CN101085733B - Method for preparing refined acrylic acid by removing micro-impurity aldehyde - Google Patents
Method for preparing refined acrylic acid by removing micro-impurity aldehyde Download PDFInfo
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- CN101085733B CN101085733B CN200710043080A CN200710043080A CN101085733B CN 101085733 B CN101085733 B CN 101085733B CN 200710043080 A CN200710043080 A CN 200710043080A CN 200710043080 A CN200710043080 A CN 200710043080A CN 101085733 B CN101085733 B CN 101085733B
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Abstract
The invention relates to a method for preparing high- purity acroleic acid. It comprises following steps: (1) water absorbing and fine distilling propone oxidate, and getting coarse acroleic acid containing foreign aldehyde of 10- 1000 ppm, said foreign aldehyde includes acrolein, acrolein and benzaldehyde; (2) adding inhibitor eldopaque and alcohol matter containing 3- 10 carbons into coarse acroleic acid, the alcohol matter and foreign aldehyde reacts at normal pressure and 25- 100 Deg. C for 0.1- 10 hours; (3) intermitten or continuous rectification material under vacuum of 0.1- 50 Kpa, getting high- purity acroleic acid with aldehyde content being zero and acroleic acid content being more than 99.8%. The invention is characterized by simple reaction, easy separation of foreigh material from product, low production cost and high- purity of product.
Description
Technical field
The present invention relates to a kind of method that micro-impurity aldehyde prepares high purity acrylic acid that removes, being particularly related to the crude acrylic acid that contains impurity aldehyde that obtains with catalytic oxidation propylene is raw material, and the alcohols material that contains 3～10 carbon atoms by adding carries out the method that aldehyde removing prepares high purity acrylic acid.
Background technology
In the catalytic oxidation process of propylene, generate aldehyde materials such as multiple by product such as furfural, these by products more or less are brought in the acrylic products, cause the purity of acrylic products to descend, thereby influence the use properties of acrylic products, when especially the user needs highly purified polymerization-grade fine propylene sour, often, can not satisfy customer requirements because of containing aldehyde type impurities.
Because aldehyde materials such as furfural are close with acrylic acid physical properties, the small amount of impurities aldehyde that contains in the vinylformic acid generally can not be removed by common rectificating method, otherwise is uneconomic.Aldehyde removing is economical and effective method, and promptly adding a small amount of compound just can be with impurity removal.Adopt chemical process to remove the early existing patent report of a spot of aldehyde in the vinylformic acid, adopt aldehyde reaction in primary amine and salt and the vinylformic acid, reach the purpose that removes aldehyde as the patent CN1106789A of BASF AG report.But generated corresponding condenses because primary amine and aldehyde carry out condensation reaction, caused Polycondensation Reactor and Esterification Reactor to generate settling.In order to eliminate this basic sediment, this patent report also will add a kind of organic Phenylsulfonic acid and carry out " neutralization ".This method operation is more numerous, and the still bottom sediment is difficult to eliminate fully.The patent CN1541199A of MIT report adopts the alkyl sulfhydryl that contains 10～16 carbon atoms, reacts in the presence of acidic cation-exchange resin, reaches the purpose of full gear.Though this method deposit-free generates, alkyl sulfhydryl is expensive, adds more expensive resin catalyst, and vinylformic acid full gear processing cost is higher.Resin catalyst needs regularly to change in addition, operates also more complicated.German Patent GB02285046A, Japanese Patent JP11060536 and JP10087552 be all with phenylhydrazine and the organic amino aldehyde removing agent as crude acrylic acid, all exist full gear not thoroughly, Polycondensation Reactor and Esterification Reactor has sedimental phenomenon.
Summary of the invention
The present invention has overcome above-mentioned shortcoming, adopts the alcohols material that contains 3～10 carbon atoms to carry out condensation reaction in acid system, generates a kind of high boiling point condensate, stays at the bottom of the still owing to its boiling point is higher during distillation, thereby reaches the purpose that removes aldehyde.
Principle of the present invention is based on the chemical property of aldehyde, for unsaturated aldehyde, its in the presence of acidic medium easily and alcohol carry out 1,4 addition reaction.For saturated aldehyde, carbonyl and alcohol carry out condensation reaction and produce condenses.Generalized case, the chemical property of acetal is more stable in alkaline medium, but meet water in acidic medium hydrolysis reaction takes place easily, is reduced to original aldehyde and alcohol.So the moisture in the crude acrylic acid material system should be low as far as possible.
One of advantage of technology of the present invention is not need an acidic catalyst, utilizes acrylic acid acidity, and system is heated to certain temperature, can accelerate speed of reaction, makes aldehyde material almost all change into corresponding condenses.Because the alcohols material carbon number of selecting is greater than 3, the boiling point of its condenses is higher, easily stays at the bottom of the still, can the quality of fine propylene acid not had a negative impact.
Another advantage of the present invention is that aldehyde is soluble in vinylformic acid with the condenses that alcohol generates, and can not be deposited on base product with the solid form, does not influence the operate continuously of device.
Not only price is lower for the alcohols material that the present invention selects, and add-on is also less, and optimum add-on is 0.1～1.5% raw materials used (quality), and the medicament of handling vinylformic acid per ton like this and being consumed is few, and production cost reduces greatly.
Thisly remove the method that micro-impurity aldehyde prepares fine propylene acid, it is characterized in that this fine propylene acid prepares as follows:
1) the propylene oxidation product obtains containing the crude acrylic acid of 10～1000ppm impurity aldehyde after water absorption and rectifying, and impurity aldehyde is propenal, furfural and phenyl aldehyde;
2) add hydroquinone of polymerization retarder and contain the alcohols material of 3～10 carbon atoms in the crude acrylic acid, the impurity aldehyde in alcohols material and the crude acrylic acid was reacted 0.1～10 hour down normal pressure and 25～100 ℃;
3) reacted material carries out intermittence or rectification under vacuum continuously under 0.1～50kPa vacuum tightness, and obtaining aldehyde is that zero-sum vinylformic acid purity reaches the high-purity fine propylene acid more than 99.80%.
Hydroquinone of polymerization retarder consumption among the present invention is 200～2000ppm, and the temperature of reaction of impurity aldehyde is 40～80 ℃ in alcohol and the crude acrylic acid, and the reaction times is 0.5～3 hour, and the vacuum tightness of rectification under vacuum is 0.5～20kPa.
The alcohols material that contains 3～10 carbon atoms among the present invention be n-propyl alcohol, propyl carbinol, 2-enanthol, sec-n-octyl alcohol, 1-chloro-2-propanol, 2-monoethanolamine, 1,3-two chloro-2-propyl alcohol or they are with the mixture of arbitrary proportion, and add-on is 0.005～8% of a raw materials used vinylformic acid quality.
The alcohols material that contains 3～10 carbon atoms among the present invention is preferably 2-enanthol, sec-n-octyl alcohol, 1-chloro-2-propanol, 2-monoethanolamine, and add-on is 0.1～1.5% of a raw materials used vinylformic acid quality.
The present invention with the propylene oxidation product through water absorption and rectifying and the crude acrylic acid that obtains containing impurity such as 10～1000ppm propenal, furfural and/or phenyl aldehyde is a raw material, in crude acrylic acid, add hydroquinone of polymerization retarder, the alcohols material that selection contains 3～10 carbon atoms be full gear reagent earlier with crude acrylic acid in aldehyde react, carry out intermittence or rectification under vacuum continuously then, rectification under vacuum vacuum tightness is 0.1～50kPa, preferred 0.5～20kPa, obtaining aldehyde is that zero-sum vinylformic acid purity reaches the polymerization-grade fine propylene acid more than 99.80%.
Before the adding alcohols material carries out the full gear reaction, in crude acrylic acid, add hydroquinone of polymerization retarder earlier, add-on is 200 raw materials used～2000ppm.Full gear is reflected under the normal pressure to be carried out, 25～100 ℃ of temperature of reaction, preferred 40～80 ℃; 0.1～10 hour reaction times, preferred 0.5～3 hour.
The alcohols material that contains 3～10 carbon atoms comprise n-propyl alcohol, propyl carbinol, 2-enanthol, sec-n-octyl alcohol, 1-chloro-2-propanol, 2-monoethanolamine, 1,3-two chloro-2-propyl alcohol or they are with the mixture of arbitrary proportion, preferred 2-enanthol, sec-n-octyl alcohol, 1-chloro-2-propanol or 2-monoethanolamine.The alcohols material add-on is 0.005～8% of a raw materials used vinylformic acid quality, preferred 0.1～1.5%.
Embodiment
Come implementation process of the present invention is described in detail below by embodiment, but protection domain is not subjected to the restriction of embodiment.
Embodiment 1-4
In the there-necked flask of 500ml, add 300 and restrain the crude acrylic acid that contains 120ppm furfural, 20ppm propenal and 150ppm phenyl aldehyde, add 1000ppm hydroquinone of polymerization retarder and 0.5% (quality) alcohols aldehyde removing agent again, under 50 ℃ temperature, react 40min.Connect the distillation filled column that is equivalent to 10 plots of theoretical slopes then and carry out rectification under vacuum and obtain the acid of product fine propylene on the there-necked flask of 500ml, experimental result sees Table 1.
The single alcohols material of table 1 is to crude acrylic acid full gear experimental result
| Embodiment | The aldehyde removing agent title | Aldehyde in the fine propylene acid, ppm | Fine propylene acid purity, wt% | Phenomenon at the bottom of the still |
| Embodiment 1 | The 2-enanthol | 0 | 99.81 | Deposit-free |
| Embodiment 2 | Sec-n-octyl alcohol | 0 | 99.80 | Deposit-free |
| Embodiment 3 | The 2-monoethanolamine | 0 | 99.83 | Deposit-free |
| Embodiment 4 | 1-chloro-2-propanol | 0 | 99.81 | Deposit-free |
Embodiment 5-8
Except that aldehyde removing agent is changed to the alcohol mixture by single alcohol, raw material composition, reaction and rectifying condition the results are shown in Table 2 all with embodiment 1.
Table 2 alcohol mixture (ratio is 1: 1) is to the full gear experimental result of crude acrylic acid
| Embodiment | The aldehyde removing agent title | Aldehyde in the fine propylene acid, ppm | Fine propylene acid purity, wt% | Phenomenon at the bottom of the still |
| Embodiment 5 | 2-enanthol+propyl carbinol | 0 | 99.85 | Deposit-free |
| Embodiment 6 | Sec-n-octyl alcohol+1,3-two chloro-2-propyl alcohol | 0 | 99.82 | Deposit-free |
| Embodiment 7 | 2-monoethanolamine+n-propyl alcohol | 0 | 99.87 | |
| Embodiment 8 | 1-chloro-2-propanol+sec-n-octyl alcohol | 0 | 99.80 | Deposit-free |
Comparative example 1-4
Except that aldehyde removing agent is changed into amine and the derivative thereof by alcohols material, raw material composition, reaction and rectifying condition the results are shown in Table 3 all with embodiment 1.
Table 3 organic amine is to crude acrylic acid full gear experimental result
| Comparative example | The aldehyde removing agent title | Aldehyde in the fine propylene acid, ppm | Phenomenon at the bottom of the still |
| Comparative example 1 | Quadrol | 2 | Reaction is violent, has polymkeric substance to produce |
| Comparative example 2 | Aniline | 0 | Caking is arranged |
| Comparative example | The aldehyde removing agent title | Aldehyde in the fine propylene acid, ppm | Phenomenon at the bottom of the still |
| Comparative example 3 | Hydrazine hydrate | 5 | Caking is arranged |
| Comparative example 4 | O-Phenylene Diamine | 1 | Settling is arranged |
Comparative example 5-8
Except that aldehyde removing agent is changed into amine and the derivative thereof by alcohols material, raw material composition, reaction and rectifying condition the results are shown in Table 4 all with embodiment 1.
Table 4 mixes organic amine (ratio is 1: 1) to crude acrylic acid full gear experimental result
| Comparative example | Organic amine | Aldehyde in the fine propylene acid, ppm | Phenomenon at the bottom of the still |
| Comparative example 5 | Mphenylenediamine+aniline | 0 | A small amount of settling is arranged |
| Comparative example 6 | Aniline+4-nitrophenyl hydrazine | 0 | Caking is arranged |
| Comparative example 7 | Hydrazine hydrate+o-toluidine | 6 | A small amount of caking is arranged |
| Comparative example 8 | 2,4 dinitrophenyl hydrazine+O-Phenylene Diamine | 3 | Settling is arranged |
Claims (4)
1. one kind removes the method that micro-impurity aldehyde prepares fine propylene acid, it is characterized in that this fine propylene acid prepares as follows:
1) the propylene oxidation product obtains containing the crude acrylic acid of 10～1000ppm impurity aldehyde after water absorption and rectifying, and impurity aldehyde is propenal, furfural and phenyl aldehyde;
2) add hydroquinone of polymerization retarder and contain the alcohols material of 3～10 carbon atoms in the crude acrylic acid, the impurity aldehyde in alcohols material and the crude acrylic acid was reacted 0.1～10 hour down normal pressure and 25～100 ℃;
3) reacted material carries out intermittence or rectification under vacuum continuously under 0.1～50kPa vacuum tightness, and obtaining aldehyde is that zero-sum vinylformic acid purity reaches the high-purity fine propylene acid more than 99.80%.
2. according to the described method of claim 1, it is characterized in that the hydroquinone of polymerization retarder consumption is 200～2000ppm, the temperature of reaction of impurity aldehyde is 40～80 ℃ in alcohol and the crude acrylic acid, and the reaction times is 0.5～3 hour, and the vacuum tightness of rectification under vacuum is 0.5～20kPa.
3. according to the described method of claim 1, the alcohols material that it is characterized in that containing 3～10 carbon atoms be n-propyl alcohol, propyl carbinol, 2-enanthol, sec-n-octyl alcohol, 1-chloro-2-propanol, 2-monoethanolamine, 1,3-two chloro-2-propyl alcohol or they are with the mixture of arbitrary proportion, and add-on is 0.005～8% of a used crude acrylic acid quality.
4. according to the described method of claim 3, the alcohols material that it is characterized in that containing 3～10 carbon atoms is 2-enanthol, sec-n-octyl alcohol, 1-chloro-2-propanol, 2-monoethanolamine, and add-on is 0.1～1.5% of a used crude acrylic acid quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710043080A CN101085733B (en) | 2007-06-29 | 2007-06-29 | Method for preparing refined acrylic acid by removing micro-impurity aldehyde |
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| CN200710043080A CN101085733B (en) | 2007-06-29 | 2007-06-29 | Method for preparing refined acrylic acid by removing micro-impurity aldehyde |
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| CN101085733B true CN101085733B (en) | 2010-05-19 |
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| CN103880649B (en) * | 2014-04-03 | 2016-08-31 | 泰兴市裕廊化工有限公司 | A kind of high yield ice crystal level method for producing acrylic acid |
| CN111253882B (en) * | 2020-01-21 | 2021-05-25 | 安徽富印新材料有限公司 | Antistatic pressure-sensitive adhesive, preparation method thereof and antistatic pressure-sensitive adhesive tape |
| CN111253872A (en) * | 2020-03-21 | 2020-06-09 | 安徽富印新材料有限公司 | Electromagnetic shielding conductive adhesive tape |
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Effective date of registration: 20170208 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. |