase obtained in step b); d) optionally, at least partial separation of at least one organic compound from the second aqueous phase obtained in step c), to obtain a third aqueous phase which is depleted in at least one organic compound compared to the second aqueous phase; and e) optionally, separation of at least a part of the extraction agent from the extraction phase to obtain an extract comprising at least one component ii.

Description

The preparation method of methacrylic acid and methacrylic ester
Technical field
The present invention relates to the preparation method of methacrylic acid, the treatment process of the preparation method of methacrylic ester and the water that comprises at least one organic compound.
Background technology
Methacrylic acid (MAA) and methacrylic ester, for example methyl methacrylate (MMA) and butyl methacrylate, for various application.The industrial production of the methacrylic acid especially gaseous oxidation of the heterogeneous catalyst by iso-butylene, the trimethyl carbinol, Methylacrylaldehyde or isobutyric aldehyde is carried out.By cooling and condensation, such obtained vapor reaction is transformed into methacrylic aqueous acid mutually, optionally separate with lower boiling material for example acetaldehyde, acetone, acetic acid, propenal and Methylacrylaldehyde, then introduce solvent extraction tower, to utilize applicable extraction agent, for example short hydrocarbon, extraction and fractionation methacrylic acid.Separated methacrylic acid is further purified, and for example, by distillation, to separate high boiling impurity, for example phenylformic acid, toxilic acid and terephthalic acid, to obtain pure methacrylic acid.This kind of known method is for example described in EP0710643, US4, in 618,709, US4,956,493, EP386117 and US5,248,819.
This kind of known method produces a large amount of waste water at each operation stage, and in them, maximum is in water form residual after quenching extracts methacrylic acid mutually.Water is mainly from steam or the water of interpolation that enters gaseous oxidation step, and the use as the quenchant in cooling and condensing steps from water, and carrys out automatic oxidation reaction itself.This waste water contains quite a large amount of organic compound and can not re-use or throw aside safely to remove at least in part these organic compound in the situation that not further not processing.This type of organic compound generally includes for example methacrylic acid of desirable product (owing to being not exclusively extracted in organic extractant), and other by product of oxidation step for example vinylformic acid, acetic acid and propionic acid, and they also have commercial value.Organic content in this waste water generally too high and not can with the processing of water technology biological example, for example activated-sludge method is compatible and do not require significant dilution, considerable time and very large treatment facility, so that in business methacrylic acid is produced, often make this waste water burning, for example, US4, described in 618,709.But, the burning of waste water is on environment and be all disadvantageous economically, requires high-energy input, causes may requiring before being discharged in environment the discharge of further processing, cause being in addition present in the loss of the potential valuable organic compound in waste water, and the loss of water itself.
Can reclaim at least in part the organic compound being present in waste water therefore will be favourable.Also at least some of recycle-water itself will be will be advantageous that, or have for its experience biological treatment and/or be discharged in environment enough low organic content, optionally further do not process, or be this water and be enough to re-use, for example, as industrial technology water or for reacting itself, for example, for being oxidized and/or the purity of quench step.CN1903738 has proposed to use membrane separation apparatus to follow waste water acrylic acid, toluene and acetic acid that rectifying tower is produced from vinylformic acid with purifying.The shortcoming of membrane filtration is generally speaking, to require a large amount of water (often using waste water itself) to rinse out the not component by strainer.Then the washing water of this organic compound substrate concentration with increase itself must further be processed or burning.
Summary of the invention
Object of the present invention is usually the shortcoming that overcomes as far as possible art methods.
Other object is to increase methacrylic acid preparation method's overall efficiency and/or productive rate by reclaiming organic compound from processing wastewater.
Another object of the present invention is to reduce as far as possible waste water can re-use by orgnic compound pollution so that this water, experience biologically pure process, or be discharged into environment, optionally after the purge process of biology or other type, be discharged into environment, rather than burn together with organic compound.
Made by the preparation method of at least one in methacrylic acid and methacrylic ester for the contribution that solves above-mentioned purpose, the method comprises following methods step:
A1) at least one C 4the gaseous oxidation of compound is to obtain the reacting phase that comprises methacrylic acid;
A2) quenching of described reacting phase is to obtain the thick water that comprises methacrylic acid;
A3) at least a portion of described methacrylic acid is extracted into organic solvent from the described thick water that comprises methacrylic acid, to obtain the thick organic phase that comprises methacrylic acid, and the first water, wherein said the first water comprises following component:
I. at least 65 % by weight, preferably 65 % by weight-99.9 % by weight, more preferably 70 % by weight-99.8 % by weight water, more more preferably 75 % by weight-99 % by weight, more preferably 76 % by weight-98.5 % by weight, more preferably 77 % by weight-98 % by weight, even more preferably 78 % by weight-97.5 % by weight, even more preferably 79 % by weight-95 % by weight, more more preferably 80 % by weight-90 % by weight water, based on the gross weight of described the first water, and
Ii. be no more than 35 % by weight, preferably 0.1 % by weight-35 % by weight, preferably 0.2 % by weight-30 % by weight, more preferably 1 % by weight-25 % by weight, more more preferably 1.5 % by weight-24 % by weight, more preferably 2 % by weight-23 % by weight, even more preferably 2.5 % by weight-22 % by weight, even more preferably 5 % by weight-21 % by weight, more more preferably 10 % by weight-20 % by weight except as method steps a3) in the organic solvent of extraction agent at least one organic compound, based on the gross weight of described the first water
Wherein the weight amount sum of i. and ii. is 100 % by weight;
A4) at least a portion of described methacrylic acid and method steps a3) in the separating and purifying optionally of the thick organic phase that obtains;
A5) optionally, step a4) in the esterification of at least a portion of the described methacrylic acid that obtains;
B) step a3) at least a portion of the first water of obtaining, preferably whole, the extraction phase that comprises component ii. with formation with the extraction of extraction agent, and the second water, described the second water compared with the first water dilution component ii.;
C) the second water and the step that step obtains in b) b) at least part of of extraction phase of acquisition separate;
D) optionally, in the second water that at least one organic compound obtains from step c) at least partly separate, and obtain compared with the second water dilution the 3rd water of at least one organic compound.
E) optionally, at least a portion of described extraction agent separates with described extraction phase, to obtain the extract that comprises at least one component ii..
Also made by the treatment process of the water that comprises at least one organic compound for the contribution that solves above-mentioned purpose, the method comprises following methods step:
A) provide the first water that comprises following component:
I. at least 65 % by weight, preferably 65 % by weight-99.9 % by weight, more preferably 70 % by weight-99.8 % by weight water, more more preferably 75 % by weight-99 % by weight, more preferably 76 % by weight-98.5 % by weight, more preferably 77 % by weight-98 % by weight, even more preferably 78 % by weight-97.5 % by weight, even more preferably 79 % by weight-95 % by weight, more more preferably 80 % by weight-90 % by weight water, based on the gross weight of described the first water, and
Ii. be no more than 35 % by weight, preferably 0.1 % by weight-35 % by weight, preferably 0.2 % by weight-30 % by weight, more preferably 1 % by weight-25 % by weight, more more preferably 1.5 % by weight-24 % by weight, more preferably 2 % by weight-23 % by weight, even more preferably 2.5 % by weight-22 % by weight, even more preferably 5 % by weight-21 % by weight, more more preferably at least one organic compound of 10 % by weight-20 % by weight, based on the gross weight of described the first water
Wherein the weight amount sum of i. and ii. is 100 % by weight;
B) at least a portion of the first water, preferably whole, with the extraction of extraction agent to form the extraction phase that comprises at least one component ii., and the second water, described the second water compared with the first water dilution at least one component ii.;
C) the second water separates with at least part of of described extraction phase;
D) optionally, at least part of separation in the second water that at least one organic compound obtains from step c), and obtain compared with the second water dilution the 3rd water of at least one organic compound;
E) optionally, at least a portion of described extraction agent and described extraction phase separate the extract that comprises at least one component ii. to obtain.
At the step a1 of the method according to this invention) in experience gaseous oxidation C 4compound is preferably selected from the C of iso-butylene, the trimethyl carbinol, isobutyric aldehyde and Methylacrylaldehyde 4compound, or two or more mixture in them.Of the present invention one preferred aspect in, C 4compound stems from the division of methyl tertiary butyl ether (MTBE) or Ethyl Tertisry Butyl Ether (ETBE).
The step a1 of the method according to this invention) in gaseous oxidation preferably under at least one oxide catalyst exists, carry out.If C 4compound is iso-butylene or the trimethyl carbinol, can in a step, carry out in order to the gaseous oxidation that obtains the gas phase that contains methacrylic acid, wherein " step " is considered to refer to that the process that becomes Methylacrylaldehyde to go forward side by side by initial oxidation oxidation step becomes methacrylic acid substantially in same reaction zone, carries out under at least one catalyzer exists in this article.Alternative, step a1) in gaseous oxidation can be in more than one step, preferably in two steps, preferably in two or more reaction zones separated from one another, carry out, wherein preferably there are two or more catalyzer, every kind of catalyzer be preferably present in another catalyzer reaction zone separated from one another in.In two step gaseous oxidations, first step is C preferably 4compound is oxidized to Methylacrylaldehyde at least partly, and then Methylacrylaldehyde is oxidized to methacrylic acid at least partly.Therefore, for example, in the first reactions steps, preferably exist and be suitable at least one C 4compound oxidation becomes at least one catalyzer of Methylacrylaldehyde, and in the second reactions steps, has at least one catalyzer that is suitable for Methylacrylaldehyde to be oxidized to methacrylic acid.
The applicable reaction conditions of catalytic gas phase oxidation is, for example, about 250 ℃-about 450 ℃, the temperature that preferably approximately is 250 ℃-about 390 ℃, and about 1 normal atmosphere-about 5 atmospheric pressure.Space velocity can be about 6000/ hour of about 100-(NTP), about 3000/ hour of preferably approximately 500-.C 4for example iso-butylene is to the oxidation of Methylacrylaldehyde and/or methacrylic acid in charging, and for example catalytic gas phase oxidation, and catalyzer used is known in the literature, for example, from US5,248,819, US5,231,226, US5,276,178, US6,596,901, US4,652,673, US6,498,270, US5,198,579, US5,583,084 is known.
Be suitable for iso-butylene or Oxidation of t-Butanol to become the especially preferred Catalyst And Method of Methylacrylaldehyde and/or methacrylic acid to be described in EP0267556, the especially preferred Catalyst And Method that is suitable for the Methylacrylaldehyde to be oxidized to methacrylic acid is described in EP0376117.These documents are accordingly as the part with reference to introducing and be formed as the disclosure of invention.
In the method according to this invention Methylacrylaldehyde to the gaseous oxidation of methacrylic acid preferably in about about 350 ℃ and following temperature of 250-, under about about 3 atmospheric pressure of 1-, and carry out under the volume load of about about 1800Nl/l/h of 800-.
As oxygenant, conventionally use oxygen, for example, be air form, or be pure oxygen or for example, oxygen form with the gas of at least one inertia under reaction conditions (at least one in nitrogen, carbon monoxide and carbonic acid gas) dilution, wherein air preferably as oxygenant and nitrogen and/or carbonic acid gas preferably as diluent gas.If carbonic acid gas as diluent gas, it is preferably from the burning of reactant gases and/or by product, the carbonic acid gas of preferred catalytic or hot burns recirculated.Experience is according to the step a1 of the inventive method) in the gas of gaseous oxidation preferably also comprise water, it is conventionally water vapour form and exists.Can be before gas-phase reaction or during, or before gas-phase reaction and during, oxygen, one or more rare gas elementes and water are introduced to reacting phase or and C 4compound combination.
In a preferred embodiment of the method according to this invention, by the mixture supplying step a1 that comprises following material): at least one C 4the oxidation reactor Exhaust Gas of compound, air or oxygen and recirculation, the oxidation reactor Exhaust Gas preferably having burnt before recirculation.Described reactor Exhaust Gas preferably comprises at least one unreacted C 4compound, at least one oxycarbide, nitrogen and oxygen, and water, this depends on existence and the effect of separation condition and combustion step.
In two step gaseous oxidations according to the present invention, the C in first step 4compound: O 2: H 2o: the preferred volume ratio of rare gas element is generally 1:0.5-5:1-20:3-30, preferably 1:1-3:2-10:7-20.Methylacrylaldehyde in second step: O 2: H 2o: preferably 1:1-5:2-20:3-30 of the volume ratio of rare gas element, preferably 1:1-4:3-10:7-18.
According to the step a2 of the inventive method) in, the cooling and condensation (being commonly referred to as quenching) of the gas phase that makes to comprise methacrylic acid and obtain the condensation product that is the thick aqueous solution form that comprises methacrylic acid.Condensation can be by well known by persons skilled in the art and seem that any means that are applicable to carry out, for example by by be cooled to containing the gas phase of methacrylic acid lower than in its component at least one dew point, particularly water and methacrylic acid at least one the temperature of dew point.Applicable method of cooling is well known by persons skilled in the art, for example, utilize at least one interchanger cooling, or by quenching, for example, by using liquid, for example water, waterborne compositions or organic solvent, for example, be selected from the organic solvent of aromatics or aliphatic hydrocrbon, or the mixture of at least two kinds in them, spray described gas phase, wherein preferred organic solvent has compared with low-vapor pressure under quenching conditions, for example heptane, toluene or dimethylbenzene, wherein water is preferably as according to quench liquid of the present invention, and at least a portion of the condensation product forming in quench step itself even more preferably.Applicable method of quenching is well known by persons skilled in the art, for example, from DE2136396, EP297445, EP297788, JP01193240, JP01242547, JP01006233, US2001/0007043, US6,596,901, US4,956,493, US4,618,709, US5,248,819 know, a part for present disclosure is introduced and be formed as to their disclosure that relates to vinylformic acid and methacrylic acid quenching accordingly.Preferably gas phase be cooled to the temperature of 40-80 ℃ according to the present invention and obtain and comprise methacrylic aqueous acid with deriving from the water of quench step and/or condensation product washing, this aqueous solution can also comprise impurity for example acetic acid, toxilic acid, fumaric acid, citraconic acid, vinylformic acid and the formic acid of variable quantity, and aldehyde for example formaldehyde, acetaldehyde, propionic aldehyde, propenal, Methylacrylaldehyde, ketone and unreacted one or more C 4compound.These impurity and water need maximum possible degree separate to obtain highly purified methacrylic acid with methacrylic acid.
At least a portion of described methacrylic acid from the extraction containing the thick aqueous solution of methacrylic acid at method steps a3) utilize organic extractant, for example, at least one organic solvent, preferably at least one carries out with the immiscible organic solvent of water substantially, so that can form water and organic phase.Method steps a3) also comprise separated from one another to described water and organic phase.Can be different from the boiling point of methacrylic acid for having according to the preferred organic solvent of the step c) of the inventive method, preferably than its lower boiling point.Preferably, in the method according to the invention, method steps a3) in the organic extractant that uses have under atmospheric pressure measure lower than the boiling point of 161 ℃.Described organic extractant then can be in principle according to the step a4 of the inventive method) in separate with methacrylic acid, for example, by distillation, preferably at least in part, preferably, to separate to a large extent, wherein it is preferably removed in the position higher than pure methacrylic acid in distiller as low-boiling-point substance at least in part.The guiding of separated organic extractant or its part can be got back to method steps a3), optionally after and/or purification step cooling at least one.The preferred organic solvent of this step is especially selected from alkane and aromatics, and the hydrocarbon of preferred alkyl aromatics is wherein selected from C 6-C 8at least one organic solvent of hydrocarbon is preferred, and wherein heptane, toluene and dimethylbenzene are especially preferred, most preferably heptane, preferably normal heptane.Method steps a3) can just look at applicable any means and carry out by those skilled in the art are known, preferably as counter-current extraction, for example, utilize solvent extraction tower, Impulse packing or packed tower, rotating extractor, washing tower, phase separator or be suitable for carrying out with organic solvent extraction water and by the miscellaneous equipment of organic phase and aqueous phase separation.According to the present invention preferably, at least a portion of methacrylic acid in methacrylic aqueous acid will be included in, preferably at least 50 % by weight, preferably at least about 70 % by weight, preferably at least about 80 % by weight, more preferably at least about 90 % by weight are extracted in organic phase.
Therefore according to the step a3 of the inventive method) in obtain two phases: the thick organic phase that comprises methacrylic acid, it is led to the step a4 according to the inventive method), and by above-described amount containing component i. and ii.(water and at least one organic compound) the first water.Can be used as the organic compound that component ii. is included in the first water is any organic compound forming during gas phase oxidation, those that are for example associated mentioned with the thick water obtaining in quench step above, and unreacted C 4compound and remain in any methacrylic acid in water.Although the first water comprises on a small quantity for method steps a2) the organic solvent of extraction be possible, for example separate with the incomplete of the first water owing to organic phase, this solvent is not considered as component ii..
At the step a4 of the method according to this invention) in, allow step a3) in the thick organic phase experience that comprises methacrylic acid that obtains separate, preferably thermal separation method with by least a portion of the described methacrylic acid wherein comprising be used as method steps a3) in the organic solvent of extraction agent separate.If use thermal separation, this preferably distills, wherein method steps a3) in preferably remove as top product or at the upper position of distillation tower for the organic solvent extracting, and methacrylic acid or be the richest in that base is acrylic acid to be removed as bottoms or in the lower position of ratio extraction solvent of distillation tower.Can also use, for example, fractionation or rectifying tower, thus boiling point is retained in bottoms and can removes more highly purified methacrylic acid in the position higher than this tower bottom higher than the impurity of methacrylic acid.If there is the boiling point higher than methacrylic acid boiling point for the organic solvent extracting, can also be at the top of tower and/or higher position remove methacrylic acid phase.Being further purified of the methacrylic acid that obtained like this or rich methacrylic acid phase can utilize further thermal process, for example distillation or rectifying, or for example undertaken by crystallization by other means.Intermediate steps also can be included in the method according to this invention, at method steps a4) before or during, for example stripping or distillation, to separate low-boiling compound or higher-boiling compound, are filtered to remove solid impurity, crystallization, in washing etc. any or multiple.The number of purifying and other separating step depends on the required purity of contamination level and methacrylic acid final product.If methacrylic acid will in statu quo use, for example use as monomer or the comonomer of preparing methacrylate polymer, higher purity may be preferred, this especially depends on final application.If methacrylic acid is by esterified, the lower purity of methacrylic acid can be acceptable, if for example ester final product can be simpler than methacrylic acid, and more effective force or the more words of efficiently purifying.
At least a portion of the methacrylic acid that obtained like this is at method steps a5) in esterification can just look at applicable any mode and carry out by those skilled in the art are known, optionally under existing, stopper carries out, to prevent the polymerization of methacrylic acid and/or methyl methacrylate.Step a5) in carry out esterification in addition restriction especially of means.Esterification can be for example, as US6, and 469,202, JP1249743, EP1254887, US4,748,268, US4,474,981, US4,956,493 or US4,464, described in 229, carry out like that, a part for present disclosure is introduced and be formed as to the disclosure of their esterification that relates to vinylformic acid and methacrylic acid accordingly.Liquid phase esterification is preferred.If esterification utilizes the direct reaction between methacrylic acid and alcohol to carry out, preferably applicable catalyst is passed through in this reaction.Esterifying catalyst is well known by persons skilled in the art and comprises, for example, and heterogeneous or for example solid catalyst of homogeneous catalyst or liquid catalyst.Esterifying catalyst is such as US6 of acidic ion exchange resin preferably, 469,292, describe in JP1249743, EP1254887 or can trade(brand)name (Rohm and Haas Corp.), (Dow Corp.) or
Figure BDA0000476910040000093
those that (Lanxess AG) is purchased, or acid that can catalytic esterification, for example sulfuric acid H 2sO 4.
According to the present invention at method steps a5) in preparation methacrylic ester preferably there is formula [CH 2=C(CH 3) C(=O) O] n-R, and can pass through to use formula R(OH) malcohol methacrylated is formed, wherein
N and m represent 1-10, preferably 1-6, and more preferably 1-5, more preferably 1-4, the more preferably integer of 1-3,
R is selected from straight or branched, saturated or unsaturated, the ring of aliphatic series or aromatics or the hydrocarbon of straight chain and straight or branched, saturated or unsaturated, the ring of aliphatic series or aromatics or straight chain containing heteroatomic hydrocarbon, for example alkyl, hydroxyalkyl, aminoalkyl group, other residue nitrogenous and/or oxygen, glycol, glycol, triol, bis-phenol, fatty acid residue, the wherein preferred represent methylidene of R, ethyl, propyl group, sec.-propyl, butyl, especially normal-butyl, isobutyl-, hydroxyethyl, preferably 2-hydroxyethyl, and hydroxypropyl, preferably 2-hydroxypropyl or 3-hydroxypropyl, 2-ethylhexyl, isodecyl, cyclohexyl, isobornyl, benzyl, 3, 3, 5-trimethylcyclohexyl, stearyl, dimethylaminoethyl, dimethylaminopropyl, 2-tertiary butyl aminoethyl, ethyl triglycol, tetrahydrofurfuryl, butyldiglycol, methoxy poly (ethylene glycol)-350, methoxy poly (ethylene glycol) 500, methoxy poly (ethylene glycol) 750, methoxy poly (ethylene glycol) 1000, methoxy poly (ethylene glycol) 2000, methoxy poly (ethylene glycol) 5000, allyl group, ethylene glycol, Diethylene Glycol, triethylene glycol, Macrogol 200, poly(oxyethylene glycol) 400, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 1, 6-hexylene glycol, glycerine, two urea alkane, ethoxylation dihydroxyphenyl propane, containing the ethoxylation dihydroxyphenyl propane of 10 ethylene oxide units, TriMethylolPropane(TMP), ethoxylation C 16-C 18fatty alcohol for example contains those of 25 ethylene oxide units, 2-trimethyl ammonium ethyl.
Methacrylic ester can also, by other method well known by persons skilled in the art, for example, by transesterify, be prepared by methyl methacrylate.In the other possible preparation of hydroxyester derivative, can be in ring-opening reaction and corresponding ether ring, for example epoxide, especially oxyethane or propylene oxide reaction according to methacrylic acid of the present invention.
Preferred methacrylic ester is alkyl methacrylate, especially methacrylic acid methyl, ethyl, propyl group, sec.-propyl, butyl ester, especially methacrylic acid methyl, normal-butyl, isobutyl-, sec-butyl ester, especially methyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, hydroxy ester methacrylate derivative, for example hydroxyethyl methylacrylate, preferable methyl HEA, and hydroxypropyl methacrylate, preferable methyl vinylformic acid 2-hydroxypropyl ester or methacrylic acid 3-hydroxypropyl ester, and such as β-dimethyl-aminoethylmethacrylate of other methacrylic ester, 2-Ethylhexyl Methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid benzyl ester, methacrylic acid 3,3,5-3-methyl cyclohexanol ester, methacrylic acid stearyl, dimethylaminoethyl methacrylate, the amino propyl ester of dimethylaminoethyl acrylate methyl base, methacrylic acid 2-tertiary butyl ammonia ethyl ester, ethyl triglycol methacrylic ester, methacrylic acid tetrahydro furfuryl ester, butyldiglycol methacrylic ester, methoxy poly (ethylene glycol)-350 methacrylic ester, methoxy poly (ethylene glycol) 500 methacrylic esters, methoxy poly (ethylene glycol) 750 methacrylic esters, methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 2000 methacrylic esters, methoxy poly (ethylene glycol) 5000 methacrylic esters, allyl methacrylate(AMA), ethoxylation (optionally, for example, containing 25mol EO) C 16-C 18the metha crylic ester of fatty alcohol, methyl chloride vinylformic acid 2-trimethyl ammonium ethyl ester, ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate, TEGDMA, Macrogol 200 dimethacrylate, poly(oxyethylene glycol) 400 dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, HDDMA, glycerine dimethacrylate, two urea alkane dimethacrylates, ethoxylation bisphenol a dimethacrylate, ethoxylation is (optionally, for example,, containing 10EO) bisphenol a dimethacrylate, trimethylolpropane trimethacrylate, wherein especially preferable methyl methyl acrylate, butyl methacrylate and hydroxy ester methacrylate derivative.
According to the method steps of the inventive method b) in, extract at least a portion of the first water that comprises component i. and ii. with extraction agent, preferably whole, to form extraction phase and the second water.According to the present invention preferably, at least a portion of at least one component ii. is extracted in extraction phase, thus the second water compared with the first water dilution at least one component ii..Extraction preferably at the temperature of envrionment temperature or rising, preferably at about 15 ℃-about 70 ℃, more preferably about 20 ℃-about 65 ℃, more more preferably about 30 ℃-about 60 ℃, more more preferably at the temperature in the scope of about 40 ℃-about 55 ℃, carry out.Extract preferably liquid-liquid extraction.Extraction can be just looked at applicable any means by those skilled in the art are known, for example, utilize the known miscellaneous equipment that is suitable for liquid-liquid extraction of just looking at of extraction tower, washing tower, phase separator or those skilled in the art to carry out.Have been found that being suitable for according to the method steps of the inventive method extraction agent b) is organic solvent, ionic liquid and organic or inorganic oil.Be suitable for being to have at least one item in following performance according to the method steps of the inventive method extraction agent (especially organic solvent) preferred feature b), preferably at least two, more preferably at least three, more preferably whole:
I) the average k value that acetic acid is measured according to method described herein in extraction agent-aqueous systems at 25 ℃ is at 0.1-100, preferred 0.2-90, and more preferably 0.3-80, more more preferably 0.3-70, more preferably in the scope of 0.4-60;
Ii) be no more than 2260kJ/kg, be preferably no more than 2000kJ/kg, be preferably no more than 1500kJ/kg, more preferably no more than 1000kJ/kg, then more preferably no more than the evaporation enthalpy of 800kJ/kg;
Iii) 35-140 ℃, preferably 35-125 ℃, more preferably 40-120 ℃, the more more preferably boiling point of 40-110 ℃;
Iv) at 25 ℃, preferably 35 ℃, more preferably 45 ℃, more preferably at the temperature of 50 ℃, be no more than 150g/l again, be preferably no more than 130g/l, more preferably no more than 110g/l, again more preferably no more than 100g/l, even more preferably no more than the solubleness in water of 90g/l.
Except as otherwise noted, under about 50 ℃ and environmental stress, measure above-mentioned performance.Term " k value " refers to partition ratio, i.e. the corresponding organic compound of component ii. of the present invention distribution proportion between organic (extraction) phase and water under equilibrium state.Be greater than 1 k value refer in corresponding organic compound, be present in organic (extraction) in mutually than being present in many in water.Although there is the effect I that the extraction agent of the k value that is less than 1 can be used for having reached, the method according to this invention, higher k value, it is preferred being for example greater than 1 k value, because they show that organic compound is extracted into extraction phase more completely from the first water.Although the k value up to 100 is possible, have up to about 5,10,20,30,40,50,60,70, the extraction agent of 80 or 90 k value may be also preferred according to the present invention.Lower k value, especially lower than 5 and k value in above-mentioned scope may be also for example acceptable, if especially extraction agent also has one or more in other preferred properties in favourable scope.If extraction agent is organic solvent, evaporate enthalpy and boiling point preferably low as far as possible in actual limit, liquid preferably especially so that at the extraction agent temperature of carrying out in extraction.Evaporation enthalpy is preferably not less than about 22kJ/mol and boiling point is preferably greater than 0 ℃, is more preferably not less than the service temperature while extraction.Evaporation enthalpy is preferably higher than evaporation of water enthalpy (2260kJ/kg or 40.65kJ/mol), so as to reduce as far as possible according to the second water in the step c) of the inventive method and extraction phase after separating by the needed energy input of any residual extractant thermal separation residual in the second water.Evaporation enthalpy is not also preferably higher than at least one evaporation enthalpy in the organic compound of component ii., to reduce as far as possible the needed energy input of one or more organic compound thermal separations of extraction agent and component ii..Especially preferably evaporate enthalpy not higher than at least one the evaporation enthalpy in methacrylic acid, vinylformic acid and acetic acid.For the same reason, with separating for facilitated extraction agent, the boiling point of extraction agent is preferably lower than at least one boiling point in the organic compound of component ii., preferably lower than at least one boiling point in methacrylic acid, vinylformic acid and acetic acid, preferably low as far as possible in preferred scope.If ionic liquid or organic or inorganic oil as extraction agent, its evaporation enthalpy and boiling point are preferably high as far as possible, preferably higher than at least one at least one organic compound of water and component ii..Extraction agent preferably only has low solubility in water, especially under extraction temperature, and preferably substantially or completely water insoluble, and preferably substantially or completely not miscible with it, to can realize separating as far as possible completely of extraction phase and the second water.
According in the step c) of the inventive method, the second water is separated with extraction phase at least in part.Can utilize according to extraction b) of the step of the inventive method and method steps separating c) that those skilled in the art are known just looks at applicable any means, preferably utilize counter-current extraction to carry out, wherein method steps is b) and c) preferably in same equipment, for example utilize extraction tower, Impulse packing or packed tower, rotating extractor, especially uses those of centrifugal force separate, washing tower, phase separator or be suitable for the miscellaneous equipment of organic phase or ionic liquid phase and water to carry out.If the with an organic solvent extraction agent in b) as method steps, extraction phase that can the after separating in c) obtains by method steps incinerates.The advantage that this kind of incineration has be substantially organically extraction phase serve as fuel, thereby reduce the demand of buying fuel.For example, if fuel cost or related request, for example carry easily and/or cost be disadvantageous and/or the organic compound of component ii. in one or more marketable value low, especially with they separate and/or the desired overall work of purifying is compared with expense, this option may be preferred.
The second water preferably comprises and is no more than 5.0 % by weight, preferably be no more than 4.5 % by weight, more preferably no more than 4.0 % by weight, again more preferably no more than 3.5 % by weight, more preferably no more than 3.0 % by weight, organic compound beyond the extraction agent even using in the eliminating method step b) more preferably no more than 2.5 % by weight, based on the gross weight of described the second water.The amount of the organic compound in the second water except extraction agent is preferably low as far as possible, preferably 0 % by weight, but 0.5 % by weight, and 0.8 % by weight, the lower limit of 1.0 % by weight or 1.2 % by weight may be acceptable.In the second water, in the total amount of organic compound, (do not comprise from method steps any residual extractant b)), generally speaking, formaldehyde can account for up to about 1.5 % by weight, and based on the gross weight of the second water, all the other are by C 2or more senior C-chain organic compound, especially C 2-C 6or C 2-C 4compound forms.The total amount of this kind of organic compound depends on extraction step that method steps extraction b) comprises or the number of extraction cycle, and the amount of the extraction agent using in this extraction.More the extraction step of high number causes organic compound content lower in the second water, but generally also require longer time and/or multistage extraction, and/or more substantial extraction agent, this may cause the extraction phase of the more volume that then must further process or incinerate.
The method according to this invention can also comprise that intermediate steps is for example for removing the stripping of low-boiling compound or for removing the distillation of low or higher-boiling compound.
According in the optional step d) of the inventive method, by least one organic compound at least in part with the second aqueous phase separation, with the 3rd water of at least one organic compound that obtained compared with the second water dilution.Described the 3rd water preferably comprises and is no more than 3 % by weight, preferably be no more than 2.8 % by weight, more preferably no more than 2.5 % by weight, again more preferably no more than 2.2 % by weight, organic compound beyond the extraction agent using in eliminating method step b) more preferably no more than 2.0 % by weight, based on the gross weight of described the 3rd water.The amount of the organic compound in the 3rd water is preferably low as far as possible, preferably 0 % by weight.If organic compound is present in the 3rd water, about 1.5 % by weight can be formaldehyde form at the most, comprise C in rest part eliminating method step b) beyond the extraction agent using 2or more senior C-chain compound, especially C 2-C 6or C 2-C 4compound.Therefore the 3rd water preferably comprises and is less than 5000ppm, is preferably less than 4000ppm, is more preferably less than 3000ppm, preferably 0-3000ppm, more preferably 0-2500ppm, more preferably 0-2200ppm, be most preferably not exceeding 2000ppm except C 1compound (formaldehyde) in addition with eliminating method step b) in organic compound beyond the extraction agent that uses, based on the gross weight of described the 3rd water, wherein 500ppm, or 1000ppm, or 1500ppm, or the lower limit of 1800ppm may be acceptable, this depends on further application and/or the processing of the expectation of the 3rd water.The separation preferably thermal separation of method steps in d), for example distillation or component distillation, preferably under normal pressure.Preferably, method steps d) in, separate to greatest extent residual method steps residual extractant b) that derives from the second water.If method steps is the middle extraction agent using and water formation azeotrope b), separate and can comprise component distillation, for example use the component distillation of entrainment agent.In aspect preferred according to one of the step d) of the inventive method, if by distillation, especially utilize the separation of fractional distillation or rectifying for method steps d), preferably separate lower boiling component at the top of tower, especially the boiling point component lower than extraction agent, extract extraction agent out at the side outlet of tower, any component ii. or together with extraction agent or at the other side outlet of tower, preferably extracts out at the low side outlet of the side outlet than extracting extraction agent out.Then the extraction agent of any separation like this can be recycled to the extraction in b) according to the step of the inventive method, and this is corresponding to according to the step of the inventive method h).If identical with any extraction agent of separation in this step mutually in one or more organic compound of separated portion ii., this can be added to mutually in the extraction phase that method steps separates in c).If different from extraction agent mutually in one or more organic compound of separated portion ii., this not homophase can be directed to according to the step f) of the inventive method or step j).Preferably carry out the step d) according to the inventive method, the wherein extraction agent in b) as the method steps of the inventive method of organic solvent, if but ionic liquid or oil extraction for method steps b), it also can carry out.
According in the step e) of the inventive method, the extraction agent that method steps is used in b) separates the extract that comprises at least one component ii. to obtain at least in part with extraction phase.If organic solvent as extraction agent, the separation of method steps in e) preferably utilizes thermal separation method to carry out.Applicable thermal separation method is well known by persons skilled in the art, and wherein distillation, fractionation, rectifying and similar approach are preferred according to the present invention, wherein preferably vacuum distilling.One or more separation methods can be included in steps of a method in accordance with the invention e) in.In preferred thermal separation method, in the time that the organic solvent of the extraction agent in b) as method steps has than the low boiling point of one or more components ii. to be separated, on the top of distillation tower, or at one or more upper positions of separation column or rectifying tower, preferably, at the first half of this tower, remove extraction agent, and in the position with respect to removing extraction agent lower one or more positions, or at this tower bottom, the extract of removing one or more components ii. or comprising at least one component ii..Use boiling point than the advantage of the low organic solvent of at least one component ii. extraction agent in b) as method steps to be, some or all of component ii., especially methacrylic acid and vinylformic acid are heat sensitive and along with temperature increase more and more trends towards dimerization, oligomeric or polymerization.Stopper is added in these compounds thermal treatment at elevated temperatures therefore general requirement.If will separate more lower boiling extraction agent, if and/or to separate be vacuum distilling, this separation can be carried out under the lesser temps of the boiling point lower than corresponding component ii., thereby reduces the tendency of polymerization and therefore also reduce the needs to stopper.
If ionic liquid or organic or inorganic oil is the extraction agent in b) as method steps, the separation of method steps in e), preferably by being separated or evaporating, preferably undertaken by the evaporation of one or more volatile constituents.
The method according to this invention can also be included in the one or more intermediate steps between any or all of method steps, for example, for removing the stripping of low-boiling compound or for removing the distillation of low or higher-boiling compound.
According in the inventive method preferred embodiment, described method also comprises following methods step:
F) at least a portion of at least one component ii. separates from described extract.
The separation preferably thermal separation method of method steps in f), preferably distillation, fractionation or rectifying, preferably vacuum distilling wherein separates at least a portion of at least one component ii. from extract.Extract may for example, also comprise extraction agent or other component ii. except at least one component ii. to be separated.If be included in extract more than a kind of component ii., for example two or more component ii., likely only separate a kind of component ii. at method steps in f), or separate two or more component ii..Number and the amount of other compound in the extract for the treatment of therefrom to separate described at least one component ii. can be easily determined and be depended primarily in distillation, fractionation or rectifying by those skilled in the art as the selection of separation means, and the boiling point separately of not intending the component that separates of one or more components ii. to be separated and extract, especially the degree of approach of the boiling point of the boiling point of other component of extract and at least one component ii. to be separated and, if will separate more than a kind of component ii., it is the boiling point proximity to one another of component ii. to be separated.The other factor of considering is the required purity of at least one component ii. to be separated.At least one component ii. is further purified may be desirable or or even necessary according to the after separating in the step f) of the inventive method.
In the method according to the invention likely, in other method steps,
G) allow the 3rd water experience at least one biologically pure processing.
Term " biologically pure processing " in the scope of the invention is intended to refer to any processing of the purity that improves water, for example, by removing pollutent or impurity, preferably have organic pollutants, utilize one or more biological organisms and/or microorganism or biology or chemical-biological activities material, for example, derived from the material of this type of organism or microorganism.Treat that pollutent and the impurity removed are like this generally the organic compound remaining in the 3rd water.Digestion or decomposition by some or all organic compound are removed.The purity of the increase of water is for example measured as follows: reduce by pollutent and/or impurity, and/or reduce by biochemical oxygen demand (BOD) (BOD) or the chemical oxygen demand (COD) (COD) of water, preferably be reduced to and mean that this waste water can re-use, for example, as industrial technology water or be used further to the method according to this invention, especially method steps a1) or a2) in one or two, maybe can be discharged into the level in environment or water supply chain, this depends on reached purity.Biologically pure processing is well known by persons skilled in the art and passable, for example, is one or more during so-called activated sludge is processed.This kind of processing is conventional and is well known to those skilled in the art.Biologically pure processing can be undertaken by one or more stages, and can be continuous or discrete.
If allow at least one the biologically pure processing in g) at method steps of the 3rd water experience, preferably at least one in aerobic treatment and anaerobic treatment of this processing.In an embodiment of processing with two or more stages, for example, the first anaerobic treatment can be followed aerobic treatment below, the first aerobic treatment can be followed anaerobic treatment below, maybe can use the sequence of anaerobism and/or aerobic treatment, for example, in order batch reactor.
According in aspect one of the inventive method, in other method steps,
H) by method steps d) with e) at least one at least a portion of the described extraction agent that separates be recycled to method steps b).
Can by method steps d) with e) in one or two in the extraction agent that separates a part or substantially all guiding get back to method steps b), optionally there are one or more intermediate steps for example cooling, purifying, for example pass through distillation, washing etc., or stripping is to remove more volatile compounds.The advantage that the recirculation of this kind of extraction agent has is the total amount of extraction agent in minimizing method, especially reduces the amount of the useless extraction agent that must throw aside.
If the separation according to the method steps of the inventive method in f) is thermal separation, by separated from one another component may be not always feasible or, for example, in economics or technical reality, if for example two or more components have closely similar boiling point.If experience method steps extract f) comprises relatively large component, if especially one or more components ii. has similar boiling point with treating at least one the component ii. separating in f) at method steps, become more difficult and make that the separation of the only a kind of component ii. in method step f) is carried out to meticulous adjusting, situation may be especially like this.Then may be more suitable or actual be two or more component ii. to be separated in j) at other method steps, this kind of the adaptation wherein particular separation of corresponding component ii. being required may be more prone to reach.Therefore, according in aspect one of the inventive method, at least one the component ii. obtaining in step f) is the mixture of at least two kinds of component ii. and in other method steps
J) at least one component ii. separates at least in part from this mixture.
Separation according to the method steps of the inventive method in j) can comprise one or more separating steps, for example thermal separation, as above to discussing according to other separating step in the inventive method, chromatographic separation, chemical separation, the reaction product that for example can separate with one or more other components ii. more easily with formation by the preferential reaction of a kind of component ii. or reaction product that can be separated from one another more easily with formation by the reaction of two or more component ii., or any other those skilled in the art are known just looks at applicable separation means.
According in the inventive method preferred embodiment, at least one organic compound of component ii., at least one the component ii. preferably separating at least in part in j) at method steps is at least one organic compound that is selected from carboxylic acid, aldehyde and ketone.In the middle of them, preferred at least one component ii. according to the present invention, at least one the component ii. preferably separating at least in part in j) at method steps is at least one in acetic acid, vinylformic acid, propionic acid and methacrylic acid.
If at least one the component ii. separating at least one in e), f) with j) of method steps is or comprises methacrylic acid, according in the inventive method preferred embodiment, add at least a portion of this methacrylic acid phase to method steps a2) in obtain thick water, and/or method steps a3) in obtain thick organic phase in.For example, if the one or more middle methacrylic acid that separate of method steps in e), f) with j) do not have the required purity of its end-use, this embodiment may be preferred.For example, if the methacrylic acid separating separates lower than the component of methacrylic acid together with one or more boiling points, may be preferred to adding in thick water.For example, if the component except methacrylic acid has the boiling point higher than methacrylic acid, may be preferred to the interpolation in thick organic phase, because being that more higher-boiling compound can be at method steps a4 for this kind) in separation.Although methacrylic acid and other component, especially the relative proportion of other component ii. also may play a role, but the character of other component at least one the component ii. separating at least one in e), f) with j) of method steps determine to add mutually to which this separate at least one in e), f) with j) at method steps aspect the phase of methacrylic acid, there is larger weight.For example, if the methacrylic acid separating at least one in e), f) with j) of method steps is purer, for example comprise, be no more than about 5 % by weight, preferably be no more than about 4 % by weight, be preferably no more than about 3 % by weight, be preferably no more than about 2 % by weight, the impurity of preferably approximately 1 % by weight-about 2 % by weight or other component ii., can be preferably by this methacrylic acid introducing method step a4) optional purification step in.
In aspect another of the inventive method, allow at least a portion of at least one the component ii. separating at least one in e), f) with j) of method steps or method steps a3) at least a portion experience following methods step of the first water of obtaining:
K) esterification is to obtain the ester phase that comprises at least one ester.
If at least one component ii. is carboxylic acid accordingly, this step may be preferred.The details of esterif iotacation step with above to according to the method steps a5 of the inventive method) describe those are identical.Replace or except obtaining corresponding at least one component ii. itself extraly, the esterification of at least one the component ii. separating at least one in e), f) with j) of method steps may be preferred, this for example depends on the obtainable purity of separated corresponding component ii., market or other application of corresponding component ii. compared with its ester.For example, if the first water only comprises the impurity of small proportion and/or does not intend the component ii. separating, for example be less than about 6 % by weight, preferably be less than about 5 % by weight, preferably be less than about 4 % by weight, be more preferably less than the impurity of about 3 % by weight and/or do not intend the total impurities of the component ii. separating, based on the gross weight of described the first water, especially for example, itself compare and may be more prone to the impurity that separates with the ester of corresponding component ii. with component ii., be included in method steps a3) in the esterification of at least one component ii. in the first water of obtaining may be preferred.
Be included according to ester of the present invention especially preferred ester group in mutually in C 1-C 4carboxylic acid and C 1-C 4alcohol, wherein based on C 2-C 4the ester of carboxylic acid is preferred.Except to method steps a5) relevant mentioned methacrylic ester extraly, especially preferred ester also has methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, sec-butyl propionate, preferred acetic ester and acrylate in them.
According to the present invention, likely described ester comprises at least two kinds of esters mutually.If at least one the component ii. or the method steps a3 that at least one in e), f) with j) of method steps, separate) at least a portion of the first water of obtaining comprise and can react at least two kinds of component ii. that form ester, especially at least two kinds of carboxylic acids, situation can be like this.If can react described at least two kinds of component ii. of formation ester is especially difficult to separate, for example, by heat or other means, for example, when their performance for example boiling point, solubleness and/or volatility in given solvent are very approaching, and their ester is not time can be not so difficultly separated from one another, this embodiment may be preferred.
The method according to this invention may further include following methods step
M) at least one ester separates with at least part of of described ester phase;
N) optionally, the m) purifying of middle at least one ester separating of method steps.
Generally speaking, except at least one ester, ester can also comprise solvent mutually, and for example water or be suitable at least one organic solvent of esterification, or their mixture, and unreacted component ii., also have one or more other esters possibly.The separation of method steps in m) is can be by those skilled in the art known and seem to be suitable for any separation means that corresponding ester and ester are separated.The example of applicable separation means is, for example, thermal separation, for example distillation, fractionation or rectifying, the separation means of the different solubilities compared with other component based at least one ester and ester phase, solid-liquid separation means is for example filtered etc.If desired or wish, also can carry out the purifying of at least one ester that method steps separates in m).Means of purification depends on ester, wherein for example, and by hot means, by chromatogram means, by washing or can considering by the purifying of crystallization.
According in the inventive method preferred embodiment, at least a portion of at least one ester obtaining in k), m) and n) at least one of method steps is made the extraction agent of method steps in b).
According in the inventive method embodiment, described method is further comprising the steps of:
Aa1) division of methyl tertiary butyl ether (MTBE) is to obtain at least one C 4compound and methyl alcohol,
Wherein said at least one C 4at least a portion of compound is as raw material supplying method steps a1) at least one gaseous oxidation.MTBE is widely used as the raw material of iso-butylene and the division of MTBE is well known in the art.The division of MTBE can be undertaken by any suitable means well known by persons skilled in the art.Applicable catalyzer and reaction conditions are described in for example with in Publication about Document: EP1149814, WO04/018393, WO04/052809; Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th edition, A4 volume, the 488th page; V.Fattore, M.Massi Mauri, G.Oriani, G.Paret, Hydrocarbon Processing, in August, 1981,101-106 page; Ullmann ' sEncyclopedia of Industrial Chemistry, the 5th edition, A16 volume, 543-550 page; A.Chauvel, G.Lefebvre, " Petrochemical Processes, Technical and Economic Characteristics ", the 1st volume, technip, Paris, 1989, the 213 pages and continued page; US5,336,841, US4,570,026 and the reference wherein quoted.The disclosure of these reference is incorporated herein for reference and is formed as the part of the disclosure of invention.
Two kinds of primary products of MTBE division are C 4compound iso-butylene and methyl alcohol.Other C 4the compound trimethyl carbinol also can be included in dissociative reaction product mutually in.In iso-butylene and the trimethyl carbinol, any or both can be used as raw material supplying method steps a1), to be configured for total C of raw material of this method steps 4compounds content or the supplementary other C that derives from another source 4content.In the middle of one or more, separation and/or purification step are at division and such at least one obtained C of MTBE 4compound is to method steps a1) in gaseous oxidation supply between be also possible, for example, with as far as possible by described at least one C 4compound and methyl alcohol are separated from one another and remove any by product that may adversely affect gaseous oxidation from described division.Separating and/or purify can be by well known by persons skilled in the art and look like applicable any means and carry out.Applicable purification and separation method for example, are described in EP1149814, WO04/018393 and WO04/052809.After separating methanol, then can optionally described C will be comprised 4compound iso-butylene is as the division phase purifying of major constituent and offer method steps a1 as raw material).Applicable method of purification be well known by persons skilled in the art and preferably include distillation, extraction, absorption, absorption, chromatography or washing at least one, preferably distill and extract at least one, preferably distillation and extracting at least one times at least one times.Can be at least in part by the C in unreacted MTBE and this step 4compound Phase separates.Can optionally the MTBE purifying of separation be also recycled to dissociative reaction at least in part.
According in the inventive method preferred embodiment, by method steps aa1) in the methyl alcohol supply method step that obtains k).In aspect the inventive method other, can be by method steps aa1) in the methyl alcohol supply method step a5 that obtains).Can, optionally by this methyl alcohol purifying, preferably utilize for example distillation of hot purifying, fractionation or rectifying, crystallization, extraction tower or washing, more preferably distillation at least one times.The example of methyl alcohol purifying is described in EP1254887.
The invention still further relates to for the preparation of at least one equipment in methacrylic acid and methacrylic ester, at least comprise the assembly that the following guiding of fluid is each other communicated with:
A1) gaseous oxidation unit,
A2) quenching unit,
A3) the first extraction cells,
A4) the first separating unit,
A5) optionally, the first esterification unit,
B) the second extraction cells.
Term " fluid guiding is communicated with " is interpreted as and refers to that unit can be that in liquid, gas, steam, supercutical fluid or any other fluid, the fluid of at least one can direct at least one other unit from a unit through connecting satisfied at this.This can be for example by via pipe or pipeline (for example, by the material of resistance to reaction reagent and leading condition, for example stainless steel or glass or any other applicable material well known by persons skilled in the art are made) direct connection reach, or utilize and be arranged in tank car between each unit or groove or reservoir and indirectly reach.If pilot gas and its should keep gaseous state, the device of pilot gas preferably maintains than at the high temperature of the dew point of this gas.If guiding liquid, the device of guiding this liquid preferably maintain than the component existing in liquid and/or this liquid solidify and/or temperature that set point is high under.This can be by means of heat insulation the device of the corresponding gas of guiding or liquid and/or heating are reached.The condition that all reactors, tower and other apparatus assembly are preferably experienced by resistance to reaction reagent and they, for example especially material manufacture of temperature and pressure condition.
Gaseous oxidation unit A1) preferably include the reactor that at least one is suitable for carrying out gas-phase reaction, especially pressure reactor, preferably at least one multitubular reactor, for example be formed as pipe and shell mould reactor, and/or at least one panel-shaped reactor and/or at least one fluidized-bed reactor, wherein multitubular reactor is preferred.Especially preferred is at least one multitubular reactor, and wherein oxide catalyst is arranged at least one pipe, and preferably wherein this pipe is filled or applied with oxide catalyst, preferably fills.According to the present invention, preferred oxide catalyst is mentioned those relevant to the inventive method above.Reactor material should be patience and preferred inertia to the reaction reagent of inside reactor and leading condition.Applicable reactor can be for example from MAN DWE GmbH, Deggendorfer Werft, Germany or from IHI Corporation, Japan is purchased and is formed as a part for general knowledge as well known to those skilled in the art.
In two stage gas phase oxidations, gaseous oxidation unit can comprise at least two reaction zones, and each reaction zone comprises oxide catalyst.Described at least two reaction zones can be at least two reaction zones in single reaction vessel, or at least two reactors.Oxide catalyst in the first reaction zone is preferably by least one C 4compound, preferably iso-butylene and/or Oxidation of t-Butanol become the oxide catalyst of Methylacrylaldehyde, and oxide catalyst in second reaction zone is preferably suitable for Methylacrylaldehyde to be oxidized to methacrylic acid.Applicable catalyzer is mentioned relatively with the method according to this invention in the above.
In aspect of present device is preferred, oxygenant, preferably oxygen, preferably at least one feedway at least one source of air, and at least one feedway of water and/or steam, is communicated with gaseous oxidation unit fluid.If gaseous oxidation unit at least comprises the first oxidation zone and other oxidation zone, this equipment can comprise at least one feedway of at least one oxidizer source and at least one feedway of water and/or steam for each oxidation zone.Equipment may further include the feedway of thinner, described thinner is nitrogen, argon gas and/or carbonic acid gas for example, preferred nitrogen or carbonic acid gas, for example, from catalytic combustion unit (CCU) or hot fuel element (TCU), the preferably CCU in downstream or the carbonated recycle gas of TCU in the device in accordance with the invention.Corresponding feedway should be made up of for example stainless steel of material or the glass of resistance to reaction reagent and leading condition.In preferred design, by C described in oxygen, thinner and water supply 4stream, then enters corresponding reactor, so that preformed mixture enters reactor.
According to the step a1 of the inventive method) preferably in gaseous oxidation unit, carry out.
According in present device preferred embodiment, quenching unit A2) be wherein to make gas oxidation phase condensation and/or absorption and the absorptive unit that forms liquid phase.Preferably make to be present in the condensation and form solution, the preferably aqueous solution as main oxidation products containing methacrylic acid in absorptive unit of methacrylic acid in the oxidation mutually of leaving catalytic reaction zone.Also can in absorptive unit, unreacted Methylacrylaldehyde be separated and if necessary, guide and get back to gaseous oxidation district for further reaction.It is known to the skilled being suitable for according to the quenching unit of present device.According to the step a2 of the inventive method) preferably in absorptive unit, carry out.
According in present device preferred embodiment, quenching unit A2) be connected to the first extraction cells A3 below).By quenching unit A2) in form be directed to the first extraction cells A3 containing methacrylic aqueous acid), organic solvent is wherein provided, methacrylic acid is preferably extracted in this solvent substantially.Organic solvent is preferably substantially immiscible with water, so that the water of methacrylic acid that formed dilution at least in part, and containing the organic phase of methacrylic acid.About the details method steps a3 in the above of preferred organic solvent) description in provide.Method steps a3) preferably at the first extraction cells A3) in carry out.Those skilled in the art are known and seem that any extraction cells being applicable to for this kind of extraction of methacrylic acid can consider as the first extraction cells A3).
Equipment according to the present invention is included in the first extraction cells A3) the first separating unit A4 in downstream).If equipment according to the present invention is for the preparation of methyl methacrylate, the first separating unit A4) at the first esterification unit A5) upstream, preferably at the first extraction cells A3) and the first esterification unit A5) between and be communicated with their fluids.The first separating unit A4) be preferably suitable for methacrylic acid to separate, preferably purifying, in particular for by methacrylic acid and the first extraction cells A3) in the extraction agent that uses separate, preferably also allow methacrylic acid and the first extraction cells A3 leaving according to present device) thick organic phase in other component of existing separate, this thick organic phase is corresponding to according to the method steps a3 of the inventive method) thick organic phase.The first separating unit A4) thermal separation unit preferably, preferably include distillation tower, separation column, rectifying tower and those skilled in the art known and seem to be suitable for the method steps a3 of the inventive method) any other heat separation device separating at least one.The first separating unit A4) comprise that more than one separation phase is possible.
The first optional purification unit of the methacrylic acid separating for purifying the first separating unit also can be arranged in the downstream of the first separating unit.The first optional purification unit can be, for example, hot purification unit, such as distillation tower, separation column, rectifying tower etc., crystalline element, or those skilled in the art are known and seem to be suitable for any miscellaneous equipment of purifying methacrylic acid.
Equipment according to the present invention may further include the one or more extra assembly between any or all mentioned unit or assembly, for example, by heat or the stripper plant of height and/or low boiling component separation, solid/liquid separation apparatus, for example at least one strainer and/or whizzer, and/or cooling and/or heating unit.In preferred design, for example, for the distillation tower of low-boiling compound and optionally in addition filter arrangement in downstream, quenching unit and extraction cells upstream.In aspect two-stage gaseous oxidation unit other preferred, quenching cell layout is between these two stages.
Unreacted Methylacrylaldehyde can be in quenching unit, the first extraction cells, the first separating unit, the first purification unit or any above-mentioned other equipment component any in separate, and gaseous oxidation unit is got back in guiding so that further reaction.
The first esterification unit A5) can be arranged in the first separating unit A4) or the downstream of optional the first purification unit.To the first esterification unit A5) not in addition restriction and can be to be suitable for esterification to be formed methacrylic ester by methacrylic acid especially, any unit of preferable methyl methyl acrylate.It is preferably suitable for liquid phase esterification.The first esterification unit A5) preferably include esterifying catalyst, it can be heterogeneous or for example solid catalyst of homogeneous catalyst or liquid catalyst, and such as US6 of acidic ion exchange resin preferably, 469,292, describe in JP1249743, EP1254887 those or with trade(brand)name
Figure BDA0000476910040000251
(Rohm and Haas Corp.),
Figure BDA0000476910040000252
(DowCorp.) or
Figure BDA0000476910040000253
those that (Lanxess AG) is purchased, or acid that can catalytic esterification, for example sulfuric acid H2SO4.
The second purification unit can be arranged in the first esterification unit A5) downstream so that by wherein produce methacrylic ester purifying.The second optional purification unit can be, for example, and hot purification unit, such as distillation tower, separation column, rectifying tower etc., crystalline element, or those skilled in the art are known and to seem to be suitable for purifying methacrylic acid be ester, especially any miscellaneous equipment of methyl methacrylate.
Also comprise the second extraction cells B according to equipment of the present invention).The second extraction cells B) for by the first extraction cells A3) at least a portion of the water that comprises in the first water of obtaining separates with at least a portion of especially above-mentioned at least one the component ii. of at least one organic compound, to obtain the second water and organic phase.According to the method steps of the inventive method b) preferably at the second extraction cells B) in carry out.
At the second extraction cells B) in, extract at least a portion of the first water with extraction agent to form the second water and extraction phase, and preferably by described the second water also with extraction phase with possible at utmost separating in technical limitation.Therefore, according at least method steps of the inventive method b), preferably also have method steps c), preferably at the second extraction cells B) in, most preferably undertaken by continuous mode.The second extraction cells B) to preferably include at least one extraction tower, washing tower, phase separator or those skilled in the art known and seem to be suitable for liquid-liquid extraction, preferably also be suitable for organic phase or ionic liquid phase and aqueous phase separation, more preferably be suitable for by the miscellaneous equipment of continuation method extraction and fractionation, for example at least one extraction tower, at least one Impulse packing and/or packed tower, at least one rotating extractor, especially at least one uses rotating extractor, at least one washing tower and/or at least one phase separator that centrifugal force separates.The second extraction cells B) preferably can be under envrionment temperature, and in the temperature except envrionment temperature, the temperature especially raising, especially above to b) and c) tolerance and operating at relevant mentioned temperature of method steps.
At least one incinerator or fuel element can be included in according in equipment of the present invention, for example, incinerate for the extraction phase that the second extraction cells is obtained.
Equipment according to the present invention can further include the 3rd separating unit D).The 3rd separating unit D) be preferably used for b) middle any residual extractant and the second aqueous phase separation using of method steps.According to the method steps of the inventive method d) preferably at the 3rd separating unit D) in carry out.The 3rd separating unit D) can be other extraction cells, but preferably thermal separation unit, such as distillation tower, separation column, rectifying tower etc., wherein those skilled in the art are known and seem that any device that is suitable for this kind of separation can be considered in the device in accordance with the invention.
Equipment according to the present invention can further include the 4th separating unit E).The 4th separating unit E) preferably include at least one thermal separation equipment at least a portion of described extraction agent is separated with extraction phase and obtain the extract comprising according at least one component ii. of the present invention, this method steps corresponding to the inventive method is e).Can also comprise at least one other thermal separation equipment to will separate with described extract according at least a portion of at least one assembly ii. of the present invention, this method steps corresponding to the inventive method f).Those skilled in the art are known and seem that being suitable for carrying out method steps e) such as can consider, for equipment according to the present invention, at least one in distillation, fractionation or rectifying tower etc. with the thermal separation equipment separating f).
Other separating unit also can be included in according in equipment of the present invention.An example of preferred other separating unit is to be suitable for by least one component ii. and according to the mixture that comprises at least two kinds of component ii. of the present invention, for example, according to the separating unit of the mixture separation obtaining in the step f) of the inventive method, this is corresponding to according to the step of the inventive method j).This kind of preferably thermal separation unit of other separating unit, preferably includes at least one distillation tower, separation column, rectifying tower etc.
According to equipment of the present invention preferably at the 4th separating unit E) and/or at least one other separating unit, and the first extraction cells A3) and/or the first separating unit A4) between comprise at least one conduit, for getting back to the first extraction cells A3 by methacrylic acid with containing at least one guiding mutually of methacrylic acid) and the first separating unit A4) at least one.
Optionally comprise at least one second esterification unit K according to equipment of the present invention) for by least one component ii. esterification to obtain ester phase, preferably at the second extraction cells B), the 3rd separating unit D) and the 4th separating unit E) at least one downstream.Method steps k) preferably carries out in the second esterification unit.Relate to the details of the second esterification unit and above regard to the first esterification unit A5) mentioned those are identical.
Can also comprise at least one ester separating unit M according to equipment of the present invention) to one or more esters are separated each other at least partly, especially at least one ester is separated mutually at least partly with the ester obtaining at least one second esterification unit, this is corresponding to according to the method steps of the inventive method m).Those skilled in the art are known and seem that any equipment that is suitable for ester separation can be used as ester separating unit M).The thermal separation equipment of the type of having mentioned, and crystallizer, extraction equipment, device for phase saparation are preferably as according to the ester separating unit M in present device).
The purification unit N that at least one is other) also can be provided in according in equipment of the present invention, for the second esterification unit is obtained or at least one ester separating unit in one or more ester purifying of separating.The method steps of the inventive method is n) preferably at other purification unit N) in carry out.The details of this other purification unit corresponding to the first esterification unit A5) those of relevant mentioned purification unit.
Can also be included in the second extraction cells B according to equipment of the present invention) and the second esterification unit K), ester separating unit M) and for the other purification unit N of purification of at least one ester) at least one between at least one ester conduit.Described at least one ester conduit is used at least one ester from the second esterification unit K), ester separating unit M) and for the other purification unit N of purification of at least one ester) at least one direct into the second extraction cells B), wherein said at least one ester can optionally be used as extraction agent.
In aspect preferred according to one of present device, described equipment is also included in gaseous oxidation unit A1) MTBE of upstream division unit AA1).The division unit dividing for MTBE and applicable catalyzer are well known in the art and are formed as a part for general knowledge as well known to those skilled in the art, for example,, Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th edition, A4 volume, the 488th page; V.Fattore, M.Massi Mauri, G.Oriani, G.Paret, Hydrocarbon Processing, in August, 1981,101-106 page; Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th edition, A16 volume, 543-550 page; A.Chauvel, G.Lefebvre, " Petrochemical Processes, Technical and Economic Characteristics ", the 1st volume,
Figure BDA0000476910040000281
technip, Paris, 1989, the 213 pages and continued page; US5,336,841, US4,570,026 and the reference wherein quoted described in.
Iso-butylene separating unit S1) preferred arrangements is at MTBE division unit AA1) and gaseous oxidation unit A1) between and guide and be communicated with its each fluid.Iso-butylene separating unit S1) be used for iso-butylene phase, preferably also have methyl alcohol to separate with the ejecta of the second catalytic reaction zone, this ejecta comprises iso-butylene and methyl alcohol as major constituent.Iso-butylene separating unit S1) can be at least one in extractor, crystallizer, tower, distillation plant, rectifying device, film, pervaporation equipment, phase separator and washing plant.Iso-butylene separating unit S1) preferably include the outlet of iso-butylene phase and the outlet of methyl alcohol phase.The outlet of described iso-butylene phase is preferably connected with gaseous oxidation unit, optionally connects via temporary location for example purification unit, interchanger and/or pressurizer.The outlet of described methyl alcohol phase is preferably connected with at least one in the first esterification unit and the second esterification unit, optionally connects via middle methyl alcohol purification unit.Can comprise that those skilled in the art are known and seem that any equipment that is suitable for purification of methanol is as methyl alcohol purification unit.The example of applicable purification unit preferably includes at least one distillation plant, crystallizer, extractor, tower or washing plant, more preferably at least one distillation plant.The example of methyl alcohol purification unit is described in EP1254887.
The invention still further relates to the method according to this invention, wherein the method is carried out in the device in accordance with the invention.
Illustrate in more detail the present invention by the following drawings and non-limiting example.
Accompanying drawing explanation
Fig. 1 schematically shows preferred embodiment of the process according to the invention with schema form.
Fig. 2 schematically shows according to present device embodiment.
According to the embodiment of Fig. 2, by C 4compound is introduced in gaseous oxidation unit A1, and wherein it is oxidized to methacrylic acid in one or two stage catalytic vapor phase oxidations.C 4the entrance that compound, oxygen, steam and inert dilution gas enter gaseous oxidation unit A1 does not illustrate.C 4it is not shown that compound can divide unit AA1(from MTBE), via iso-butylene separating unit, S1(is not shown) provide.Via pipeline 1, the gaseous state methacrylic acid obtaining in gaseous oxidation unit A1 is directed to quenching unit A2 mutually, wherein it is cooled and absorbs in water or water and form the water containing methacrylic acid.The entrance that quench liquid enters quenching unit A2 does not show.Via pipeline 2, moisture methacrylic acid is directed to the first extraction cells A3 mutually, its extraction is formed organic phase and water (according to first water of the inventive method) by the organic solvent that is wherein used as extraction agent.These two separate in the first extraction cells A3.
Via pipeline 3, described organic phase is directed to the first separating unit A4 from the first extraction cells A3, wherein its distillation is separated to methacrylic acid and extraction agent.Can extraction agent be recycled to the first extraction cells A3 via pipeline 6.Can collect methacrylic acid purifying in one or more purification unit (not shown) in downstream optionally via pipeline 5, or can it be directed to the first esterification unit A5 via pipeline 4, optionally via purifying (not shown).In the first esterification unit A5, can by methacrylated, for example, use methyl alcohol, for example not shown at separating unit S1() in divide with MTBE the methyl alcohol being separated, to form methyl methacrylate.Can also be with other alcohol as above by methacrylic acid esterification in the first esterification unit A5.Via pipeline 7 collect the ester that produces in the first esterification unit A5 and can be optionally not shown at polymerized unit A6() in polymerization, optionally there is the purifying in centre and/or downstream.
Via pipeline 8, the water separating in the first extraction cells A3 is directed to the second extraction cells B, the organic solvent that is wherein used as the second extraction agent extracts to form water (corresponding to second water of the inventive method) and organic phase by it.Via pipeline 9, this water is directed to the 3rd separating unit D, wherein can separates at least in part from the residual extractant of the second extraction step and also optionally follow again the second separating unit B via pipeline 25.Can by residual water (corresponding to the 3rd water of the inventive method) recirculation, for example, be recycled to gaseous oxidation unit A1(and not show conduit), as process water, be directed to biologically pure unit (not shown) or discharge, via pipeline 20.Can the organic phase separating in the second extraction cells B be directed to the 4th separating unit E via pipeline 10, wherein can separating at least one component ii..Can collect at least a portion of at least one the component ii. separating in the 4th separating unit E and by its purifying (not shown) optionally via pipeline 11.If the mixture of separated portion ii. in the 4th separating unit E, can be directed to other separating unit by this mixture so that by (not shown) separated from one another component ii..If separate methacrylic acid or the phase containing methacrylic acid in the 4th separating unit E, can be via pipeline 15 by this methacrylic acid or being directed to mutually the first extraction cells A3 or being directed to the first separating unit A4 via pipeline 16 containing methacrylic acid.Also at least a portion of at least one the component ii. separating in the 4th separating unit E can be directed to the second esterification unit K via pipeline 14.Any in the organic phase and the water that separate in the second extraction cells B or the 3rd separating unit D can be directed to the second esterification unit K.In the second esterification unit K, with alcohol by least one component ii. esterification to form corresponding ester.If alcohol is methyl alcohol, this methyl alcohol can for example, be introduced from MTBE splitter AA1 via the separating unit S1 optionally with intermediate purification (not shown).If the ester obtaining in the second esterification unit K comprises mutually more than a kind of ester, can be in ester separating unit M separating at least one ester.Can be not shown at the ester purification unit N(in downstream) in by least one ester purifying.At least one ester of one or more middle acquisitions in the second esterification unit K, ester separating unit M and ester purification unit N can be directed to the second extraction cells B so that as extraction agent.
Test method
The measurement of partition ratio (k value)
The organic solvent of the water that comprises predetermined amount acetic acid and same volume (extraction agent) is merged.At 50 ℃, shake and/or stir these two phase 15-30 minutes to guarantee to reach the equilibrium distribution of acetic acid in water and organic phase.Then allow this mixture separate at 50 ℃ and get back to organic phase and water mutually separated from one another by these two.Measure the amount of the acetic acid existing in the organic phase separating by gas-chromatography (GC) or high pressure liquid chromatography (HPLC).
·HPLC: Agilent1200
Pump: quaternary gradient pump
O eluent: acetonitrile KH 2pO 4(0.02mol/L) pH2
Gradient 3min 0% 100%
· 15min 50% 50%
· 30min 70% 30%
O flow: 1.0ml/min
O stand-by time: 30min
Operation (post) time: 5min after o
O control pressure: 190 bar, maximum 250 bar
Self-actuated sampler: self-actuated sampler
O volume injected: 20 μ L
Post stove: comprise post switching controls
O temperature: 30 ℃
O post: Agilent SB-Aq
Dimensions length 150mm, d i4.6mm, 3.5 μ m material detector MWD or DAD
O UV 210nm, 241nm, 254nm, 265nm (DAD is preferred)
·GC: Perkin Elmer Autosystem
Self-actuated sampler: Perkin Elmer
O cleaning solvent THF
O volume injected 1.0 μ L
Syringe:
O shunts splitting ratio 100
200 ℃ of o temperature program(me)s
Constant flow pressure 12.0
Post stove:
O post J & W Scientific DB225
O dimensions length 30m, d i0.25mm, 0.25 μ m material
O temperature program(me)
Speed temperature (℃) stand-by time (min)
Initially 40 5.0
15 180 4.0
O working time: 18.3min
Detector FID
260 ℃ of o set(ting)values
Embodiment
Embodiment 1:
According to carrying out this embodiment in the pilot plant of Fig. 3.Mixed the first water of synthetic being incorporated in B-100 stored.This first water is filtered, preheat and be pumped into the top of liquid-liquid extraction tower K-100.K-100 is the extraction tower of glass mould filling and jacketed, and it controls to 50 ℃ via the heat-transfer fluid in double-jacket by temperature.Move this fluid-fluid extraction by countercurrent mode, raw material is sent to the top of this tower simultaneously and extraction agent is sent to the bottom of this tower.As extraction agent, the extraction agent/raw material ratio by 2.5 is used ethyl acetate.K-100 is pulsation (stroke of 10mm and the 56min filling with random packing and use external phase -1frequency) operation.The extraction agent using is also therefore moving in continuous recirculation loop of cyclic regeneration.Extraction phase is preheated and is fed extractant regeneration glass mould distillation tower K-200.This distillation tower K-200 has structured packing steam heated vaporizer and has the condenser operation of water coolant.Overhead product is by the extraction agent mark of regeneration and be collected in storage receptacle.At the bottom of tower, ejecta is the final extract that is sent to separating unit.Take out the second water from the bottom of K-100, preheat 90 ℃ and feed the second extractant regeneration glass mould distillation tower K-300.This distillation tower K-300 is filled with structured packing steam heated vaporizer and operates continuously with the condenser of water coolant operation.From taking out the 3rd water at the bottom of the tower of K-300 and feeding the pit tank for the 3rd water.Top at K-300 is taken out the extraction agent of regeneration and feeds storage receptacle together with the regenerating extracting agent from K-200.
Figure BDA0000476910040000331
ACA=acetic acid
AA=vinylformic acid
MAA=methacrylic acid
PRA=propionic acid
EtAC=ethyl acetate
EtOH=ethanol
ACK=acetone
FOL=formaldehyde

Claims (21)

1. the method for preparing in methacrylic acid and methacrylic ester at least one, comprises following methods step:
A1) at least one C 4the gaseous oxidation of compound is to obtain the reacting phase that comprises methacrylic acid;
A2) quenching of described reacting phase, to obtain the thick water that comprises methacrylic acid;
A3) at least a portion of described methacrylic acid is extracted into organic solvent from the described thick water that comprises methacrylic acid, to obtain the thick organic phase that comprises methacrylic acid, and the first water, wherein said the first water comprises following component:
I. at least 65 % by weight, preferably 65 % by weight-99.9 % by weight, more preferably 70 % by weight-99.8 % by weight water, more more preferably 75 % by weight-99 % by weight, more preferably 76 % by weight-98.5 % by weight, more preferably 77 % by weight-98 % by weight, even more preferably 78 % by weight-97.5 % by weight, even more preferably 79 % by weight-95 % by weight, more more preferably 80 % by weight-90 % by weight water, based on the gross weight of described the first water, and
Ii. be no more than 35 % by weight, preferably 0.1 % by weight-35 % by weight, preferably 0.2 % by weight-30 % by weight, more preferably 1 % by weight-25 % by weight, more more preferably 1.5 % by weight-24 % by weight, more preferably 2 % by weight-23 % by weight, even more preferably 2.5 % by weight-22 % by weight, even more preferably 5 % by weight-21 % by weight, more more preferably 10 % by weight-20 % by weight except as method steps a3) in the organic solvent of extraction agent at least one organic compound, based on the gross weight of described the first water
Wherein the weight amount sum of i. and ii. is 100 % by weight;
A4) at least a portion of described methacrylic acid and method steps a3) in the separating and purifying optionally of the thick organic phase that obtains;
A5) optionally, step a4) in the esterification of at least a portion of the described methacrylic acid that obtains;
B) step a3) at least a portion extraction of extraction agent of the first water of obtaining, to form the extraction phase that comprises component ii., with the second water, described the second water compared with the first water dilution component ii.;
C) the second water and the step that step obtains in b) b) at least part of of extraction phase of acquisition separate;
D) optionally, at least part of separation in the second water that at least one organic compound obtains from step c), and obtain compared with the second water dilution the 3rd water of at least one organic compound;
E) optionally, at least a portion of described extraction agent separates with described extraction phase, to obtain the extract that comprises at least one component ii..
2. pack processing, containing the method for the water of at least one organic compound, comprises following methods step:
A) provide the first water that comprises following component
I. at least 65 % by weight, preferably 65 % by weight-99.9 % by weight, more preferably 70 % by weight-99.8 % by weight water, more more preferably 75 % by weight-99 % by weight, more preferably 76 % by weight-98.5 % by weight, more preferably 77 % by weight-98 % by weight, even more preferably 78 % by weight-97.5 % by weight, even more preferably 79 % by weight-95 % by weight, more more preferably 80 % by weight-90 % by weight water, based on the gross weight of described the first water, and
Ii. be no more than 35 % by weight, preferably 0.1 % by weight-35 % by weight, preferably 0.2 % by weight-30 % by weight, more preferably 1 % by weight-25 % by weight, more more preferably 1.5 % by weight-24 % by weight, more preferably 2 % by weight-23 % by weight, even more preferably 2.5 % by weight-22 % by weight, even more preferably 5 % by weight-21 % by weight, more more preferably at least one organic compound of 10 % by weight-20 % by weight, based on the gross weight of described the first water
Wherein the weight amount sum of i. and ii. is 100 % by weight;
B) extraction of extraction agent at least a portion of the first water, to form the extraction phase that comprises at least one component ii., with the second water, described the second water compared with the first water dilution at least one component ii.;
C) the second water separates with at least part of of described extraction phase;
D) optionally, at least part of separation in the second water that at least one organic compound obtains from step c), and obtain compared with the second water dilution the 3rd water of at least one organic compound;
E) optionally, at least a portion of described extraction agent separates with described extraction phase, to obtain the extract that comprises at least one component ii..
3. according to the method for any one in the claims, also comprise following methods step
F) separation of at least a portion of at least one component ii. from described extract.
4. according to the method for any one in the claims, wherein the second water comprises and is no more than 5.0 % by weight, preferably be no more than 4.5 % by weight, more preferably no more than 4.0 % by weight, again more preferably no more than 3.5 % by weight, more preferably no more than 3.0 % by weight, the organic compound beyond the extraction agent even using in the eliminating method step b) more preferably no more than 2.5 % by weight, based on the gross weight of described the second water.
5. according to the method for any one in the claims, wherein said the 3rd water comprises and is no more than 3 % by weight, preferably be no more than 2.8 % by weight, more preferably no more than 2.5 % by weight, again more preferably no more than 2.2 % by weight, organic compound beyond the extraction agent using in eliminating method step b) more preferably no more than 2.0 % by weight, based on the gross weight of described the 3rd water.
6. according to the method for any one in the claims, wherein other method steps g) in, allow described the 3rd water experience at least one biologically pure processing.
7. according to the method for claim 6, wherein said at least one biologically pure processing is at least one in aerobic treatment and anaerobic treatment.
8. according to the method for any one in the claims, wherein other method steps h) in, by method steps d) with e) at least one at least a portion of the extraction agent that separates be recycled to method steps b).
9. according to the method for any one in claim 3-8, at least one the component ii. wherein obtaining in step f) is the mixture of at least two kinds of component ii., and wherein other method steps j) in, by least one component ii. at least in part with this mixture separation.
10. according to the method for any one in the claims, wherein at least one organic compound of component ii. is at least one organic compound that is selected from carboxylic acid, aldehyde and ketone.
11. according to the method for any one in the claims, and the extraction agent that wherein method steps uses in b) is characterised in that in following performance at least one, and preferably at least two, more preferably at least three, more preferably at least four:
I) the average k value that acetic acid is measured according to method described herein in extraction agent-aqueous systems at 25 ℃ is at 0.1-100, preferred 0.2-90, and more preferably 0.3-80, more more preferably 0.3-70, more preferably in the scope of 0.4-60;
Ii) be no more than 2260kJ/kg, be preferably no more than 2000kJ/kg, be preferably no more than 1500kJ/kg, more preferably no more than 1000kJ/kg, then more preferably no more than the evaporation enthalpy of 800kJ/kg;
Iii) 35-140 ℃, preferably 35-125 ℃, more preferably 40-120 ℃, the more more preferably boiling point of 40-110 ℃;
Iv) at 25 ℃, preferably 35 ℃, more preferably 45 ℃, more preferably at the temperature of 50 ℃, be no more than 150g/l again, be preferably no more than 130g/l, more preferably no more than 110g/l, then more preferably no more than 100g/l, even more preferably no more than the solubleness in water of 90g/l.
12. according to the method for any one in the claims, and wherein said at least one component ii. is at least one in acetic acid, vinylformic acid, propionic acid and methacrylic acid.
13. according to the method for claim 12, and described at least one the component ii. wherein separating at least one in e), f) with j) of method steps is or comprises methacrylic acid and add at least a portion of this methacrylic acid to method steps a2) in the thick water or the method steps a3 that obtain) in the thick organic phase that obtains.
14. according to the method for any one in the claims, wherein allow at least a portion of described at least one the component ii. separating at least one in e), f) with j) of method steps or method steps a3) at least a portion experience following methods step of the first water of obtaining:
K) esterification is to obtain the ester phase that comprises at least one ester.
15. according to the method for claim 14, and wherein said ester comprises at least two kinds of esters mutually.
16. according to the method for claim 14 or claim 15, also comprises following methods step:
M) at least one ester at least part of separation mutually from described ester;
N) optionally, the m) purifying of middle described at least one ester separating of method steps.
17. according to the method for any one in claim 14-16, and at least a portion of described at least one ester wherein obtaining at least one in k), m) and n) of step is the extraction agent in b) as method steps.
18. according to the method for any one in claim 14-17, and wherein said at least one ester group is in C 1-C 4carboxylic acid and C 1-C 4alcohol.
19. according to the method for any one in the claims, further comprising the steps of:
Aa1) division of methyl tertiary butyl ether, to obtain at least one C 4compound and methyl alcohol,
Wherein said at least one C 4at least a portion of compound is as raw material supplying method steps a1) at least one gaseous oxidation.
20. according to the method for claim 19, wherein by method steps aa1) the middle methyl alcohol supply method step obtaining is k).
21. for the preparation of at least one equipment in methacrylic acid and methacrylic ester, at least comprises the assembly that the following guiding of fluid is each other communicated with:
A1) gaseous oxidation unit,
A2) quenching unit,
A3) the first extraction cells,
A4) the first separating unit,
A5) optionally, the first esterification unit,
B) the second extraction cells.
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