CN100389103C - Preparation method of methyl acetate and reactive distillation column with three-dimensional mass transfer tray - Google Patents
Preparation method of methyl acetate and reactive distillation column with three-dimensional mass transfer tray Download PDFInfo
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 28
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000066 reactive distillation Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000003054 catalyst Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000003595 mist Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- QZJVWTNHFOMVHX-UHFFFAOYSA-N methanol;methyl acetate Chemical compound OC.COC(C)=O QZJVWTNHFOMVHX-UHFFFAOYSA-N 0.000 description 3
- ANLISICGYWBHKU-UHFFFAOYSA-N methyl acetate;hydrate Chemical compound O.COC(C)=O ANLISICGYWBHKU-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 ethylene glycol ethylene monomethyl ether Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
本发明公开了一种乙酸甲酯的制备方法和具有立体传质塔板的反应精馏塔。其特征在于，出口堰高度∶间距＝0.2～0.5∶1，塔板出口堰的高度＝40mm～200mm。采用本发明的具有立体传质塔板的反应精馏塔，塔板上的持液量明显提高，却没有明显的雾沫夹带，单塔的生成效率明显提高，塔顶醋酸甲酯含量产品纯度可达到99.3%以上。
The invention discloses a method for preparing methyl acetate and a reactive distillation column with three-dimensional mass transfer trays. It is characterized in that the outlet weir height: spacing = 0.2-0.5: 1, and the height of the tray outlet weir = 40mm-200mm. Adopting the reactive distillation column with three-dimensional mass transfer trays of the present invention, the liquid holdup on the trays is significantly improved, but there is no obvious mist entrainment, the generation efficiency of the single tower is obviously improved, and the methyl acetate content at the top of the tower is higher than the product purity. It can reach more than 99.3%.
Description
技术领域 technical field
本发明涉及一种反应精馏制备乙酸甲酯的方法和设备，具体涉及采用一种具有立体传质塔板的反应精馏塔制备乙酸甲酯的方法。The invention relates to a method and equipment for preparing methyl acetate by reactive distillation, in particular to a method for preparing methyl acetate by using a reactive distillation column with three-dimensional mass transfer trays.
技术背景technical background
乙酸甲酯是羰基化生产醋酐的原料之一。也是一种良好的溶剂，用于硝酸纤维、醋酸纤维等多种纤维、树脂、油脂以及合成革生产中，还适用于香精生产等。Methyl acetate is one of the raw materials for carbonylation to produce acetic anhydride. It is also a good solvent, which is used in the production of various fibers, resins, oils and synthetic leathers such as cellulose nitrate and cellulose acetate, and is also suitable for the production of flavors.
酸和醇在酸性催化剂作用下，生成水和相应的酯，是一种可逆反应，乙酸酯类中，以乙酸和甲醇为原料，以酸为催化剂，生成乙酸甲酯的平衡常数为最高，为5.2，只有当甲醇与乙酸之间长时间充分接触才能达到化学平衡。所说的酸可以是任何形式的酸，可以是无机类的盐酸、硫酸、磷酸，也可以是有机类的对甲基苯磺酸，甚至是酸性的树脂。Under the action of acidic catalyst, acid and alcohol generate water and corresponding ester, which is a reversible reaction. Among acetates, acetic acid and methanol are used as raw materials, and acid is used as catalyst to generate methyl acetate. The equilibrium constant is the highest, which is 5.2, the chemical equilibrium can be reached only when methanol and acetic acid are fully contacted for a long time. Said acid can be any form of acid, which can be inorganic hydrochloric acid, sulfuric acid, phosphoric acid, or organic p-toluenesulfonic acid, or even acidic resin.
受反应平衡的限制且形成了醋酸甲酯——水和醋酸甲酯——甲醇两种恒沸物，这两种共沸物与乙酸甲酯的沸点极其接近，要想由甲醇与醋酸反应生产高纯度的醋酸甲酯是极其困难的。Restricted by the reaction balance, two azeotropes of methyl acetate-water and methyl acetate-methanol are formed. These two azeotropes are extremely close to the boiling point of methyl acetate. If they are to be produced by the reaction of methanol and acetic acid High purity methyl acetate is extremely difficult.
乙酸甲酯传统的生产方法是，将乙酸、甲醇、催化剂加入到间歇釜内，反应一定时间后，将该物料送入到下游的多个精馏塔中，为使其中一种反应物达到高的转化率而将另一种反应物过量很多。精制的乙酸甲酯从未反应物中分离出来，而乙酸甲酯——甲醇的共沸物则返回反应器内。有些生产企业采用了一系列真空的和常压的精馏塔，用以破坏醋酸甲酯——水的共沸组成。还有一些生产商采用了多个常压精馏塔和一个萃取塔，以乙二醇乙烯单甲基醚为萃取剂，将醋酸甲酯从甲醇中分离出来。The traditional production method of methyl acetate is to add acetic acid, methanol, and a catalyst into a batch kettle. After a certain period of reaction, the material is sent to a plurality of rectification towers downstream. In order to make one of the reactants reach a high The conversion of the other reactant is in large excess. The refined methyl acetate is separated from the unreacted product, and the methyl acetate-methanol azeotrope is returned to the reactor. Some manufacturers have adopted a series of vacuum and atmospheric distillation columns to destroy the azeotropic composition of methyl acetate-water. There are also some manufacturers who use multiple atmospheric distillation towers and an extraction tower to separate methyl acetate from methanol with ethylene glycol ethylene monomethyl ether as the extractant.
在EP0060717和EP0060719中，反应釜连接在一座精馏塔底。将乙酸、甲醇、催化剂-对甲基苯磺酸、夹带剂-乙酸正丁酯共同加入到反应釜中，生成的乙酸甲酯在精馏塔顶采出，塔中段采出夹带剂和水，最终得到的乙酸甲酯含量仅为95％。In EP0060717 and EP0060719, the reactor is connected at the bottom of a rectifying column. Add acetic acid, methanol, catalyst-p-toluenesulfonic acid, and entrainer-n-butyl acetate into the reactor, and the generated methyl acetate is extracted from the top of the rectification tower, and the entrainer and water are extracted from the middle section of the tower. The resulting methyl acetate content is only 95%.
在US4435595中，提出了以反应精馏法生产乙酸甲酯的方法，该工艺采用泡罩塔板作为气液接触界面，得到高纯度的乙酸甲酯，但是，受雾沫夹带上限的限制，该类型的塔板持液量不能做到很大，因此需要大量的塔板来保证反应物在塔内的长接触时间。In US4435595, a method for producing methyl acetate by reactive distillation is proposed. This process adopts bubble cap trays as the gas-liquid contact interface to obtain high-purity methyl acetate. However, limited by the upper limit of mist entrainment, this The liquid holding capacity of the type tray cannot be very large, so a large number of trays are needed to ensure the long contact time of the reactants in the column.
中国专利CN2475448Y公开了一种立体传质塔板，该立体传质塔板的主要特点之一就是塔板上安装有分离板，因分离板的作用，塔板上气液分离很彻底。但是，由于该塔板持液量大，塔板上液层高度落差较大，导致的塔板上液层压降不均，同时，用于制备乙酸甲酯时，还容易产生雾沫夹带现象，必须进行改进。Chinese patent CN2475448Y discloses a three-dimensional mass transfer tray. One of the main features of the three-dimensional mass transfer tray is that a separation plate is installed on the tray. Due to the effect of the separation plate, the gas-liquid separation on the tray is very thorough. However, due to the large liquid holding capacity of the tray, the height drop of the liquid layer on the tray is relatively large, resulting in uneven pressure drop of the liquid layer on the tray. At the same time, when it is used to prepare methyl acetate, it is also prone to mist entrainment. Improvements must be made.
发明内容 Contents of the invention
本发明需要解决的技术问题是公开一种乙酸甲酯的制备方法和具有立体传质塔板的反应精馏塔，以克服现有技术存在的缺陷。The technical problem to be solved in the present invention is to disclose a method for preparing methyl acetate and a reactive distillation column with three-dimensional mass transfer trays, so as to overcome the defects in the prior art.
本发明的具有立体传质塔板的反应精馏塔，包括立式的塔体、水平塔板和设置在水平塔板上的降液管；The reactive distillation column with three-dimensional mass transfer trays of the present invention comprises a vertical tower body, a horizontal tray and a downcomer arranged on the horizontal tray;
所说的水平塔板上开有升气孔，在升气孔对应处装有喷射罩，喷射罩上开有喷射孔，喷射罩与水平塔板之间有底隙，在喷射罩的顶部分别通过支承架装有三层立体排布的分离板，三层立体排布的分离板由平板组成，每一块分离板与喷射罩的水平夹角为-45～45°，下面一层分离板和中间一层分离为开放型，上面一层分离板为封闭型，降液管靠设置在水平塔板上，近降液管处设有出口堰。为了满足乙酸甲酯的制备，发明人对塔板之间的间距和塔板出口堰的结构做了大量试验，其特征在于，水平塔板之间的间距与出口堰高度之间的比例关系为：The said horizontal tray is provided with an air lift hole, and a spray cover is installed at the corresponding place of the lift hole, and a spray hole is opened on the spray cover, and there is a bottom gap between the spray cover and the horizontal tray, and the top of the spray cover is respectively passed through a support The rack is equipped with three-layer separation plates arranged three-dimensionally. The three-layer separation plates are composed of flat plates. The horizontal angle between each separation plate and the spray hood is -45~45°. The lower layer of separation plate and the middle layer The separation is open type, the upper separation plate is closed type, the downcomer is arranged on the horizontal tray, and the outlet weir is arranged near the downcomer. In order to meet the preparation of methyl acetate, the inventor has done a lot of tests to the structure of the spacing between the trays and the outlet weir of the trays, and it is characterized in that the proportional relationship between the spacing between the horizontal trays and the height of the outlet weir is: :
出口堰高度∶间距＝0.2～0.5∶1，优选0.3～0.45∶1；Height of outlet weir: spacing=0.2～0.5:1, preferably 0.3～0.45:1;
塔板出口堰的高度＝40mm～200mm；The height of the tray outlet weir = 40mm ~ 200mm;
出口堰的顶端为齿状，同时为了进一步消除塔板上的液相死角，出口堰为中间高两端低的拱形。The top of the outlet weir is tooth-shaped, and at the same time, in order to further eliminate the dead angle of the liquid phase on the tray, the outlet weir is arched with a high middle and low ends.
采用上述具有立体传质塔板的反应精馏塔制备乙酸甲酯的方法包括如下步骤：The method for preparing methyl acetate by adopting the above-mentioned reactive distillation tower with three-dimensional mass transfer tray may further comprise the steps:
将乙酸从塔体上部的乙酸进料口、催化剂从塔体中部的催化剂入口、甲醇从塔体下部的甲醇进料口送入反应精馏塔，塔顶和乙酸进料口之间为精馏段，乙酸和乙酸甲酯在这里进行分离，乙酸进料口和催化剂进料口之间为萃取段，在该区域，乙酸破坏乙酸甲酯-甲醇、乙酸甲酯-水的共沸组成，催化剂进料口和甲醇进料口之间为反应段，在这里，乙酸与甲醇在催化剂作用下生成乙酸甲酯和水，甲醇进料口以下是提馏段，甲醇从水中提馏出来。塔顶得到高纯度乙酸甲酯，塔釜排出水。Acetic acid is fed into the reactive distillation column from the acetic acid feed port in the upper part of the tower body, the catalyst is fed from the catalyst inlet in the middle of the tower body, and methanol is sent into the reactive distillation column from the methanol feed port in the lower part of the tower body. Section, where acetic acid and methyl acetate are separated, between the acetic acid feed inlet and the catalyst feed inlet is the extraction section, in this area, acetic acid destroys the azeotropic composition of methyl acetate-methanol and methyl acetate-water, and the catalyst Between the feed inlet and the methanol feed inlet is a reaction section, where acetic acid and methanol generate methyl acetate and water under the action of a catalyst, and below the methanol feed inlet is a stripping section, where methanol is extracted from water. High-purity methyl acetate is obtained at the top of the tower, and water is discharged from the tower kettle.
原料甲醇和乙酸的摩尔比为0.8∶1～1.4∶1，优选按1.0～1.3；The molar ratio of raw material methanol and acetic acid is 0.8:1～1.4:1, preferably 1.0～1.3;
所说的催化剂优选为硫酸，硫酸用量为甲醇和乙酸总进料量的0.3～1.2％，优选0.5～1.0％；Said catalyst is preferably sulfuric acid, and the sulfuric acid consumption is 0.3～1.2% of the total feed amount of methanol and acetic acid, preferably 0.5～1.0%;
回流比为1～2，塔底温度为88～90℃，塔顶温度为56.5～57.5℃；The reflux ratio is 1-2, the temperature at the bottom of the tower is 88-90°C, and the temperature at the top of the tower is 56.5-57.5°C;
塔底压力为表压0.05MPa，塔顶压力为常压；The pressure at the bottom of the tower is 0.05MPa gauge, and the pressure at the top of the tower is normal pressure;
反应段的塔板可以是10～60块，优选15～29块；The number of trays in the reaction section can be 10 to 60, preferably 15 to 29;
精馏段塔板可以是5～18块，优选8～14块；The number of trays in the rectifying section can be 5 to 18, preferably 8 to 14;
萃取段塔板可以是14～30块，优选14～24块；The number of trays in the extraction section can be 14 to 30, preferably 14 to 24;
采用本发明的具有立体传质塔板的反应精馏塔，塔板上的持液量明显提高，却没有明显的雾沫夹带，单塔的生成效率明显提高，塔顶醋酸甲酯含量产品纯度可达99.3％以上。Adopting the reactive distillation column with three-dimensional mass transfer trays of the present invention, the liquid holdup on the trays is significantly improved, but there is no obvious mist entrainment, the generation efficiency of the single tower is obviously improved, and the methyl acetate content at the top of the tower is higher than the product purity. It can reach more than 99.3%.
附图说明 Description of drawings
图1为立体传质塔板结构示意图。Figure 1 is a schematic diagram of the structure of a three-dimensional mass transfer tray.
图2为塔板的平面示意图。Figure 2 is a schematic plan view of the tray.
图3为反应精馏塔示意图。Figure 3 is a schematic diagram of a reactive distillation column.
具体实施方式 Detailed ways
参见图1，图2和图3，本发明的具有立体传质塔板的反应精馏塔，包括立式的塔体1、水平塔板9和设置在水平塔板9上的降液管7；Referring to Fig. 1, Fig. 2 and Fig. 3, the reactive distillation column with three-dimensional mass transfer tray of the present invention includes a
所说的水平塔板9上开有三排升气孔10，在升气孔10对应处装有喷射罩2，喷射罩2上开有喷射孔3，喷射罩2与水平塔板9之间有底隙8，在喷射罩2的顶部分别通过支承架11装有三层立体排布的分离板4、5和6，三层立体排布的分离板由平板组成，每一块分离板与喷射罩2的水平夹角为-45～45°，下面一层分离板和中间一层分离为开放型，上面一层分离板为封闭型，降液管7靠设置在水平塔板9上，近降液管7处设有出口堰12，其特征在于，出口堰高度∶间距＝0.2～0.5∶1，优选0.3～0.45∶1；塔板出口堰12的高度＝40mm～200mm，出口堰12的顶端为齿状，出口堰12为中间高两端低的拱形。Said horizontal tray 9 is provided with three rows of air-
实施例1～4Embodiment 1-4
采用如图1，图2和图3所示的反应精馏塔，甲醇和乙酸分别从下部和上部加入到反应精馏塔内，硫酸从中部加入反应精馏塔内。Adopt the reactive distillation column shown in Figure 1, Figure 2 and Figure 3, methanol and acetic acid are respectively added in the reactive distillation column from the bottom and the top, and sulfuric acid is added in the reactive distillation column from the middle.
出口堰为齿状结构，出口堰高度为200mm；The outlet weir is a toothed structure, and the height of the outlet weir is 200mm;
塔板间距为450mm；The tray spacing is 450mm;
反应段塔板数量为21块；The number of trays in the reaction section is 21;
精馏段塔板14块；14 trays in the rectification section;
萃取段塔板18块；There are 18 trays in the extraction section;
原料摩尔比：甲醇∶乙酸＝1.2；Raw material molar ratio: methanol: acetic acid=1.2;
硫酸加入量为甲醇和乙酸总进料重量的0.6％。采用不同的回流比，结果见下表The amount of sulfuric acid added was 0.6% of the total feed weight of methanol and acetic acid. Using different reflux ratios, the results are shown in the table below
实施例5Example 5
采用与实施例1～4相同的方法与装置，反应段塔板数量为29块，原料进料摩尔比：甲醇/乙酸＝1.0，回流比控制在1.1，塔顶得到的乙酸甲酯含量为99.5％。Using the same method and device as in Examples 1 to 4, the number of trays in the reaction section is 29, the molar ratio of raw material feed: methanol/acetic acid=1.0, the reflux ratio is controlled at 1.1, and the methyl acetate content obtained at the top of the tower is 99.5 %.
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| CN101328119B (en) * | 2008-06-20 | 2011-03-23 | 中国石油大学(华东) | A kind of synthetic process method and device of methyl acetate |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0060719A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| EP0060717A1 (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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| EP0060719A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| EP0060717A1 (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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