CN100389103C - Method for preparing methyl acetate, and reaction rectification tower possessing spatial column plates of mass transfer - Google Patents
Method for preparing methyl acetate, and reaction rectification tower possessing spatial column plates of mass transfer Download PDFInfo
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- CN100389103C CN100389103C CNB2004100990690A CN200410099069A CN100389103C CN 100389103 C CN100389103 C CN 100389103C CN B2004100990690 A CNB2004100990690 A CN B2004100990690A CN 200410099069 A CN200410099069 A CN 200410099069A CN 100389103 C CN100389103 C CN 100389103C
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- acetate
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- outlet weir
- methyl acetate
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Abstract
The present invention discloses a method for preparing methyl acetate, and a reaction rectification tower which is provided with a stereoscopic mass transfer tower plate. The present invention is characterized in that the ratio of the height and the space of an outlet weir is 0.2 to 0.5:1, and the height of the outlet weir of the tower plate is from 40mm to 200mm. The adopted the present invention is provided with a reaction rectification tower of the stereoscopic mass transfer tower plate; the liquid holdup on the tower plate is obviously increased; obvious entrainment does not exist; the generation efficiency of the single tower is obviously increased, and the methyl acetate content and the purity of methyl acetate product on the tower top can be over 99.3%.
Description
Technical field
The present invention relates to the method and apparatus that a kind of reactive distillation prepares methyl acetate, be specifically related to adopt a kind of reaction fractionating tower to prepare the method for methyl acetate with combined trapezoid spray tray.
Technical background
Methyl acetate is one of raw material of carbonylation production aceticanhydride.Also be a kind of good solvent, be used for the productions of multiple fibers such as cellulose nitrate, cellulose acetate, resin, grease and synthetic leather, also be applicable to essence production etc.
Acid and alcohol are under an acidic catalyst effect, generate water and corresponding ester, it is a kind of reversible reaction, in the acetate esters, with acetate and methyl alcohol is raw material, is catalyzer with acid, and the equilibrium constant that generates methyl acetate is for the highest, be 5.2, have only when fully contacting just for a long time between methyl alcohol and the acetate to reach chemical equilibrium.Said acid can be any type of acid, can be hydrochloric acid, sulfuric acid, the phosphoric acid of mineral-type, also can be the p-methyl benzenesulfonic acid of organic class, or even the tart resin.
Be subjected to the restriction of molecular balance and formed ritalin two kinds of azeotropes of---water and ritalin---methyl alcohol, the boiling point of these two kinds of azeotropes and methyl acetate is extremely approaching, and it is extremely difficult wanting to produce highly purified ritalin by methyl alcohol and acetic acid reaction.
The traditional production method of methyl acetate is, acetate, methyl alcohol, catalyzer are joined in the batch still, behind the reaction certain hour, this material is sent in a plurality of rectifying tower in downstream, for making wherein a kind of reactant reach high transformation efficiency that another kind of reactant is excessive a lot.The purified methyl acetate is separated from unreacted reactant, methyl acetate---and the azeotrope of methyl alcohol is then in the Returning reactor.Some manufacturing enterprise has adopted a series of vacuum and non-pressurized rectifying tower, in order to destroy ritalin---and the azeotropic of water is formed.Also having some manufacturers to adopt a plurality of atmospheric distillation towers and an extraction tower, is extraction agent with ethylene glycol ethene monomethyl ether, and ritalin is separated from methyl alcohol.
In EP0060717 and EP0060719, reactor is connected at the bottom of the rectifying tower.Acetate, methyl alcohol, catalyzer-p-methyl benzenesulfonic acid, entrainment agent-n-butyl acetate are joined in the reactor jointly, and the methyl acetate of generation is in the rectifying tower top extraction, and midsection extraction entrainment agent and water, the methyl acetate content that finally obtains only are 95%.
In US4435595, proposed to produce the method for methyl acetate with reaction rectification method, this process using bubble cap plate is as the gas-to-liquid contact interface, obtain highly purified methyl acetate, but, therefore be subjected to the restriction of the entrainment upper limit, the column plate liquid holdup of the type can not be accomplished very big, needs a large amount of column plates to guarantee the long duration of contact of reactant in tower.
Chinese patent CN2475448Y discloses a kind of combined trapezoid spray tray, and one of principal feature of this combined trapezoid spray tray is exactly that spacer plate is installed on the column plate, and because of the effect of spacer plate, gas-liquid separation is very thorough on the column plate.But because this column plate liquid holdup is big, the height of liquid layer drop is bigger on the column plate, and liquid layer pressure drop inequality on the column plate that causes simultaneously, when being used to prepare methyl acetate, also is easy to generate the entrainment phenomenon, must improve.
Summary of the invention
The technical issues that need to address of the present invention are the reaction fractionating towers that disclose a kind of preparation method of methyl acetate and have combined trapezoid spray tray, to overcome the defective that prior art exists.
Reaction fractionating tower with combined trapezoid spray tray of the present invention comprises vertical tower body, horizontal column plate and is arranged on downtake on the horizontal column plate;
Have air rising hole on the said horizontal column plate, in the air rising hole corresponding position jet cover is housed, have jet hole on the jet cover, between jet cover and the horizontal column plate crack, the end is arranged, the spacer plate that three-layer stereo is arranged is equipped with by resting support respectively in top at jet cover, the spacer plate that three-layer stereo is arranged is made up of flat board, the horizontal sextant angle of each piece spacer plate and jet cover is-45～45 °, following one deck spacer plate and middle one deck are separated into style of opening, top one deck spacer plate is a dead front type, downtake is by being arranged on the horizontal column plate, and nearly downtake place is provided with outlet weir.In order to satisfy the preparation of methyl acetate, the contriver has done a large amount of tests to the structure on spacing between the column plate and tray outlet weir, it is characterized in that, the proportionlity between spacing between the horizontal column plate and the outlet weir height is:
Outlet weir height: spacing=0.2～0.5: 1, preferred 0.3～0.45: 1;
Height=the 40mm on tray outlet weir～200mm;
The top of outlet weir is a dentation, and in order further to eliminate the liquid phase dead angle on the column plate, outlet weir is the low arches in middle high two ends simultaneously.
The method that adopts above-mentioned reaction fractionating tower with combined trapezoid spray tray to prepare methyl acetate comprises the steps:
With the acetic acid feed mouth of acetate from tower body top, catalyzer is from the catalyst inlet at tower body middle part, methyl alcohol is sent into reaction fractionating tower from the methanol feeding mouth of tower body bottom, be rectifying section between cat head and the acetic acid feed mouth, acetate here separates with methyl acetate, it between acetic acid feed mouth and the catalyst feeds extraction section, in this zone, acetate destroys methyl acetate-methyl alcohol, the azeotropic of methyl acetate-water is formed, be conversion zone between catalyst feeds and the methanol feeding mouth, here, acetate and methyl alcohol generate methyl acetate and water under catalyst action, be stripping section below the methanol feeding mouth, methyl alcohol is carried from water and is distillated.Cat head obtains the high purity methyl acetate, the drainage water of tower still.
The mol ratio of material benzenemethanol and acetate is 0.8: 1～1.4: 1, preferably by 1.0～1.3;
Said catalyzer is preferably sulfuric acid, and the sulfuric acid consumption is 0.3～1.2%, preferred 0.5～1.0% of methyl alcohol and an acetate total feed;
Reflux ratio is 1～2, and column bottom temperature is 88～90 ℃, and tower top temperature is 56.5～57.5 ℃;
Tower bottom pressure is gauge pressure 0.05MPa, and tower top pressure is a normal pressure;
The column plate of conversion zone can be 10～60, preferred 15～29;
The rectifying section column plate can be 5～18, preferred 8～14;
The extraction section column plate can be 14～30, preferred 14～24;
Adopt the reaction fractionating tower with combined trapezoid spray tray of the present invention, the liquid holdup on the column plate obviously improves, and does not but have tangible entrainment, and the formation efficiency of single tower obviously improves, and cat head ritalin content product purity can reach more than 99.3%.
Description of drawings
Fig. 1 is the combined trapezoid spray tray structural representation.
Fig. 2 is the floor map of column plate.
Fig. 3 is the reaction fractionating tower synoptic diagram.
Embodiment
Referring to Fig. 1, Fig. 2 and Fig. 3, the reaction fractionating tower with combined trapezoid spray tray of the present invention comprises vertical tower body 1, horizontal column plate 9 and is arranged on downtake 7 on the horizontal column plate 9;
Have three row's air rising holes 10 on the said horizontal column plate 9, in air rising hole 10 corresponding positions jet cover 2 is housed, have jet hole 3 on the jet cover 2, between jet cover 2 and the horizontal column plate 9 crack, the end 8 is arranged, the spacer plate 4 that three-layer stereo is arranged is equipped with by resting support 11 respectively in top at jet cover 2,5 and 6, the spacer plate that three-layer stereo is arranged is made up of flat board, the horizontal sextant angle of each piece spacer plate and jet cover 2 is-45～45 °, following one deck spacer plate and middle one deck are separated into style of opening, top one deck spacer plate is a dead front type, downtake 7 is by being arranged on the horizontal column plate 9, nearly downtake 7 places are provided with outlet weir 12, it is characterized in that the outlet weir height: spacing=0.2～0.5: 1, preferred 0.3～0.45: 1; Height=the 40mm on tray outlet weir 12～200mm, the top of outlet weir 12 is a dentation, outlet weir 12 is the low arches in middle high two ends.
Adopt as Fig. 1, Fig. 2 and reaction fractionating tower shown in Figure 3, methyl alcohol and acetate join in the reaction fractionating tower from bottom and top respectively, and sulfuric acid adds in the reaction fractionating tower from the middle part.
Outlet weir is a dentalation, and the outlet weir height is 200mm;
Tray spacing is 450mm;
Conversion zone column plate quantity is 21;
14 of rectifying section column plates;
18 of extraction section column plates;
Material molar ratio: methyl alcohol: acetate=1.2;
The sulfuric acid add-on is 0.6% of methyl alcohol and an acetate combined feed total feed weight.Adopt different reflux ratios, the results are shown in following table
| Reflux ratio | Ritalin content % in the overhead product |
| 1.0 | 99.3 |
| 1.2 | 99.5 |
| 1.4 | 99.6 |
| 1.8 | 99.1 |
Embodiment 5
Adopt the method and apparatus identical with embodiment 1～4, conversion zone column plate quantity is 29, the raw material raw materials components mole ratio: methyl alcohol/acetate=1.0, control of reflux ratio are 1.1, and the methyl acetate content that cat head obtains is 99.5%.
Claims (9)
1. reaction fractionating tower with combined trapezoid spray tray, comprise vertical tower body (1), horizontal column plate (9) and be arranged on downtake (7) on the horizontal column plate (9), downtake (7) is by being arranged on the horizontal column plate (9), nearly downtake (7) locates to be provided with outlet weir (12), it is characterized in that, outlet weir height: spacing=0.2～0.5: 1, the height=40mm on tray outlet weir～200mm.
2. the reaction fractionating tower with combined trapezoid spray tray according to claim 1 is characterized in that, the outlet weir height: spacing=0.3～0.45: 1.
3. the reaction fractionating tower with combined trapezoid spray tray according to claim 1 is characterized in that, the top of outlet weir (12) is a dentation.
4. according to claim 1 or 3 described reaction fractionating towers, it is characterized in that outlet weir (12) is the low arches in middle high two ends with combined trapezoid spray tray.
5. adopt each described reaction fractionating tower of claim 1～4, prepare the method for methyl acetate, it is characterized in that, comprise the steps: with combined trapezoid spray tray
Acetate is sent into reaction fractionating tower from catalyst inlet, the methyl alcohol at tower body middle part from the methanol feeding mouth of tower body bottom from acetic acid feed mouth, the catalyzer on tower body top, and cat head obtains the high purity methyl acetate, the drainage water of tower still;
The mol ratio of material benzenemethanol and acetate is 0.8: 1～1.4: 1;
Said catalyzer is a sulfuric acid;
Reflux ratio is 1～2.1.
6. method according to claim 5 is characterized in that, the mol ratio of material benzenemethanol and acetate is 1.0～1.3.
7. method according to claim 5 is characterized in that, the sulfuric acid consumption is 0.3～1.2% of methyl alcohol and an acetate total feed.
8. method according to claim 5 is characterized in that, column bottom temperature is 88～90 ℃, and tower bottom pressure is gauge pressure 0.05MPa, and tower top temperature is 56.5～57.5 ℃, and tower top pressure is a normal pressure.
9. method according to claim 5, it is characterized in that, be conversion zone between catalyst feeds and the methanol feeding mouth, the column plate of conversion zone is 10～60, be rectifying section between cat head and the acetic acid feed mouth, the rectifying section column plate is 5～18, is extraction section between acetic acid feed mouth and the catalyst feeds, and the extraction section column plate is 14～30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100990690A CN100389103C (en) | 2004-12-27 | 2004-12-27 | Method for preparing methyl acetate, and reaction rectification tower possessing spatial column plates of mass transfer |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100990690A CN100389103C (en) | 2004-12-27 | 2004-12-27 | Method for preparing methyl acetate, and reaction rectification tower possessing spatial column plates of mass transfer |
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| CN1796358A CN1796358A (en) | 2006-07-05 |
| CN100389103C true CN100389103C (en) | 2008-05-21 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328119B (en) * | 2008-06-20 | 2011-03-23 | 中国石油大学(华东) | Synthetic process of methyl acetate and apparatus thereof |
| CN101691325B (en) * | 2009-09-28 | 2012-11-28 | 中国石化集团南京设计院 | Preparation method and device of raw materials needed in preparing acetic anhydride by carbonylation |
| CN102000534A (en) * | 2010-10-02 | 2011-04-06 | 中国石油大学(华东) | Synthesis device of methyl acetate and technological method thereof |
| CN102766044A (en) * | 2012-08-07 | 2012-11-07 | 天津凯赛特科技有限公司 | Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution |
| EP3904280A1 (en) * | 2020-04-29 | 2021-11-03 | Yara International ASA | Absorption column comprising a feed box having a serrated weir and a structured packing and process for the production of nitric acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0060717A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| EP0060719A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| US4435595A (en) * | 1982-04-26 | 1984-03-06 | Eastman Kodak Company | Reactive distillation process for the production of methyl acetate |
| CN2475448Y (en) * | 2001-04-26 | 2002-02-06 | 河北工业大学 | Stereoscopic mass transfer tower plate |
-
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- 2004-12-27 CN CNB2004100990690A patent/CN100389103C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0060717A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| EP0060719A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| US4435595A (en) * | 1982-04-26 | 1984-03-06 | Eastman Kodak Company | Reactive distillation process for the production of methyl acetate |
| CN2475448Y (en) * | 2001-04-26 | 2002-02-06 | 河北工业大学 | Stereoscopic mass transfer tower plate |
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Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
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Address after: 200241 No. 4280 Wu Long Road, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Patentee after: Hebei University of Technology Address before: 200241 No. 4280 Wu Long Road, Shanghai Patentee before: Shanghai Coking Co., Ltd. Patentee before: Hebei University of Technology |