CN101219948B - Method for producing high purity extractive (methyl) acrylic acid - Google Patents
Method for producing high purity extractive (methyl) acrylic acid Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity fine (cymene) acrylic acid, which adds a composite ethyleneurea consisting of a guanidine compound or the salt or urea or thiourea of the guanidine compound into crude (cymene) acrylic acid to be reacted, then introduces the reaction liquid to a distillation column to carry out intermittent or continuous distillation to obtain a high-purity fine (methyl) acrylic acid product without aldehyde or maleic. The composite ethyleneurea can remove the aldehyde and maleic in the crude (cymene) acrylic acid completely with no solid impurity generated.
Description
Technical field
The invention provides a kind of high purity (methyl) method for producing acrylic acid, that is by in thick (methyl) vinylformic acid, add compound aldehyde removing agent remove wherein impurity aldehyde and the method for toxilic acid.Particularly, the present invention relates in thick (methyl) vinylformic acid that contains impurity such as the 10～5000ppm that has an appointment (methyl) propenal, furfural, phenyl aldehyde and/or toxilic acid, add the compound aldehyde removing agent that guanidine compound and urea or thiourea are formed, itself and aldehyde and toxilic acid in thick (methyl) vinylformic acid are reacted, then under vacuum intermittently or continuous rectification do not contained high purity (methyl) vinylformic acid of aldehyde and toxilic acid.
Background technology
At C such as propane, propylene, Virahol and/or propenal
3C such as compound or Trimethylmethane, iso-butylene, the trimethyl carbinol and/or Methylacrylaldehyde
4Generating in the catalytic oxidation process of compound has multiple by product, these by products more or less to be brought in (methyl) acrylic products, causes the purity of (methyl) acrylic products to descend, thus the use properties of influence (methyl) acrylic products.When especially the user needed highly purified essence (methyl) vinylformic acid as polymerization single polymerization monomer, because the existence of impurity in (methyl) vinylformic acid can cause (methyl) acroleic acid polymerization time lengthening, the polymerization degree can not satisfy customer requirements.
Unsaturated carboxylic acid is very easily polymerization under comparatively high temps, and the small amount of impurities of separating wherein must be carried out under higher vacuum and lower temperature.But (methyl) acrylic acid boiling point and the boiling point of small amount of impurities wherein are near (161.7 ℃ of furfural boiling points, 178.9 ℃ of phenyl aldehydes, 160 ℃ of methacrylic acid boiling points, 141.6 ℃ of vinylformic acid boiling points) under higher vacuum tightness, though can remove by the method for direct rectifying theoretically, but it is a lot of that the rectifying number of theoretical plate is wanted, and is extremely uneconomic.Chemical method is to reach the purpose that removes impurity by adding a small amount of chemical reagent with aldehyde and toxilic acid reaction in thick (methyl) vinylformic acid, and this method operating procedure is simple, and temperature of reaction low (normal temperature to 50 ℃) is economical and effective method therefore.
Adopt chemical method to remove the existing patent report of a spot of aldehyde in the vinylformic acid, as aldehyde reaction in the patent CN1106789A of BASF AG report employing primary amine especially aminoguanidine and salt and the vinylformic acid, reach the purpose that removes aldehyde, but the method for this patent has a large amount of settlings to generate and residue in Polycondensation Reactor and Esterification Reactor in removing aldehyde process, cause the pipeline and the heat-exchange system of production equipment to stop up, influence the device continuous production.In order to eliminate this settling, this patent report also will add a kind of organic Phenylsulfonic acid and carry out " neutralization ".Therefore the operation of the method for this patent is more numerous, and the still bottom sediment is difficult to eliminate, and primary amine is relatively poor to the toxilic acid removal effect in the crude acrylic acid.The patent CN1541199A of MIT report, the alkyl sulfhydryl of 10～16 carbon of employing reacts in the presence of acidic cationic resin, and reaches the purpose of full gear.Though present method deposit-free generates, alkyl sulfhydryl is expensive, adds more expensive and unrenewable resin catalyst, causes vinylformic acid full gear processing cost higher; Resin catalyst needs regularly to change in addition, operates also more loaded down with trivial details.The patent CN1149573A of rom Haars Co., Ltd report, add the various kinds of amine compounds at the rectifying tower different sites and carry out full gear, but this method not only has a large amount of residues to generate, and relatively poor to aldehyde in the crude acrylic acid and toxilic acid removal effect, and particularly toxilic acid is difficult to remove totally.
The present invention is in order to overcome the shortcoming of above-mentioned patent, be that full gear is reacted the settling block system of back generation and influenced continuous production, and full gear especially removes the weak effect of toxilic acid, selected guanidine compound or its salt and urea or thiourea to form compound aldehyde removing agent, its with thick (methyl) vinylformic acid in impurity aldehyde and toxilic acid reaction back generate the acrylic acid higher-boiling compound of a kind of dissolving in (methyl), stay at the bottom of the still owing to the boiling point of these compounds is higher during distillation, thereby reach the purpose that removes aldehyde and toxilic acid.
Summary of the invention
The objective of the invention is to the compound aldehyde removing agent formed with guanidine compound or its salt and urea or thiourea, impurity such as a small amount of aldehyde material in thick (methyl) vinylformic acid and toxilic acid are removed completely, obtain highly purified essence (methyl) vinylformic acid by rectifying then.
The present invention is achieved by the following technical solutions: C such as propane, propylene and/or propenal
3C such as compound or Trimethylmethane, iso-butylene, the trimethyl carbinol and/or Methylacrylaldehyde
4The product gas that the compound for catalysis oxidation generates is through absorbing and rectifying, obtains containing thick (methyl) vinylformic acid of 10～5000ppm (methyl) propenal, furfural, phenyl aldehyde and toxilic acid impurity of having an appointment.With this thick (methyl) vinylformic acid is raw material, mixture with at least a composition at least a in guanidine compound or its salt and urea or the thiourea is an aldehyde removing agent, after adding the hydroquinone of polymerization retarder account for thick (methyl) vinylformic acid consumption 500～2000ppm of raw material, compound aldehyde removing agent is added the aldehyde that makes in thick (methyl) vinylformic acid in aldehyde removing agent and thick (methyl) vinylformic acid and toxilic acid 25～100 ℃ of following synthesis under normal pressure 0.1～10 hour; Under the vacuum tightness of 0.1～50kPa, this reaction solution is carried out intermittence or continuous rectification again, do not contained aldehyde and toxilic acid and purity reach essence (methyl) vinylformic acid more than 99.80%.
Guanidine compound or its salt comprise nitroguanidine, dicyanodiamide, hydroxyl guanidine, aminoguanidine, Guanidinium hydrochloride, Guanidinium nitrate, aminoguanidine monohydrochloride, aminoguanidine sulfate, aminoguanidine sulfate, aminoguanidine nitrate, N-alkyl guanidine or its salt or N in the above-mentioned compound aldehyde removing agent, N-dialkyl group guanidine or its salt, preferred hydroxyl guanidine, aminoguanidine, aminoguanidine sulfate, aminoguanidine nitrate, N, N-diethyl guanidine or N, N-diethyl guanidinesalt hydrochlorate; Urea or thiourea comprise urea, Urea,amino-, thiocarbamide, thiosemicarbazide, bis-thiourea, N, N '-diamino thiocarbamide, N-alkyl urea, N, N-dialkyl ureas, N-alkoxy ureas, N-alkyl thiourea or N, the N-dialkyl thiourea, preferred urea, Urea,amino-, thiocarbamide, thiosemicarbazide, N-tert butyl urea, N, N-dimethyl urea, N, N-di-isopropyl urea, N-methoxyl group urea, N-methylthiourea or N, N-diethyl thiourea.The mass ratio of aminoguanidine or its esters compound and urea or thiourea is 1: 50～50: 1 in the compound aldehyde removing agent, preferred 1: 10～10: 1; The aldehyde in the add-on of compound aldehyde removing agent and thick (methyl) vinylformic acid and the mol ratio of toxilic acid total amount are 1: 10～20: 1, preferred 1: 2～4: 1.
Preparation essence (methyl) acrylic acid that the present invention adopts has following advantage:
1) do not need catalyzer in the removing aldehyde process, the compound aldehyde removing agent that utilizes guanidine compound or its salt and urea or thiourea to form, not only aldehyde material and toxilic acid in thick (methyl) vinylformic acid there is good removal effect, and no solid deposits generates in the reaction solution, does not influence the continuous production of device.
2) two compounds in the compound aldehyde removing agent respectively have characteristics to full gear and toxilic acid, guanidine compound is better for removing the aldehyde material effect, carbamide compounds is better to the removal effect of toxilic acid, and advantage production high purity just (methyl) vinylformic acid that has concurrently after the two is compound separately is needed.
3) compound aldehyde removing agent is not only cheap, and add-on is also less, and it is few to handle thick (methyl) medicament that vinylformic acid consumed like this, and it is lower to produce smart (methyl) acrylic acid cost.
Embodiment
To be illustrated with specific embodiment below, but content of the present invention is not limited to these embodiment.
Embodiment 1-8
In the there-necked flask of 500mml, add 300 and restrain the crude acrylic acid that contains 120ppm furfural, 20ppm propenal, 150ppm phenyl aldehyde, 2000ppm toxilic acid, and the hydroquinone of polymerization retarder that accounts for raw materials used quality 1000ppm, add aldehyde removing agent again, at 50 ℃ of 20min of following reaction times of temperature, on the there-necked flask of 500mml, connect the filler distillation column be equivalent to 10 plots of theoretical slopes then and carry out rectifying and obtain the fine propylene acid product.The purity of fine propylene acid product adopts the analysis of gas-chromatography marker method, and moisture content is measured by automatic moisture determination instrument.
The mixture that adopts guanidine compound or its salt and urea or thiourea to form is an aldehyde removing agent, and test-results sees Table 1.Obviously, the content of impurity aldehyde material and toxilic acid is zero in the fine propylene acid behind the engaging aldehyde refinement, and vinylformic acid purity reaches more than the 99.83 weight %.
The compound aldehyde removing agent of table 1 is to crude acrylic acid full gear experimental result
| Embodiment | Compound aldehyde removing agent title | Add-on (wt%) | Aldehyde (ppm) | Toxilic acid (ppm) | Fine propylene acid (wt%) | Give birth to the slag situation |
| 1 | Hydroxyl guanidine+thiocarbamide | 0.5 | 0 | 0 | 99.83 | Do not have |
| 2 | Aminoguanidine sulfate+thiocarbamide | 0.5 | 0 | 0 | 99.86 | Do not have |
| 3 | Aminoguanidine monohydrochloride+thiosemicarbazide | 0.5 | 0 | 0 | 99.89 | Do not have |
| 4 | Aminoguanidine sulfate+Urea,amino- | 0.5 | 0 | 0 | 99.83 | Do not have |
| 5 | Aminoguanidine sulfate+thiosemicarbazide | 0.5 | 0 | 0 | 99.85 | Do not have |
| 6 | Hydroxyl guanidine+thiosemicarbazide | 0.5 | 0 | 0 | 99.90 | Do not have |
| 7 | Hydroxyl guanidine+Urea,amino- | 0.5 | 0 | 0 | 99.91 | Do not have |
| 8 | Aminoguanidine nitrate+Urea,amino- | 0.5 | 0 | 0 | 99.86 | Do not have |
Comparative example 1-8
Other condition is with embodiment 1, and aldehyde removing agent changes independent amine, guanidine class or carbamide compounds into, and test-results sees Table 2.As seen, adopting single amine, guanidine class or carbamide compounds is aldehyde removing agent, still contains a certain amount of impurity aldehyde and toxilic acid in the fine propylene acid after making with extra care, and vinylformic acid purity is all below 99.82 weight %.
Independent amine, guanidine class or the carbamide compounds of table 2 is to crude acrylic acid full gear experimental result
| Comparative example | The aldehyde removing agent title | Add-on (wt%) | Aldehyde (ppm) | Toxilic acid (ppm) | Fine propylene acid (wt%) | Give birth to the slag situation |
| 1 | Thiosemicarbazide | 0.5 | 158 | 10 | 99.74 | Do not have |
| 2 | Aniline | 0.5 | 2 | 150 | 99.80 | Have |
| 3 | Hydrazine hydrate | 0.5 | 5 | 134 | 99.78 | Have |
| 4 | Mphenylenediamine | 0.5 | 0 | 176 | 99.73 | Have |
| 5 | Monoethanolamine MEA BASF | 0.5 | 3 | 243 | 99.71 | On a small quantity |
| 6 | O-Phenylene Diamine | 0.5 | 4 | 147 | 99.82 | Have |
| 7 | The hydroxyl guanidine | 0.5 | 0 | 256 | 99.78 | Have |
| 8 | Aminoguanidine sulfate | 0.5 | 0 | 247 | 99.75 | Have |
Embodiment 9-16
In the there-necked flask of 500ml, add 300 and restrain the crude methacrylic acid that contains 60ppm furfural, 20ppm Methylacrylaldehyde, 1000ppm toxilic acid, and the hydroquinone of polymerization retarder that accounts for raw materials used quality 1000ppm, add aldehyde removing agent again, at 50 ℃ of 20min of following reaction times of temperature, on the there-necked flask of 500mml, connect the filler distillation column be equivalent to 10 plots of theoretical slopes then and carry out rectifying and obtain smart methacrylic acid product.Finishing methacrylic acid product purity adopts the analysis of gas-chromatography marker method, and moisture content is measured by automatic moisture determination instrument.
The mixture that adopts guanidine compound or its salt and urea or thiourea to form is an aldehyde removing agent, and test-results sees Table 3.Obviously, the content of impurity aldehyde material and toxilic acid is zero in the smart methacrylic acid behind the engaging aldehyde refinement, and vinylformic acid purity reaches more than the 99.84 weight %.
The compound aldehyde removing agent of table 3 is to crude methacrylic acid full gear experimental result
| Embodiment | Compound aldehyde removing agent title | Add-on (wt%) | Furfural (ppm) | Toxilic acid (ppm) | Smart methacrylic acid (wt%) | Give birth to the slag situation |
| 1 | N, N-diethyl guanidine+urea | 0.5 | 0 | 0 | 99.92 | Do not have |
| 2 | Aminoguanidine sulfate+N-tert butyl urea | 0.5 | 0 | 0 | 99.87 | Do not have |
| 3 | Aminoguanidine monohydrochloride+thiocarbamide | 0.5 | 0 | 0 | 99.85 | Do not have |
| 4 | Aminoguanidine sulfate+Urea,amino- | 0.5 | 0 | 0 | 99.90 | Do not have |
| 5 | Aminoguanidine sulfate+N-methoxyl group urea | 0.5 | 0 | 0 | 99.84 | Do not have |
| 6 | Hydroxyl guanidine+N-methylthiourea | 0.5 | 0 | 0 | 99.86 | Do not have |
| 7 | N, N-diethyl guanidine+N-methoxyl group urea | 0.5 | 0 | 0 | 99.89 | Do not have |
| 8 | Aminoguanidine nitrate+N, N-di-isopropyl urea | 0.5 | 0 | 0 | 99.90 | Do not have |
[0028]Comparative example 9-16
Other condition is with embodiment 9, and aldehyde removing agent changes independent amine, guanidine class or carbamide compounds into, and test-results sees Table 4.As seen, adopting single amine, guanidine class or carbamide compounds is aldehyde removing agent, still contains a certain amount of impurity aldehyde and toxilic acid in the smart methacrylic acid after making with extra care, and methacrylic acid purity is less than 99.83 weight %.
Independent amine, guanidine class and the carbamide compounds of getting of table 4 is to crude methacrylic acid full gear experimental result
| Comparative example | The aldehyde removing agent title | Add-on (wt%) | Furfural (ppm) | Toxilic acid (ppm) | Smart methacrylic acid (wt%) | Give birth to the slag situation |
| 1 | Quadrol | 0.5 | 0 | 10 | 99.83 | Have |
| 2 | Hydrazine hydrate | 0.5 | 15 | 150 | 99.80 | Have |
| 3 | The N-methylthiourea | 0.5 | 135 | 2 | 99.78 | Do not have |
| 4 | Mphenylenediamine | 0.5 | 0 | 82 | 99.83 | Have |
| 5 | O-Phenylene Diamine | 0.5 | 3 | 243 | 99.75 | On a small quantity |
| 6 | Thiosemicarbazide | 0.5 | 147 | 4 | 99.70 | Do not have |
| 7 | The hydroxyl guanidine | 0.5 | 0 | 256 | 99.76 | Have |
| 8 | Aminoguanidine sulfate | 0.5 | 0 | 247 | 99.71 | Have |
Claims (3)
1. (methyl) method for producing acrylic acid is characterized in that: C
3Compound propane, propylene, Virahol and/or propenal or C
4The product gas that compound Trimethylmethane, iso-butylene, the trimethyl carbinol and/or Methylacrylaldehyde catalyzed oxidation generate obtains containing thick (methyl) vinylformic acid of 10～5000ppm (methyl) propenal, furfural, phenyl aldehyde and toxilic acid through absorbing and rectifying; With this thick (methyl) vinylformic acid is raw material, mixture with at least a composition at least a and urea in guanidine compound or its salt or the thiourea is compound aldehyde removing agent, and this aldehyde removing agent is added the aldehyde that makes in thick (methyl) vinylformic acid in aldehyde removing agent and thick (methyl) vinylformic acid and toxilic acid 25～100 ℃ of following synthesis under normal pressure 0.1～10 hour; Again under the vacuum tightness of 0.1～50kPa with this reaction solution intermittently or continuous rectification, do not contained aldehyde and toxilic acid and purity be above (methyl) vinylformic acid of 99.80 weight %; Guanidine compound or its salt are hydroxyl guanidine, aminoguanidine monohydrochloride, aminoguanidine sulfate, aminoguanidine nitrate or N in the described compound aldehyde removing agent, N-diethyl guanidine; In the described compound aldehyde removing agent urea or thiourea comprise urea, Urea,amino-, thiocarbamide, thiosemicarbazide, N-tert butyl urea, N, N-di-isopropyl urea, N-methoxyl group urea or N-methylthiourea.
2. according to the described method of claim 1, the aldehyde in the add-on that it is characterized in that described compound aldehyde removing agent and thick (methyl) vinylformic acid and the mol ratio of toxilic acid total amount are 1: 10～20: 1.
3. according to the described method of claim 2, the aldehyde in the add-on that it is characterized in that described compound aldehyde removing agent and thick (methyl) vinylformic acid and the mol ratio of toxilic acid total amount are 1: 2～4: 1.
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Effective date of registration: 20170209 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |
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