CN1207262C - Process for producing (Methyl) propenoic acid ester - Google Patents
Process for producing (Methyl) propenoic acid ester Download PDFInfo
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- CN1207262C CN1207262C CNB011228725A CN01122872A CN1207262C CN 1207262 C CN1207262 C CN 1207262C CN B011228725 A CNB011228725 A CN B011228725A CN 01122872 A CN01122872 A CN 01122872A CN 1207262 C CN1207262 C CN 1207262C
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- 238000000034 method Methods 0.000 title claims description 47
- -1 (Methyl) propenoic acid ester Chemical class 0.000 title abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 49
- 239000003960 organic solvent Substances 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 230000008676 import Effects 0.000 claims description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 14
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000013459 approach Methods 0.000 claims description 5
- 210000005239 tubule Anatomy 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000007788 liquid Substances 0.000 abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 216
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 112
- 239000002904 solvent Substances 0.000 description 41
- 230000032050 esterification Effects 0.000 description 31
- 238000005886 esterification reaction Methods 0.000 description 31
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 17
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 241001550224 Apha Species 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 210000003298 dental enamel Anatomy 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000003472 neutralizing effect Effects 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- CCRIVCWOXSIYEP-UHFFFAOYSA-N methyl prop-2-enoate;hydrochloride Chemical compound Cl.COC(=O)C=C CCRIVCWOXSIYEP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
To provide a method for producing a (meth)acrylic ester with good hue by recovering an organic solvent at relatively low temperatures in a short time which is used in the synthetic reaction for the (meth)acrylic ester. SOLUTION: This method for producing a (meth)acrylic ester involves distilling off an organic solvent used in the synthetic reaction for the (meth) acrylic ester, by distillation under reduced pressures at relatively low temperatures while introducing reduced pressure steam into a liquid comprising the (meth)acrylic ester and the organic solvent.
Description
Technical field
The present invention relates to the manufacture method of (methyl) acrylate (meaning of acrylate or methacrylic ester).
Background technology
Manufacture method as in the past (methyl) acrylate, known have a following method, for example, (methyl) vinylformic acid and alcohols are dissolved in the organic solvent that has as azeotropic dehydration solvent function, in the presence of stopper and an acidic catalyst, as required, import the air of trace on one side, carry out esterification on one side, reaction finishes the back and adopts alkaline aqueous solution neutral method to remove unreacted (methyl) vinylformic acid and an acidic catalyst, wash with water as required then for several times, and then the organic solvent that reclaims in the oil reservoir is removed in underpressure distillation in the presence of stopper, thereby obtained as target product (methyl) acrylate.
When organic solvent is removed in decompression, for fear of (methyl) acrylate generation thermopolymerization, must under 60 ℃～95 ℃ lower like this temperature, carry out, therefore as target product, just must spend long time for boiling off organic solvent, thereby cause the low and cost up of productivity.
In order to address this problem, the method for Cai Yonging is when remaining solvent strength becomes 10～30 weight % traditionally, imports a large amount of air in system, promotes the steaming of solvent to remove whereby.
Yet according to this method, product is because oxidation by air and painted, and the utilization of product is had bad influence, and in addition, the effect that the time is shortened is also good inadequately, and this is the problem of its existence.
In addition, open the spy and disclose a kind of method that in system, adds entry and boil off solvent by azeotropism in the flat 7-206769 communique.Yet, according to this method, in system, the vaporization heat of organic solvent will add together with evaporation of water latent heat and calculates, thereby make that the heat of importing from the outside is more than the heat of the need of traditional method, and because the producing apparatus costliness, Gu this is unfavorable to manufacturing cost.In addition, under the situation that can not import enough heats, offset the effect of adding water, and the effect that the time shortens is good inadequately, this is the problem of its existence.
Goal of the invention
The present invention is in view of above-mentioned practical situation, its objective is provides a kind of manufacture method that can mass production above-mentioned (methyl) acrylate, according to this method, in the technology of making (methyl) acrylate, can distill at short notice and remove the solvent that when esterification, uses, and can suppress the time of the painted of goods and shortening manufacturing processed (operation).
The present invention is a problem that exists at prior art and the invention made.That is to say that the present invention is the manufacture method of a kind of (methyl) acrylate, it is characterized in that, coming to comprise following operation when organic solvent is removed in distillation from reclaim oil reservoir by underpressure distillation in the method, that is:
On one side in above-mentioned oil reservoir, import reduced steam, on one side the underpressure distillation operation of removing above-mentioned organic solvent.
The manufacturing of (methyl) acrylate
As the manufacture method of (methyl) acrylate, can use the method for conventional known, for example: the method for direct esterification method, ester-interchange method, chloride thing etc.
So-called direct esterification method, briefly, make (methyl) vinylformic acid and high boiling alcohol in the presence of the dehydration and azeotropic solvent, carry out esterification exactly, after with the alkaline aqueous solution neutralization, when separating water layer, reclaim oil reservoir, remove organic solvent by underpressure distillation distillation from the oil reservoir that reclaims then.
So-called ester-interchange method briefly, makes (methyl) methyl acrylate and alcohol carry out transesterify exactly in the presence of alkaline catalystss such as lithium hydroxide, thereby obtains the thick product of (methyl) acrylate.In reaction, also use solvent sometimes.Under the situation of the ester that can not distill processing,, can carry out oily water separation then to wherein adding solvent for above-mentioned thick product is washed purifying.
The method of so-called chloride thing briefly, just is to use alkali such as sodium hydroxide or organic amine to make (methyl) acrylate chloride and alcohol carry out esterification as desalination acid agent, thereby obtain the thick product of (methyl) acrylate, wherein, as reaction solvent, can use the solvent of toluene etc.
According to each above-mentioned method, in its manufacturing process, all must remove organic solvent by distilling from reclaim oil reservoir, by finishing this operation, finally just can obtain (methyl) acrylate as target product.
Describe based on above-mentioned direct esterification method below.
Alcohol
According to the present invention, as the alcohol that when making (methyl) acrylate, uses, so long as have 1 or 2 above hydroxyls and have high boiling point, just boiling point is (we can say more than 180 ℃, its upper limit is the highest to allow to reach " decomposition temperature of this compound ") alcohol all can use, this is not particularly limited.In addition, as the derivative of alcohol, the compound etc. of epoxide that also can use addition.For these alcohol, can use wherein a kind of separately, also it can be used in combination.
For example can enumerate; The affixture of the aklylene glycol of phenyl glycol ex hoc genus anne thing, methoxyl group glycol, polyoxyethylene glycol, polypropylene glycol, dihydroxyphenyl propane, TriMethylolPropane(TMP), tetramethylolmethane, glycerine and their epoxide affixture etc.
(methyl) vinylformic acid
By making (methyl) vinylformic acid and alcohol carry out esterification when making (methyl) acrylate, (methyl) acrylic acid consumption, with respect to each equivalent of the hydroxyl of alcohol, (methyl) vinylformic acid should be 1～2 times of equivalent, is preferably 1.1～1.5 times of equivalents.When it uses quantity not sufficient 1 equivalent, the overlong time of esterification, in addition, the content of the high molecular weight material in (methyl) acrylate that is obtained etc. increases, and is therefore bad.On the other hand, when using above 2 times of normal (methyl) vinylformic acid, (methyl) vinylformic acid of the surplus of not reacting left behind, thereby it is unfavorable economically, and, from react thick product, remove unreacted (methyl) vinylformic acid and in operation, bother, therefore bad.
Catalyzer
As the catalyzer of esterification, can use known traditionally various catalyzer.For example can enumerate: sulfuric acid, tosic acid, methylsulfonic acid etc.In addition, as its usage quantity, measure 100 weight parts with respect to raw alcohol and (methyl) acrylic acid total, above-mentioned catalyst consumption is preferably 1～10 weight part, is preferably 2～8 weight parts.
Organic solvent
As the organic solvent that in esterification, uses, can illustration benzene, toluene, hexane, hexanaphthene, dimethylbenzene etc., can use wherein a kind of separately, also it can be used in combination.
The esterification condition
The temperature of reaction of esterification is about 60～140 ℃, is preferably 70～130 ℃.When temperature of reaction during less than 60 ℃, the reaction times is long; On the other hand, when temperature of reaction surpasses 140 ℃, produce and be not suitable for the situation of polyreaction, and cause the content of byproduct to increase, therefore also bad.
When esterification,, can use stopper in order to prevent (methyl) vinylformic acid, (methyl) acrylate generation polymerization.For example can enumerate: known stoppers such as hydroquinone monomethyl ether, quinhydrones, para benzoquinone, 2,4 dimethyl 6 tert butyl phenol.In addition, also can in reaction solution, import micro amount of oxygen or air with fine bubble.
Till esterification proceeded to and do not have water to steam, the reaction times was about 5～20 hours.After reaction finished, in order to remove catalyzer contained in the thick product of dereaction and superfluous (methyl) vinylformic acid, available alkaline aqueous solution neutralized it, removes water layer, as required, can remove water layer again with the salt solution washing, obtained oil reservoir.
For organic solvent is removed in distillation from obtaining oil reservoir, can under reduced pressure and at 60～95 ℃ descend one side heated and stirred, Yi Bian distill.In order to prevent (methyl) polymerizing acrylic acid, can be toward the oxygen or the air that wherein import trace.Owing under lower temperature, operate, make therefore that when the remaining quantity of solvent with respect to acrylate 100 weight parts becomes 40～10 weight parts the recovery speed of solvent just begins to reduce.
Reduced steam
According to the present invention, when the recovery speed of solvent begins when slack-off, just in (methyl) acrylate that contains solvent, import the reduced steam that is equivalent to remaining quantity of solvent 10～200 weight %, to promote the evaporation of solvent, should illustrate, according to the present invention, also it doesn't matter even just import reduced steam from the initial stage that organic solvent steams, and is to begin to import reduced steam when the remaining quantity of solvent with respect to (methyl) vinylformic acid 100 weight parts becomes 40～10 weight parts than effective means still.That is to say, if just import reduced steam during still greater than 40 weight parts in remaining quantity of solvent, then in order to ensure being used to make the required heat of solvent gasification, just must give too much investment to heating installation, in addition, if treat just to import when remaining quantity of solvent is less than 10 weight parts reduced steam, then just elongated in order to steam the required time of whole solvents, thus make that effect of the present invention is not ideal enough.
Said reduced steam is meant that its pressure is lower than the water vapor of normal atmosphere (760mmHg) among the present invention, for making the shown temperature of reduced steam approach liquid temperature in the still, the pressure of water vapor is preferably below 600mmHg, more preferably below 500mmHg, below 300mmHg, most preferably below 150mmHg, the water vapor that shows vapour pressure like this is exactly gasiform water.Be provided with particular determination as the means that obtain reduced steam, for example can make have normal atmosphere with the pressured steam of upward pressure by orifice pipe or needle valve, its importing is had in the system of required decompression degree, so can obtain required reduced steam.
Import volume to reduced steam does not have particular determination, but is preferably 10～200 weight % of remaining organic solvent amount.When water vapor import volume less than 10 weight %, be difficult to obtain effect of sufficient, and when the water vapor import volume surpassed 200 weight %, moisture remained in the goods, in order to remove the moisture in the goods, time of overspending possibly.In addition, preferred scope is 20～120 weight %.
After boiling off solvent, raffinate is filtered, just can obtain colourless or faint yellow transparent (methyl) acrylate.
When making (methyl) of the present invention acrylate, desolventize the required time in order to steam, need 10～15 hours by traditional method, but the present invention can shorten 4～6 hours with it.More particularly, can be in 10 hours, preferably in 9 hours, more preferably in 8 hours for the final remaining concentration that the makes organic solvent 0.1 weight % institute estovers underpressure distillation time that was reduced to.
One example of following notebook invention embodiment.
1, (methyl) acrylate manufacture method, in pressing the method for direct esterification manufactured (methyl) acrylate, make (methyl) vinylformic acid and high boiling point (more than 180 ℃, be limited to decomposition temperature on it) alcohol in the presence of the dehydration and azeotropic solvent, carry out esterification, neutralize with alkaline aqueous solution, separate water layer then and reclaim oil reservoir simultaneously, and then remove the organic solvent that uses as the dehydration and azeotropic solvent by underpressure distillation distillation from the oil reservoir that reclaims, it is characterized in that, operation during as above-mentioned distillation, comprise following operation, that is: on one side in above-mentioned oil reservoir, import reduced steam, on one side the underpressure distillation operation of removing above-mentioned organic solvent.
2, (methyl) acrylate manufacture method, in pressing the method for direct esterification manufactured (methyl) acrylate, make (methyl) vinylformic acid and high boiling point (more than 180 ℃, be limited to decomposition temperature on it) alcohol in the presence of the dehydration and azeotropic solvent, carry out esterification, neutralize with alkaline aqueous solution, separate water layer then and reclaim oil reservoir simultaneously, and then remove the organic solvent that uses as the dehydration and azeotropic solvent by underpressure distillation distillation from the oil reservoir that reclaims, it is characterized in that, operation during as above-mentioned distillation, comprise following operation, that is: in above-mentioned oil reservoir, import reduced steam on one side, above-mentioned organic solvent is removed in underpressure distillation on one side, shortens distillation by this step and removes the above-mentioned organic solvent operation of required time.
3, (methyl) acrylate manufacture method, in pressing the method for direct esterification manufactured (methyl) acrylate, make (methyl) vinylformic acid and high boiling point (more than 180 ℃, be limited to decomposition temperature on it) alcohol in the presence of the dehydration and azeotropic solvent, carry out esterification, neutralize with alkaline aqueous solution, separate water layer then and reclaim oil reservoir simultaneously, and then remove the organic solvent that uses as the dehydration and azeotropic solvent by underpressure distillation distillation from the oil reservoir that reclaims, it is characterized in that, operation during as above-mentioned distillation, comprise following operation, that is: have the pressured steam of normal atmosphere by other approach manufacturing with upward pressure, it is passed through and decompression gradually in tubule, then this reduced steam is imported in the above-mentioned oil reservoir underpressure distillation and remove above-mentioned organic solvent, shorten distillation by this step and remove above-mentioned organic machine solvent operation of required time.
4, (methyl) acrylate manufacture method, in pressing the method for direct esterification manufactured (methyl) acrylate, make (methyl) vinylformic acid and high boiling point (more than 180 ℃, be limited to decomposition temperature on it) alcohol in the presence of the dehydration and azeotropic solvent, carry out esterification, neutralize with alkaline aqueous solution, separate water layer then and reclaim oil reservoir simultaneously, and then remove the organic solvent that uses as the dehydration and azeotropic solvent by underpressure distillation distillation from the oil reservoir that reclaims, it is characterized in that, operation during as above-mentioned distillation, comprise following operation, that is: have the pressured steam of normal atmosphere by other approach manufacturing with upward pressure, it is passed through and decompression gradually in tubule, then this reduced steam is imported in the above-mentioned oil reservoir underpressure distillation and remove above-mentioned organic solvent, come the required time decreased to 10 of the underpressure distillation that is reduced to 0.1 weight % for the final remaining concentration that makes above-mentioned organic solvent hour with interior operation by this step.
According to the present invention, can distill expeditiously at short notice and remove the solvent that when esterification, uses, the painted of goods can be suppressed, and the time of manufacturing processed (operation) can be shortened.And,, therefore can carry out (methyl) acrylic acid mass production owing to shortened the time of manufacturing processed (operation).
Embodiment
Embodiment
Describe the present invention particularly below by embodiment, but the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
In being blown into the reactor of the pipe and the enamel 300L capacity of airtight whipping appts, condenser, thermometer, an air that is equipped with the band water trap adds polyoxyethylene glycol (MW=400) 85kg, toluene 100kg, tosic acid 6kg, quinhydrones 0.15kg and vinylformic acid 37kg, on one side to wherein being blown into air, on one side in chuck, feed steam, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 102 ℃, begin to have water to steam, after about 8 hours, when the liquid temperature reaches 123 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The ester reactivity that calculates from the water that steams is 99.5%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then.Add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 180kg of toluene 100kg.Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
Beginning to import pressure by needle valve when remaining toluene amount is reduced to 20% (with respect to acrylate 100 weight parts, the toluene amount is 25 weight parts) is 2kg/cm
2The pressured steam of (about 130 ℃), the condition when importing water vapor comprises that the speed with 10kg/hr is blown into 2 hours in the depressurized system of 30mmHg, imports 20kg steam (for 100 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 30 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Steam from toluene and to begin to calculate, want 4.5 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 76kg as goods.The form and aspect APHA of the goods that obtain is 10, and acid number is 0.10mgKOH/g, and moisture is 0.02%.
Embodiment 2
Ethylene oxide adduct (average EO addition mole number is 10) 88kg, the toluene 134kg, tosic acid 5.8kg, quinhydrones 0.2kg, the methacrylic acid 29kg that in a reactor similarly to Example 1, add dihydroxyphenyl propane, then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 107 ℃, begin to have water to steam, after about 10 hours, when the liquid temperature reaches 122 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.0%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous methacrylic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 220kg of toluene 134kg.Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
Beginning to import pressure by needle valve when remaining toluene amount is reduced to 25% (with respect to methacrylic ester 100 weight parts, the toluene amount is 33 weight parts) is 2kg/cm
2The pressured steam of (about 130 ℃), the condition when importing water vapor comprises that the speed with 7kg/hr is blown into 2.5 hours in the depressurized system of about 50mmHg, imports 17.5kg steam (for 82 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 30 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Steam from toluene and to begin to calculate, want 5 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 85kg as goods.The form and aspect APHA of the goods that obtain is 20, and acid number is 0.05mgKOH/g, and moisture is 0.01%.
Embodiment 3
Ethylene oxide adduct (average EO addition mole number is 3) 70kg, the toluene 138kg, tosic acid 7kg, quinhydrones 0.2kg, the vinylformic acid 68kg that in a reactor similarly to Example 1, add TriMethylolPropane(TMP), then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 110 ℃, begin to have water to steam, after about 5 hours, when the liquid temperature reaches 125 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.4%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 240kg of toluene 138kg.Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
Beginning to import pressure by needle valve when remaining toluene amount is reduced to 10% (with respect to acrylate 100 weight parts, the toluene amount is 10 weight parts) is 1.5kg/cm
2Pressured steam, the condition when importing water vapor comprises that the speed with 10kg/hr is blown into 2 hours in the depressurized system of about 50mmHg, imports 20kg water vapor (for 20 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 30 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Steam from toluene and to begin to calculate, want 5 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 100kg as goods.The form and aspect APHA of the goods that obtain is 10, and acid number is 0.1mgKOH/g, and moisture is 0.02%.
Embodiment 4
Ethylene oxide adduct (average EO addition mole number is 4) 100kg, the toluene 100kg, tosic acid 6kg, quinhydrones 0.15kg, the vinylformic acid 43kg that in a reactor similarly to Example 1, add dihydroxyphenyl propane, then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 110 ℃, begin to have water to steam, after about 4 hours, when the liquid temperature reaches 123 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.7%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 208kg of toluene 100kg.
Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
When remaining toluene amount was reduced to 33% (with respect to acrylate 100 weight parts, the toluene amount is 50 weight parts), beginning to import pressure by needle valve was 2.0kg/cm
2Pressured steam, the condition when importing water vapor comprises in the system of 80mmHg with 40kg/h
2Speed be blown into 3 hours, import 120kg water vapor (for 228 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 30 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Steam from toluene and to begin to calculate, want 5.5 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 107kg as goods.The form and aspect APHA of the goods that obtain is 15, and acid number is 0.09mgKOH/g, and moisture is 0.05%.
Embodiment 5
In a reactor similarly to Example 1, add polyoxyethylene glycol (MW=300) 80kg, toluene 130kg, tosic acid 6kg, quinhydrones 0.2kg, vinylformic acid 46kg, then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 105 ℃, begin to have water to steam, after about 9 hours, when the liquid temperature reaches 120 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.4%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 217kg of toluene 130kg.
Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
Beginning to import pressure by needle valve when remaining toluene amount is reduced to 33% (with respect to acrylate 100 weight parts, the toluene amount is 50 weight parts) is 2.0kg/cm
2Pressured steam, the condition when importing water vapor is included in that the speed with 1kg/hr is blown into 2 hours in the system of about 75mmHg, imports 2kg water vapor (for 5 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 120 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Begin to calculate from toluene distillation, want 6 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 87kg as goods.The form and aspect APHA of the goods that obtain is 10, and acid number is 0.14mgKOH/g, and moisture is 0.02%.
Embodiment 6
In a reactor similarly to Example 1, add polyoxyethylene glycol (MW=400) 85kg, toluene 100kg, tosic acid 6kg, quinhydrones 0.15kg, vinylformic acid 37kg, then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 102 ℃, begin to have water to steam, after about 8 hours, when the liquid temperature reaches 122 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.4%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 180kg of toluene 100kg.
Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
Beginning to import pressure by needle valve when remaining toluene amount is reduced to 4.8% (with respect to acrylate 100 weight parts, the toluene amount is 5 weight parts) is 2.0kg/cm
2Pressured steam, the condition when importing water vapor comprises that the speed with 4.5kg/hr is blown into 2 hours in the system of about 30mmHg, imports 9kg water vapor (for 225 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 30 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Begin to calculate from toluene distillation, want 6 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 78kg as goods.The form and aspect APHA of the goods that obtain is 10, and acid number is 0.10mgKOH/g, and moisture is 0.04%.
Embodiment 7
Ethylene oxide adduct (average EO addition mole number is 4) 100kg, the toluene 100kg, tosic acid 6kg, quinhydrones 0.15kg, the vinylformic acid 43kg that in a reactor similarly to Example 1, add dihydroxyphenyl propane, then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 110 ℃, begin to have water to steam, after about 4 hours, when the liquid temperature reaches 123 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.7%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 208kg of toluene 100kg.
Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 100～30mmHg steam toluene on one side.
Beginning to import pressure by needle valve when remaining toluene amount is reduced to 4.8% (with respect to acrylate 100 weight parts, the methyl amount is 5 weight parts) is 2.0kg/cm
2Pressured steam, the condition when importing water vapor comprises that the speed with 0.15kg/hr is blown into 2 hours in the system of about 50mmHg, imports 0.3kg water vapor (for 5.6 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 30 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Begin to calculate from toluene distillation, want 6.5 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 106.5kg as goods.The form and aspect APHA of the goods that obtain is 10, and acid number is 0.11mgKOH/g, and moisture is 0.02%.
Embodiment 8
Ethylene oxide adduct (average EO addition mole number the is 4) 100kg, toluene 100 kg, tosic acid 6kg, quinhydrones 0.15kg, the vinylformic acid 43kg that in a reactor similarly to Example 1, add dihydroxyphenyl propane, then on one side to wherein being blown into air, on one side in chuck, feed water vapor, heat whereby and stir.When reaction solution temperature (temperature of reaction) reaches 110 ℃, begin to have water to steam, after about 4 hours, when the liquid temperature reaches 123 ℃, water steam termination, at this moment it is cooled to below 30 ℃.The esterification rate that calculates from the water that steams is 99.7%.
In this reaction solution, add alkaline aqueous solution at leisure, neutralizing below 40 ℃, superfluous vinylformic acid and catalyzer are extracted in the tank, remove the water of sub-cloud.Then, add 10% salt solution 20kg, stir, leave standstill the water that sub-cloud is removed in the back, obtained to contain the oil reservoir 208kg of toluene 100kg.
Be equipped with the oil reservoir that condenser, thermometer, water vapor are blown into the above-mentioned acquisition of adding in the still kettle of enamel system 300L capacity that pipe, air be blown into pipe and airtight whipping appts to one, one side feeds 70 ℃ warm water in the chuck, under the decompression of interior temperature 70 ℃ and vacuum tightness 200～100mmHg steam toluene on one side.
When remaining toluene amount was reduced to 20% (with respect to acrylate 100 weight parts, the toluene amount is 25 weight parts), beginning to import pressure by needle valve was 2.0kg/cm
2Pressured steam, the condition when importing water vapor comprises in the system of 170mmHg with 15kg/h
2Speed be blown into 2 hours, import 30kg water vapor (for 110 weight % of remaining quantity of solvent) altogether.After finishing, the importing of water vapor 120 minutes the time, confirms that remaining toluene amount is 0.1 weight %.Begin to calculate from toluene distillation, want 8 hours altogether.
This raffinate is filtered, obtained light yellow transparent liquid 106.7kg as goods.The form and aspect APHA of the goods that obtain is 15, and acid number is 0.13mgKOH/g, and moisture is 0.06%.
Comparative example 1
As the control experiment of embodiment 1, carried out following comparative experiments.That is to say that when remaining toluene amount is reduced to 19%, imports air and replace water vapour, the import volume of air is 0.5 liter/minute, is equivalent to 5 times of embodiment 1, continues underpressure distillation with this understanding.After 13 hours, confirm that remaining toluene amount is 0.13%.
This raffinate is filtered, obtained yellow transparent liquid 76kg as goods.The form and aspect APHA of the goods that obtain is 15, and acid number is 0.15mgKOH/g, and moisture is 0.01%.
Comparative example 2
As the control experiment of embodiment 1, carried out following comparative experiments.That is to say, when remaining toluene amount is reduced to 20%, do not import water vapour, and the import volume of air do not increase yet, after 15 hours, confirm that remaining toluene amount is 0.15%.
This raffinate is filtered, obtained yellow transparent liquid 76kg as goods.The form and aspect APHA of the goods that obtain is 25, and acid number is 0.1mgKOH/g, and moisture is 0.01%.
Comparative example 3
As the control experiment of embodiment 2, carried out following comparative experiments.That is to say, when remaining toluene amount is reduced to 25%, obstructedly goes into water vapour but add the water 37kg of normal temperature, proceed underpressure distillation.In the stage of adding water, intrasystem liquid temperature reduces rapidly.And then return to original temperature (wanting 5 hours approximately) at leisure, proceed underpressure distillation.Confirm after 12 hours that the toluene amount is 0.12%.
This raffinate is filtered, obtained yellow transparent liquid 84kg as goods.The form and aspect APHA of the goods that obtain is 250, and acid number is 0.1mgKOH/g, and moisture is 0.01%.
Comparative example 4
As the control experiment of embodiment 3, carried out following comparative experiments.That is to say, when remaining toluene amount is reduced to 9%, obstructedly goes into water vapour but add entry 20kg, proceed underpressure distillation.In the stage of adding water, intrasystem liquid temperature reduces rapidly.And then return to original temperature (wanting 5 hours approximately) at leisure, proceed underpressure distillation.Confirm after 14 hours that the toluene amount is 0.1%.
This raffinate is filtered, obtained yellow transparent liquid 101kg as goods.The form and aspect APHA of the goods that obtain is 150, and acid number is 0.1mgKOH/g, and moisture is 0.01%.
Above experimental result gathered be shown in [table 1] and [table 2].
Table 1
| Opportunity when importing reduced steam is with respect to the toluene by weight umber of (methyl) acrylate 100 weight parts | Import the pressure (mmHg) of water vapour | Boot speed (kg/hr) | Time and total amount, (total amount is the % with respect to remaining quantity of solvent) | Solvent distillation required time (hrs) | APHA | Acid number mgKO H/g | The ultimate density of toluene (weight %) | |
| Embodiment 1 | When reaching 25 weight parts | 30 | 10 | 2 hours 100 weight % | 4.5 | 10 | 0.10 | 0.1 |
| Embodiment 2 | When reaching 33 weight parts | About 50 | 7 | 2.5 hour 82 weight % | 5 | 20 | 0.05 | 0.1 |
| Embodiment 3 | When reaching 10 weight parts | 50 | 10 | 2 hours 20 weight % | 5 | 10 | 0.1 | 0.1 |
| Embodiment 4 | When reaching 50 weight parts | 80 | 40 | 3 hours 228 weight % | 5.5 | 15 | 0.09 | 0.1 |
| Embodiment 5 | When reaching 50 weight parts | 75 | 1 | 2 hours 5 weight % | 6 | 10 | 0.14 | 0.1 |
| Embodiment 6 | When reaching 5 weight parts | 30 | 4.5 | 2 hours 225 weight % | 6 | 10 | 0.10 | 0.1 |
| Embodiment 7 | When reaching 5 weight parts | 50 | 0.15 | 2 hours 5.6 weight % | 6.5 | 10 | 0.11 | 0.1 |
| Embodiment 8 | When reaching 25 weight fraction | 170 | 15 | 2 hours 110 weight % | 8 | 15 | 0.13 | 0.1 |
Table 2
| Residual solvent steams the situation of removing | APHA | Acid number mgKOH/g | The final remaining concentration (weight %) of toluene | |
| Comparative example 1 | Confirm after 13 hours that remaining content of toluene is 0.13% | 200 | 0.15 | 0.13 |
| Comparative example 2 | Confirm after 15 hours that remaining content of toluene is 0.15% | 25 | 0.1 | 0.15 |
| Comparative example 3 | Confirm after 15 hours that remaining content of toluene is 0.12% | 250 | 0.1 | 0.12 |
| Comparative example 4 | Confirm after 14 hours that remaining content of toluene is 0.10% | 150 | 0.1 | 0.10 |
Claims (10)
1, the manufacture method of acrylate or methacrylic ester is characterized in that, in the method, is coming to comprise following operation when organic solvent is removed in distillation from the oil reservoir that reclaims by underpressure distillation, that is:
On one side in above-mentioned oil reservoir, import reduced steam, on one side the underpressure distillation operation of removing above-mentioned organic solvent.
2, the manufacture method of acrylate or methacrylic ester is characterized in that, in the method, is coming to comprise following operation when organic solvent is removed in distillation from the oil reservoir that reclaims by underpressure distillation, that is:
Have the pressured steam of normal atmosphere by other approach manufacturing with upward pressure, it is passed through and decompression gradually in tubule, then this reduced steam is imported in the above-mentioned oil reservoir underpressure distillation and remove above-mentioned organic solvent, shorten distillation by this step and remove the above-mentioned organic solvent operation of required time.
3, the manufacture method of acrylate or methacrylic ester is characterized in that, in the method, is coming to comprise following operation when organic solvent is removed in distillation from the oil reservoir that reclaims by underpressure distillation, that is:
Have the pressured steam of normal atmosphere by other approach manufacturing with upward pressure, it is passed through and decompression gradually in tubule, then this reduced steam is imported in the above-mentioned oil reservoir underpressure distillation and remove above-mentioned organic solvent, come the required time decreased to 10 of the underpressure distillation that is reduced to 0.1 weight % for the final remaining concentration that makes above-mentioned organic solvent hour with interior operation by this step.
4, the method described in each of claim 1～3, wherein, when remaining organic solvent with respect to acrylate or methacrylic ester 100 weight parts, begin to import above-mentioned reduced steam when being reduced to 40～10 weight parts.
5, the method described in each of claim 1～3, wherein, the import volume of above-mentioned reduced steam is 10～200 weight % of remaining organic solvent amount.
6, method as claimed in claim 4, wherein, the import volume of above-mentioned reduced steam is 10～200 weight % of remaining organic solvent amount.
7, the method described in each of claim 1～3, wherein the vapour pressure of above-mentioned reduced steam is below 300mmHg.
8, method as claimed in claim 4, wherein the vapour pressure of above-mentioned reduced steam is below 300mmHg.
9, method as claimed in claim 5, wherein the vapour pressure of above-mentioned reduced steam is below 300mmHg.
10, method as claimed in claim 6, wherein the vapour pressure of above-mentioned reduced steam is below 300mmHg.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000228329A JP4080677B2 (en) | 2000-07-28 | 2000-07-28 | Method for producing (meth) acrylic acid ester |
| JP228329/2000 | 2000-07-28 |
Publications (2)
| Publication Number | Publication Date |
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| CN1335297A CN1335297A (en) | 2002-02-13 |
| CN1207262C true CN1207262C (en) | 2005-06-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011228725A Expired - Fee Related CN1207262C (en) | 2000-07-28 | 2001-07-12 | Process for producing (Methyl) propenoic acid ester |
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| Country | Link |
|---|---|
| JP (1) | JP4080677B2 (en) |
| KR (1) | KR20020010476A (en) |
| CN (1) | CN1207262C (en) |
| TW (1) | TW574207B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005102984A1 (en) * | 2004-04-26 | 2005-11-03 | Daikin Industries, Ltd. | Process for producing fluorinated acrylic ester |
| JP5002905B2 (en) * | 2005-04-05 | 2012-08-15 | 東亞合成株式会社 | Method for removing volatile substances in (meth) acrylic acid ester |
| DE102009048774A1 (en) * | 2009-10-08 | 2011-04-28 | Oxea Deutschland Gmbh | Process for the color lightening of polyol esters |
| CN106966903B (en) * | 2017-04-12 | 2021-05-14 | 中国矿业大学(北京) | Separation method of methyl methacrylate and toluene mixture |
| CN114573736B (en) * | 2022-03-17 | 2024-03-15 | 苏州星日化学有限公司 | Method for reducing volatile matter content in poly (methyl) acrylic ester |
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- 2000-07-28 JP JP2000228329A patent/JP4080677B2/en not_active Expired - Fee Related
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- 2001-06-28 KR KR1020010037347A patent/KR20020010476A/en not_active Application Discontinuation
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| JP2002047248A (en) | 2002-02-12 |
| KR20020010476A (en) | 2002-02-04 |
| CN1335297A (en) | 2002-02-13 |
| JP4080677B2 (en) | 2008-04-23 |
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