CN107098810A - A kind of process for separation and purification for preparing electronic grade propylene glycol methyl ether acetate - Google Patents
A kind of process for separation and purification for preparing electronic grade propylene glycol methyl ether acetate Download PDFInfo
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 53
- 230000018044 dehydration Effects 0.000 claims abstract description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 238000012856 packing Methods 0.000 claims description 11
- 238000005191 phase separation Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
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- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 44
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- 239000012043 crude product Substances 0.000 abstract description 5
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- 238000006243 chemical reaction Methods 0.000 description 11
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- 238000010586 diagram Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YENIOYBTCIZCBJ-UHFFFAOYSA-N acetic acid;1-methoxypropan-2-ol Chemical compound CC(O)=O.COCC(C)O YENIOYBTCIZCBJ-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种制备电子级丙二醇甲醚醋酸酯的分离提纯方法。通过采用分离主塔附带侧线塔的精馏装置代替原有的双塔精馏装置，同时结合脱水塔的方式，对含有丙二醇甲醚，醋酸，水及少数重组分的粗产品丙二醇甲醚醋酸酯进行分离提纯，并通过离子交换树脂床对其中含有的金属离子如Fe3+，Na+，K+，Ca2+，Mg2+等进一步脱除，获得酸度小于80ppm，水含量小于200ppm，每种金属离子含量低于1ppb的电子级丙二醇甲醚醋酸酯产品，满足当下市场对电子化学品的质量要求。不降低产品质量的前提下，避免物料重复精馏，降低塔设备投资，减少产品蒸汽消耗，所用离子交换树脂通过再生重复使用，具有较好的经济效益和环境效益。
The invention relates to a separation and purification method for preparing electronic grade propylene glycol methyl ether acetate. By adopting the rectification device with the side line tower attached to the separation main tower to replace the original double-tower rectification device, combined with the dehydration tower, the crude product propylene glycol methyl ether acetate containing propylene glycol methyl ether, acetic acid, water and a few heavy components Carry out separation and purification, and further remove the metal ions contained therein such as Fe 3+ , Na + , K + , Ca 2+ , Mg 2+ etc. through an ion exchange resin bed to obtain an acidity of less than 80ppm and a water content of less than 200ppm. An electronic-grade propylene glycol methyl ether acetate product with a metal ion content of less than 1ppb, which meets the quality requirements of the current market for electronic chemicals. Under the premise of not reducing product quality, it avoids repeated rectification of materials, reduces tower equipment investment, and reduces product steam consumption. The ion exchange resin used is regenerated and reused, which has good economic and environmental benefits.
Description
技术领域technical field
本发明涉及一种制备电子级丙二醇甲醚醋酸酯的提纯方法，属于分离提纯领域。The invention relates to a purification method for preparing electronic-grade propylene glycol methyl ether acetate, which belongs to the field of separation and purification.
背景技术Background technique
电子级丙二醇甲醚醋酸酯是一类性能优良的精细化学品，由于其具有三个化学功能很强的溶解力因子(基团)—醚键、羟基和酯基，对极性和非极性的物质均有很强的溶解能力，素有“万能”溶剂之称，作为溶剂或有机原料被广泛用于涂料、油漆、印刷、燃料、皮革、感光材料、电子化学品、高级清洗剂、合成制动液和喷气燃料添加剂等工业领域。Electronic grade propylene glycol methyl ether acetate is a class of fine chemicals with excellent performance. Because it has three chemically powerful solvency factors (groups)—ether bond, hydroxyl group and ester group, it is compatible with polar and nonpolar All substances have strong dissolving power, known as "universal" solvents, as solvents or organic raw materials are widely used in coatings, paints, printing, fuels, leather, photosensitive materials, electronic chemicals, advanced cleaning agents, synthetic Industrial fields such as brake fluid and jet fuel additives.
作为一种常见的电子化学品，在现代集成电路(IC)行业和平板显示器(FDP)行业，电子级丙二醇甲醚醋酸酯主要用于光刻胶制备溶剂及光刻胶剥离剂组成，有时也用于集成电路的清洗剂。随着智能穿戴及面板领域快速发展，电子级丙二醇甲醚醋酸酯的需求量越来越大，产品质量要求也不断提高。电子级丙二醇甲醚醋酸酯的质量指标除了常规行业要求的沸程、折光率、酸度及水分含量外，还包括金属离子的含量。目前，一些电子产品生产厂家要求各种金属离子含量小于5ppb(μg/kg)，有的电子产品生产厂家提出了更高要求，要求每一种金属离子的含量小于1ppb，随着集成电路线宽越来越窄，对金属离子含量的要求也会更高。As a common electronic chemical, in the modern integrated circuit (IC) industry and flat panel display (FDP) industry, electronic grade propylene glycol methyl ether acetate is mainly used in the composition of photoresist preparation solvent and photoresist stripper, sometimes also Cleaning agent for integrated circuits. With the rapid development of smart wear and panel fields, the demand for electronic grade propylene glycol methyl ether acetate is increasing, and the product quality requirements are also continuously improving. The quality index of electronic grade propylene glycol methyl ether acetate includes the content of metal ions in addition to the boiling range, refractive index, acidity and moisture content required by conventional industries. At present, some electronic product manufacturers require the content of various metal ions to be less than 5ppb (μg/kg), and some electronic product manufacturers have put forward higher requirements, requiring the content of each metal ion to be less than 1ppb. Narrower and narrower, the requirements for metal ion content will be higher.
专利CN101993360A公开了一种电子级丙二醇甲醚醋酸酯的制备方法，该专利主要是采用强酸性阳离子交换树脂固体催化剂代替原来的有机酸均相催化剂，使得反应结束后不需要通过加碱中和除去残余酸催化剂，从而避免了反应生成物料中因为加入无机碱而引入金属离子，同时新催化体系催化剂与反应产物容易分离。在后续产品的分离过程中，首先向反应体系中加环己烷或甲苯作为水的夹带剂，通过共沸精馏从塔顶脱除产物中的水；脱水后物料进入下一级精馏处理，塔顶的轻馏分为未反应的醋酸和丙二醇甲醚，返回反应系统循环再利用，塔釜馏分为普通级丙二醇甲醚醋酸酯，再通过脱离子塔，塔顶为电子级产品丙二醇甲醚醋酸酯，塔釜为重组分以及要脱除的金属离子，通过该方法制得的电子级产品丙二醇甲醚醋酸酯中各种金属离子含量低于5ppb。Patent CN101993360A discloses a preparation method of electronic-grade propylene glycol methyl ether acetate. This patent mainly uses a strong acidic cation exchange resin solid catalyst to replace the original organic acid homogeneous catalyst, so that it does not need to be removed by neutralization after the reaction. Residual acid catalyst, thereby avoiding the introduction of metal ions in the reaction product due to the addition of inorganic bases, and the new catalyst system is easy to separate the catalyst from the reaction product. In the subsequent product separation process, cyclohexane or toluene is first added to the reaction system as an entrainer for water, and the water in the product is removed from the top of the tower through azeotropic distillation; after dehydration, the material enters the next stage of rectification treatment , the light distillate at the top of the tower is unreacted acetic acid and propylene glycol methyl ether, which is returned to the reaction system for recycling. Acetate, the tower still contains heavy components and metal ions to be removed, and the content of various metal ions in the electronic grade product propylene glycol methyl ether acetate prepared by this method is lower than 5ppb.
专利CN202519181 U公开了一种连续生产电子级丙二醇甲醚醋酸酯装置的实用新型专利，它的主要措施也是通过改变催化方式进行产品生产优化，把原有的均相催化剂改为为非均相复合固体酸催化剂，将釜式反应器改为两级固定床反应器，从反应器出来的酯化混合物料首先通过脱轻塔脱除混合物中的醋酸和丙二醇甲醚轻组分，塔釜采出粗的丙二醇甲醚醋酸酯进入脱离子塔，塔顶出料为电子级丙二醇甲醚醋酸酯，塔底出料为重组分残液。产品中各种金属含量均小于10ppb，该专利没有涉及反应混合物中水如何脱除。Patent CN202519181 U discloses a utility model patent for a device for continuous production of electronic grade propylene glycol methyl ether acetate. Its main measures are also to optimize product production by changing the catalytic method, changing the original homogeneous catalyst to heterogeneous composite Solid acid catalyst, change the tank reactor into a two-stage fixed bed reactor, the esterification mixture material coming out of the reactor firstly removes the acetic acid and propylene glycol methyl ether light components in the mixture through the delightening tower, and extracts from the tower The crude propylene glycol methyl ether acetate enters the deionization tower, the output from the top of the tower is electronic grade propylene glycol methyl ether acetate, and the output from the bottom of the tower is the heavy component raffinate. The content of various metals in the product is less than 10ppb, and the patent does not involve how to remove water from the reaction mixture.
从以上专利公开的内容可以发现，现有制备电子级丙二醇甲醚醋酸酯的专利实质内容大体类似，都是通过改变催化剂的形态来实现优化，将原本的均相反应改为液固非均相反应，这样催化剂与反应物料可以通过相态不同进行分离，避免了均相反应体系反应结束后，为了把液体酸催化剂从反应物料中脱除，加无机碱进行的中和反应过程。没有加无机碱的步骤，也就是说没有引入金属离子进入反应物料体系中，后续分离过程更容易得到金属离子含量十分低的电子级产品。脱除金属离子普遍采用精馏方式。From the content disclosed in the above patents, it can be found that the existing patents for the preparation of electronic grade propylene glycol methyl ether acetate are generally similar in essence, and are all optimized by changing the shape of the catalyst, changing the original homogeneous reaction to liquid-solid heterogeneous phase In this way, the catalyst and the reaction material can be separated by different phase states, avoiding the neutralization reaction process of adding an inorganic base to remove the liquid acid catalyst from the reaction material after the reaction of the homogeneous reaction system is completed. There is no step of adding an inorganic base, that is to say, no metal ions are introduced into the reaction material system, and it is easier to obtain electronic-grade products with very low metal ion content in the subsequent separation process. Removal of metal ions generally adopts rectification method.
现有专利对反应产物的后续分离过程，存在反应物料重复精馏，产品能耗高，产品纯度低的缺点，本发明提供了一种对丙二醇甲醚醋酸酯粗产品进行分离提纯的新方法，该方法通过主塔附带侧线塔的精馏方式代替原有的脱轻塔和脱重塔的双塔精馏方式去除产物中轻组分，精馏后产品进一步通过离子交换树脂床脱除产品中各种金属离子如Fe3+，Na+，K+，Ca2+，Mg2+，以达到电子级产品的要求。采用该方法对粗产品进行分离提纯，能够很好解决生产能耗高，产品纯度低的缺点，所得到产品中酸度(以醋酸计)小于80ppm，水含量小于200ppm，每种金属离子含量低于1ppb，满足了现有电子行业对丙二醇甲醚醋酸酯产品的质量要求。The subsequent separation process of the reaction product in the existing patent has the disadvantages of repeated rectification of the reaction material, high product energy consumption, and low product purity. The present invention provides a new method for separating and purifying the crude product of propylene glycol methyl ether acetate. In this method, the rectification method of the main tower with a side line tower replaces the original two-tower rectification method of the light removal tower and the weight removal tower to remove the light components in the product. After rectification, the product is further removed from the product through an ion exchange resin bed. Various metal ions such as Fe 3+ , Na + , K + , Ca 2+ , Mg 2+ , to meet the requirements of electronic grade products. Using this method to separate and purify the crude product can well solve the shortcomings of high production energy consumption and low product purity. The acidity (in terms of acetic acid) in the obtained product is less than 80ppm, the water content is less than 200ppm, and the content of each metal ion is less than 200ppm. 1ppb, which meets the quality requirements of the existing electronics industry for propylene glycol methyl ether acetate products.
发明内容Contents of the invention
本发明提供了一种电子级丙二醇甲醚醋酸酯的分离提纯方法。对于现有的丙二醇甲醚醋酸酯分离方法，其采用工艺装置主要采用脱轻塔和脱重塔的双塔精馏方式，整个流程重复精馏，蒸汽消耗量大，且不利于产品中金属离子浓度的降低。为了解决以上不足，获得更高质量的产品，将原有的精馏方式替换为分离主塔附带侧线塔的精馏方式，并将精馏后产品进一步通过离子交换树脂床脱除金属离子。该方法制得的丙二醇甲醚醋酸酯产品纯度高，达到电子化学品质量要求，其中酸度小于80ppm，水含量小于200ppm，每种金属离子含量低于1ppb。The invention provides a method for separating and purifying electronic grade propylene glycol methyl ether acetate. For the existing separation method of propylene glycol methyl ether acetate, the process device mainly adopts a double-tower rectification method of a light removal tower and a weight removal tower. The whole process repeats rectification, and the steam consumption is large, which is not conducive to the metal ions in the product. decrease in concentration. In order to solve the above deficiencies and obtain higher quality products, the original rectification method is replaced by the rectification method of the separation main tower with a side line tower, and the rectified product is further removed from metal ions through an ion exchange resin bed. The propylene glycol methyl ether acetate product prepared by the method has high purity and meets the quality requirements of electronic chemicals, wherein the acidity is less than 80 ppm, the water content is less than 200 ppm, and the content of each metal ion is less than 1 ppb.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种电子级丙二醇甲醚醋酸酯的分离提纯方法是：反应器出口含水、丙二醇甲醚和醋酸等轻组分的丙二醇甲醚醋酸酯混合物料从脱水塔中部进料，水在塔中通过夹带剂作用进行分离从塔顶采出，脱水后物料经塔釜采出通过循环泵打进丙二醇甲醚醋酸酯精馏主塔中部，轻重组分分离，未反应原料丙二醇甲醚、醋酸及微量水混合物从塔顶馏出返回反应器循环利用，夹带金属离子和重组分的气态混合物经连接管线进入精馏侧线塔底部，在塔中，丙二醇甲醚醋酸酯向上迁移，重组分协同金属离子通过传质分离返回主塔并塔釜排出，侧线塔塔顶采出丙二醇甲醚醋酸酯产品，后续进入离子交换树脂床进一步脱除金属离子，最终获得金属离子浓度十分低的电子级丙二醇甲醚醋酸酯产品。A separation and purification method of electronic grade propylene glycol methyl ether acetate is: the mixture of propylene glycol methyl ether acetate containing water, propylene glycol methyl ether and acetic acid and other light components at the outlet of the reactor is fed from the middle of the dehydration tower, and the water passes through the entrainment in the tower. The dehydrated material is extracted from the tower tank and sent to the middle part of the main column of propylene glycol methyl ether acetate rectification through a circulating pump, and the light and heavy components are separated. The unreacted raw materials propylene glycol methyl ether, acetic acid and trace water The mixture is distilled from the top of the tower and returned to the reactor for recycling. The gaseous mixture entrained with metal ions and heavy components enters the bottom of the rectification side line column through the connecting pipeline. In the tower, propylene glycol methyl ether acetate migrates upward, and the heavy components cooperate with metal ions to pass through The substance is separated and returned to the main tower and discharged from the tower kettle. The propylene glycol methyl ether acetate product is extracted from the top of the side line tower, and then enters the ion exchange resin bed to further remove metal ions, and finally obtains electronic grade propylene glycol methyl ether acetate with a very low metal ion concentration. product.
本发明来自反应器合成后丙二醇甲醚醋酸酯混合物料从脱水塔中部进入，采取常压操作。所述脱水塔的操作压力约为0.1MPa，塔顶温度为80-90℃，优选88℃，塔内回流比为1.5-3。The invention comes from the fact that the mixed material of propylene glycol methyl ether acetate enters from the middle of the dehydration tower after being synthesized in a reactor, and is operated under normal pressure. The operating pressure of the dehydration tower is about 0.1 MPa, the temperature at the top of the tower is 80-90°C, preferably 88°C, and the reflux ratio in the tower is 1.5-3.
本发明脱水后混合物料从丙二醇甲醚醋酸酯精馏主塔中部进入，采取加压操作。所述丙二醇甲醚醋酸酯精馏主塔的操作压力为0.12-0.2MPa，塔顶温度为130-160℃，主塔回流比为3-8。The mixed material after dehydration in the present invention enters from the middle part of the main column of propylene glycol methyl ether acetate rectification, and adopts pressurized operation. The operating pressure of the propylene glycol methyl ether acetate rectification main tower is 0.12-0.2 MPa, the tower top temperature is 130-160° C., and the reflux ratio of the main tower is 3-8.
本发明丙二醇甲醚醋酸酯和夹带的重组分一起通过主塔和侧线塔的连接管线进入侧线塔，采取加压操作。所述丙二醇甲醚醋酸酯精馏侧线塔的操作压力为0.1-0.18MPa，塔顶温度为130-170℃，塔内回流比为0.5-2。The propylene glycol methyl ether acetate of the present invention enters the side line tower through the connecting pipeline of the main tower and the side line tower together with entrained heavy components, and adopts pressurization operation. The operation pressure of the propylene glycol methyl ether acetate rectification side line column is 0.1-0.18MPa, the temperature at the top of the column is 130-170°C, and the reflux ratio in the column is 0.5-2.
所述脱水塔塔顶设置采出水相管线并连接废水槽，塔釜设置采出脱水后物料管线并连接丙二醇甲醚醋酸酯精馏主塔中部；丙二醇甲醚醋酸酯精馏主塔提馏段侧线引出气相连接管线连接丙二醇甲醚醋酸酯精馏侧线塔；精馏主塔塔顶设置采出轻组分混合物管线并返回反应器，塔釜设置采出重组分混合物管线并连接重组分槽；精馏侧线塔塔顶设置采出丙二醇甲醚醋酸酯粗产品管线并连接离子交换树脂床，塔釜设置液相连接管线使重组分返回主塔；离子交换树脂床底部设置采出丙二醇甲醚醋酸酯产品管线并连接产品罐。脱水塔塔顶设置冷凝器连接分相罐，夹带剂物料管线连接分相罐，夹带剂相层顶部设置萃取剂回流管线，水相层底部连接采出管线，塔釜设置再沸器，采用蒸汽加热；脱水后物料管线前端设置循环泵，将物料打入精馏主塔中部；精馏主塔塔顶设置冷凝器，轻组分混合物一部分流入采出管线，一部分通过回流管线返回塔顶，塔釜设置再沸器，加热方式同上；侧线塔塔顶设置冷凝器，丙二醇甲醚醋酸酯粗产品一部分流入采出管线，一部分通过回流管线返回塔顶；脱水塔、精馏主塔及侧线塔塔顶均采用冷却水冷却。The top of the dehydration tower is provided with a production water phase pipeline and is connected to a waste water tank, and the tower bottom is provided with a material pipeline after production and dehydration and is connected to the middle part of the main tower of propylene glycol methyl ether acetate rectification; the stripping section of the main tower of propylene glycol methyl ether acetate rectification The gas phase connection pipeline drawn from the side line is connected to the rectification side line tower of propylene glycol methyl ether acetate; the top of the rectification main tower is provided with a pipeline for extracting light component mixture and returning to the reactor, and the column tank is provided with a pipeline for producing heavy component mixture and connected to the heavy component tank; The top of the rectification side line column is equipped with a crude product pipeline of propylene glycol methyl ether acetate and connected to the ion exchange resin bed. Ester product line and connection to product tank. The top of the dehydration tower is equipped with a condenser connected to the phase separation tank, the material pipeline of the entrainer is connected to the phase separation tank, the top of the entrainer phase layer is equipped with an extraction agent return line, the bottom of the water phase layer is connected to the production pipeline, and a reboiler is installed in the tower kettle. Heating; after dehydration, a circulation pump is installed at the front end of the material pipeline to drive the material into the middle of the rectification main tower; a condenser is installed on the top of the rectification main tower, part of the light component mixture flows into the production pipeline, and part returns to the top of the tower through the return pipeline, and the tower A reboiler is installed in the kettle, and the heating method is the same as above; a condenser is installed at the top of the side line tower, part of the crude product of propylene glycol methyl ether acetate flows into the production pipeline, and part of it returns to the top of the tower through the return line; the dehydration tower, the rectification main tower and the side line tower The roof is cooled by cooling water.
所述夹带剂为甲苯，在脱水塔中，甲苯与水形成最低温度共沸物，经塔顶采出进入分相罐进行分相，上层甲苯相返回脱水塔，下层水相由底部采出。The entraining agent is toluene. In the dehydration tower, toluene and water form an azeotrope at the lowest temperature, which is extracted from the top of the tower and enters a phase separation tank for phase separation. The upper toluene phase is returned to the dehydration tower, and the lower water phase is extracted from the bottom.
所述脱水塔、丙二醇甲醚醋酸酯精馏主塔和侧线塔采用板式塔或填料塔，优选填料塔。若脱水塔、精馏主塔与侧线塔均采用板式塔，塔板采用浮阀或筛孔塔板，降液区设置溢流堰和降液管；若脱水塔、精馏主塔与侧线塔均采用填料塔，填料采用规整填料，如塑料规整填料，陶瓷规整填料或碳纤维规整填料，优选型号为125Y-700X的陶瓷波纹规整填料。The dehydration tower, the propylene glycol methyl ether acetate rectification main tower and the side line tower adopt a plate tower or a packed tower, preferably a packed tower. If the dehydration tower, rectification main tower and side line tower all adopt tray tower, the tray adopts float valve or sieve tray, and the downcomer area is equipped with overflow weir and downcomer; if the dehydration tower, rectification main tower and side line tower All adopt packed towers, and the packing adopts structured packing, such as plastic structured packing, ceramic structured packing or carbon fiber structured packing, preferably the ceramic corrugated structured packing of model 125Y-700X.
所述侧线塔为仅有精馏段的提纯塔。The side line column is a purification column with only a rectification section.
所述离子交换树脂床中，选用选用强酸型阳离子交换树脂，优选型号为D001-CC的大孔强酸性苯乙烯系阳离子交换树脂，由于其表面空隙多，表面积大，使用时，所需处理时间短，效率高；同时，其结构牢固，反复转型膨胀率低，在有机溶液中具有很好的交换吸附性能。In the ion-exchange resin bed, strong-acid cation-exchange resins are selected for use, and the preferred model is the macroporous strongly acidic styrene-based cation-exchange resin of D001-CC. Short, high efficiency; at the same time, its structure is firm, the expansion rate of repeated transformation is low, and it has good exchange adsorption performance in organic solution.
所述丙二醇甲醚醋酸酯精馏主塔，其侧线塔及产品贮罐的材料选用不锈钢内衬全氟烷氧基树脂(PFA塑料)，可以避免在精馏提纯及存储过程发生二次金属离子污染。The main tower of the propylene glycol methyl ether acetate rectification, the material of its side line tower and the product storage tank is made of stainless steel lining perfluoroalkoxy resin (PFA plastics), which can avoid the occurrence of secondary metal ions in the process of rectification, purification and storage. pollute.
本发明一种电子级丙二醇甲醚醋酸酯的分离提纯方法，其优点为通过采用精馏主塔并在提馏段增加仅有精馏段侧线塔的新装置替代原有的脱轻塔和脱重塔双塔精馏装置，同时结合脱水塔及离子交换树脂床的方式，在不降低产品质量的前提下，避免物料重复精馏，降低塔设备投资，减少产品蒸汽消耗。另外，通过该方法，分离物料得到有效再利用，降低排放污水处理成本，并获得酸度(以醋酸计)小于80ppm，水含量小于200ppm，每种金属离子含量低于1ppb的电子级丙二醇甲醚醋酸酯产品，该方法降低塔设备投资，减少产品蒸汽消耗，所用离子交换树脂可以通过再生重复使用，节约能源，具有较好的经济效益和环境效益。The separation and purification method of a kind of electronic grade propylene glycol methyl ether acetate of the present invention, its advantage is that by adopting rectification main tower and increasing the new device that only rectification section side line tower replaces original delightening tower and de-lightening tower in stripping section The double-tower rectification device with heavy towers, combined with the dehydration tower and ion exchange resin bed, avoids repeated rectification of materials, reduces tower equipment investment, and reduces product steam consumption without reducing product quality. In addition, through this method, the separated materials can be effectively reused, the cost of sewage treatment can be reduced, and electronic grade propylene glycol methyl ether acetic acid with acidity (calculated as acetic acid) less than 80ppm, water content less than 200ppm, and each metal ion content less than 1ppb can be obtained. Ester products, this method reduces tower equipment investment, reduces product steam consumption, the ion exchange resin used can be reused through regeneration, saves energy, and has good economic and environmental benefits.
附图说明Description of drawings
图1为本发明的工艺流程图。Fig. 1 is a process flow diagram of the present invention.
图1表示说明：Figure 1 shows the description:
图中包括的设备有T-1脱水塔，T-2丙二醇甲醚醋酸酯精馏主塔，TS-2丙二醇甲醚醋酸酯精馏侧线塔，CC离子交换树脂床，E-1脱水塔冷凝器，E-2脱水塔再沸器，E-3丙二醇甲醚醋酸酯精馏主塔冷凝器，E-4丙二醇甲醚醋酸酯精馏主塔再沸器，E-5丙二醇甲醚醋酸酯精馏侧线塔冷凝器，P-1循环泵，V-1脱水塔分相罐，V-2废水槽，V-3重组分槽，V-4电子级丙二醇甲醚醋酸酯产品罐。The equipment included in the picture includes T-1 dehydration tower, T-2 propylene glycol methyl ether acetate rectification main tower, TS-2 propylene glycol methyl ether acetate rectification side column, CC ion exchange resin bed, E-1 dehydration tower condensing E-2 dehydration tower reboiler, E-3 propylene glycol methyl ether acetate rectification main column condenser, E-4 propylene glycol methyl ether acetate rectification main column reboiler, E-5 propylene glycol methyl ether acetate Rectification side column condenser, P-1 circulation pump, V-1 dehydration tower phase separation tank, V-2 waste water tank, V-3 heavy component tank, V-4 electronic grade propylene glycol methyl ether acetate product tank.
图中还包括如下管线：1-脱水塔进料管线，2-夹带剂甲苯进料管线 3-脱水塔萃取剂回流管线，4-脱水塔水出料管线，5-脱水塔塔釜出料连接管线，6-丙二醇甲醚醋酸酯精馏主塔回流管线，7-丙二醇甲醚醋酸酯精馏主塔塔顶轻组分采出管线，8-丙二醇甲醚醋酸酯精馏塔塔釜重组分采出管线，9-精馏主塔与侧线塔的气相连接管线，10-精馏主塔与侧线塔的液相连接管线，11-侧线塔回流管线，12-侧线塔塔顶产品采出管线，13-电子级丙二醇甲醚醋酸酯的产品管线。The figure also includes the following pipelines: 1-dehydration tower feed pipeline, 2-entrainer toluene feed pipeline 3-dehydration tower extractant return pipeline, 4-dehydration tower water discharge pipeline, 5-dehydration tower kettle discharge connection Pipeline, 6-propylene glycol methyl ether acetate rectification main tower reflux pipeline, 7-propylene glycol methyl ether acetate rectification main tower top light component extraction pipeline, 8-propylene glycol methyl ether acetate rectification tower tank heavy component Production pipeline, 9- gas phase connection pipeline between rectification main tower and side tower, 10- liquid phase connection pipeline between rectification main tower and side tower, 11- side tower return pipeline, 12- side tower top product extraction pipeline , 13-Product pipeline of electronic grade propylene glycol methyl ether acetate.
具体实施方式detailed description
附图1工艺体现了本发明的优点，但是本发明不限于附图1的工艺，本领域的技术人员可以设计出在本发明理念的技术范围内的各种修改和变动，应该说明的是，这些修改和变动也落在本发明的保护范围内。以下借助图1工艺流程图的辅助，说明本发明的内容、特色，以便本发明能被进一步理解。Accompanying drawing 1 technique embodies advantage of the present invention, but the present invention is not limited to the technique of accompanying drawing 1, those skilled in the art can devise various modifications and variations within the technical scope of the concept of the present invention, it should be noted that, These modifications and variations also fall within the protection scope of the present invention. With the aid of the process flow diagram in Fig. 1, the content and characteristics of the present invention will be described below, so that the present invention can be further understood.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
采用附图1所示的连续分离提纯电子级丙二醇甲醚醋酸酯的方法，主要包括：脱水塔、丙二醇甲醚醋酸酯精馏主塔、丙二醇甲醚醋酸酯精馏侧线塔、泵、以及连接设备之间的管线，脱水塔和精馏主塔塔顶设置冷凝器，塔釜设置再沸器，侧线塔塔顶设置冷凝器，塔釜与主塔相连。Adopt the method for the continuous separation and purification of electronic grade propylene glycol methyl ether acetate shown in accompanying drawing 1, mainly comprise: dehydration tower, propylene glycol methyl ether acetate rectification main column, propylene glycol methyl ether acetate rectification side line tower, pump and connection The pipelines between the equipment, the dehydration tower and the rectification main tower are equipped with a condenser at the top of the tower, a reboiler is installed at the bottom of the tower, and a condenser is installed at the top of the side line column, and the bottom of the tower is connected with the main tower.
来自合成反应器的混合物通过进料管线1从脱水塔T-1中部进料采取常压操作，从塔顶通过管线2引入夹带剂甲苯与塔中水形成最低温度共沸物，经塔顶馏出，通过冷凝器E-1冷凝后流入分相罐V-1进行分相，上层甲苯相作为夹带剂通过回流管线3返回脱水塔T-1，下层水相通过物料管线4流入废水罐V-2作进一步处理。脱水后物料通过管线5从塔釜排出由循环泵P-1打入丙二醇甲醚醋酸酯精馏主塔T-2中部采取加压操作，在塔中轻组分向上迁移，主塔塔顶采出未反应原料丙二醇甲醚、醋酸及微量水混合物，经冷凝器E-3冷凝后分为两部分，一部分通过回流管线6返回主塔塔顶，一部分通过管线7返回反应系统循环利用，重组分通过管线8从塔釜排出流入重组分残液槽V-3。从精馏主塔提馏段侧线引出夹带金属离子和重组分的气态物料通过气相连接管线9进入精馏侧线塔TS-2底部采取加压操作。在侧线塔中，丙二醇甲醚醋酸酯进一步提纯，经过传质分离夹带金属离子的重组分通过侧线塔塔釜液相连接管线10返回精馏分离主塔并从塔釜排除，侧线塔顶部采出丙二醇甲醚醋酸酯，经冷凝器E-5冷凝后，也分为两部分，一部分通过回流管线11返回侧线塔顶部，一部分作为产品通过管线12然后进入后续的离子交换树脂床CC进一步脱除金属离子，最终电子级丙二醇甲醚醋酸酯产品通过产品管线13流入产品罐V-4。The mixture from the synthesis reactor is fed from the middle of the dehydration tower T-1 through the feed line 1 to adopt normal pressure operation, and the entrainer toluene is introduced from the top of the tower through the line 2 to form the lowest temperature azeotrope with the water in the tower, and is distilled at the top of the tower. After being condensed by the condenser E-1, it flows into the phase separation tank V-1 for phase separation. The upper toluene phase is used as an entrainer and returns to the dehydration tower T-1 through the return line 3, and the lower water phase flows into the waste water tank V- through the material line 4. 2 for further processing. After dehydration, the material is discharged from the tower kettle through the pipeline 5, and is pumped into the middle part of the propylene glycol methyl ether acetate rectification main tower T-2 by the circulation pump P-1 to adopt a pressurized operation, and the light components in the tower migrate upwards, and the top of the main tower is extracted The unreacted raw material propylene glycol methyl ether, acetic acid and trace water mixture is condensed by the condenser E-3 and divided into two parts, one part is returned to the top of the main tower through the reflux line 6, and the other part is returned to the reaction system for recycling through the line 7, and the heavy component It is discharged from the tower kettle through the pipeline 8 and flows into the heavy component raffinate tank V-3. The gaseous material entrained with metal ions and heavy components drawn from the side line of the stripping section of the rectification main column enters the bottom of the rectification side line column TS-2 through the gas phase connection line 9 for pressurization. In the side line tower, the propylene glycol methyl ether acetate is further purified, and the heavy components entrained with metal ions after mass transfer separation are returned to the rectification and separation main tower through the liquid phase connection line 10 of the side line tower and the bottom of the tower, and are discharged from the bottom of the side line tower. Propylene glycol methyl ether acetate, after being condensed by the condenser E-5, is also divided into two parts, one part returns to the top of the side line tower through the reflux line 11, and one part passes through the line 12 as a product and then enters the subsequent ion exchange resin bed CC to further remove metals The ionic, final electronic grade propylene glycol methyl ether acetate product flows through product line 13 into product tank V-4.
分离提纯制备电子级丙二醇甲醚醋酸酯的方法中：脱水塔的塔顶采用常压，压力值约为0.1MPa，塔顶温度为80-90℃，优选88℃，脱水塔回流比为1.5-3；丙二醇甲醚醋酸酯精馏分离主塔的塔顶压力为0.12-0.2MPa，塔顶温度为130-160℃，主塔回流比为3-8；丙二醇甲醚醋酸酯侧线塔的塔顶压力为0.1-0.18MPa，塔顶温度为130-170℃，侧线塔回流比为0.5-2。In the method of separating and purifying to prepare electronic grade propylene glycol methyl ether acetate: the top of the dehydration tower adopts normal pressure, the pressure value is about 0.1MPa, the temperature at the top of the tower is 80-90°C, preferably 88°C, and the reflux ratio of the dehydration tower is 1.5- 3. The pressure at the top of the main column of propylene glycol methyl ether acetate rectification and separation is 0.12-0.2MPa, the temperature at the top of the tower is 130-160°C, and the reflux ratio of the main tower is 3-8; the top of the side line tower of propylene glycol methyl ether acetate The pressure is 0.1-0.18MPa, the temperature at the top of the tower is 130-170°C, and the reflux ratio of the side column is 0.5-2.
以下根据实施例更进一步具体说明本发明Further specify the present invention according to the following examples
实施例1Example 1
从丙二醇甲醚醋酸酯合成反应器出来的物料组成如表1中数据所示，The composition of the material coming out from the propylene glycol methyl ether acetate synthesis reactor is as shown in the data in table 1,
表1丙二醇甲醚醋酸酯合成反应器出口物料组分Table 1 propylene glycol methyl ether acetate synthesis reactor outlet material components
利用附图1所示的工艺流程图进行丙二醇甲醚醋酸酯的分离提纯，本实施例中，脱水塔、丙二醇甲醚醋酸酯精馏主塔及侧线塔均采用填料塔，其中脱水塔的塔顶压力为0.1MPa，脱水塔的回流比为1.5，脱水塔的塔顶温度为88℃，丙二醇甲醚醋酸酯精馏分离主塔的塔顶压力为0.12MPa，对应的塔顶温度为134℃，主塔的回流比为6，丙二醇甲醚醋酸酯侧线塔的塔顶压力为0.18MPa，侧线塔的塔顶温度为149℃，侧线塔的回流比为1.0。最终得到丙二醇甲醚醋酸酯产品中酸度(以醋酸计)小于80ppm，水含量小于200ppm，每一种金属离子含量低于1ppb。Utilize the process flow diagram shown in accompanying drawing 1 to carry out the separation and purification of propylene glycol methyl ether acetate, in the present embodiment, dehydration tower, propylene glycol methyl ether acetate rectification main tower and side line tower all adopt packing tower, wherein the tower of dehydration tower The top pressure is 0.1MPa, the reflux ratio of the dehydration tower is 1.5, the top temperature of the dehydration tower is 88°C, the top pressure of the propylene glycol methyl ether acetate distillation and separation main tower is 0.12MPa, and the corresponding top temperature is 134°C , the reflux ratio of the main tower is 6, the overhead pressure of the propylene glycol methyl ether acetate side tower is 0.18MPa, the tower top temperature of the side tower is 149°C, and the reflux ratio of the side tower is 1.0. In the finally obtained propylene glycol methyl ether acetate product, the acidity (in terms of acetic acid) is less than 80 ppm, the water content is less than 200 ppm, and the content of each metal ion is less than 1 ppb.
实施例2Example 2
进料组成同实施例1，利用附图1所示的工艺流程图进行丙二醇甲醚醋酸酯的分离提纯，本实施例中，脱水塔、丙二醇甲醚醋酸酯精馏主塔及侧线塔均采用填料塔，其中脱水塔的塔顶压力为0.1MPa，脱水塔的回流比为3，脱水塔的塔顶温度为90℃，丙二醇甲醚醋酸酯精馏分离主塔的塔顶压力为0.2MPa，对应的塔顶温度为152℃，主塔的回流比为8，丙二醇甲醚醋酸酯侧线塔的塔顶压力为0.18MPa，侧线塔的塔顶温度为167℃，侧线塔的回流比为2。最终得到丙二醇甲醚醋酸酯产品中酸度(以醋酸计)小于300ppm，水含量小于180ppm，每一种金属离子含量低于1ppb。Feed composition is the same as embodiment 1, utilizes the process flow sheet shown in accompanying drawing 1 to carry out the separation and purification of propylene glycol methyl ether acetate, in the present embodiment, dehydration tower, propylene glycol methyl ether acetate rectification main tower and side line tower all adopt Packed tower, wherein the top pressure of the dehydration tower is 0.1MPa, the reflux ratio of the dehydration tower is 3, the top temperature of the dehydration tower is 90°C, and the top pressure of the main tower of propylene glycol methyl ether acetate distillation and separation is 0.2MPa, The corresponding tower top temperature is 152°C, the reflux ratio of the main tower is 8, the top pressure of the propylene glycol methyl ether acetate side line tower is 0.18MPa, the tower top temperature of the side line tower is 167°C, and the reflux ratio of the side line tower is 2. In the finally obtained propylene glycol methyl ether acetate product, the acidity (in terms of acetic acid) is less than 300ppm, the water content is less than 180ppm, and the content of each metal ion is less than 1ppb.
实施例3Example 3
进料组成同实施例1，利用附图1所示的工艺流程图进行丙二醇甲醚醋酸酯的分离提纯，本实施例中，脱水塔、丙二醇甲醚醋酸酯精馏主塔及侧线塔均采用填料塔，其中脱水塔的塔顶压力为0.1MPa，脱水塔的回流比为2，脱水塔的塔顶温度为80℃，丙二醇甲醚醋酸酯精馏分离主塔的塔顶压力为0.12MPa，对应的塔顶温度为146℃，主塔的回流比为3，丙二醇甲醚醋酸酯侧线塔的塔顶压力为0.10MPa，侧线塔的塔顶温度为134℃，侧线塔的回流比为0.5。最终得到丙二醇甲醚醋酸酯产品中酸度(以醋酸计)小于150ppm，水含量小于270ppm，每一种金属离子含量低于1ppb。Feed composition is the same as embodiment 1, utilizes the process flow sheet shown in accompanying drawing 1 to carry out the separation and purification of propylene glycol methyl ether acetate, in the present embodiment, dehydration tower, propylene glycol methyl ether acetate rectification main tower and side line tower all adopt Packed tower, wherein the top pressure of the dehydration tower is 0.1MPa, the reflux ratio of the dehydration tower is 2, the top temperature of the dehydration tower is 80°C, and the top pressure of the main tower of propylene glycol methyl ether acetate rectification separation is 0.12MPa, The corresponding tower top temperature is 146°C, the reflux ratio of the main tower is 3, the top pressure of the propylene glycol methyl ether acetate side line tower is 0.10MPa, the tower top temperature of the side line tower is 134°C, and the reflux ratio of the side line tower is 0.5. In the finally obtained propylene glycol methyl ether acetate product, the acidity (in terms of acetic acid) is less than 150 ppm, the water content is less than 270 ppm, and the content of each metal ion is less than 1 ppb.
综上所述，本发明提出的一种电子级丙二醇甲醚醋酸酯的分离提纯方法，已通过上述优选实施例进行具体描述，但应当认识到上述描述不应被认为是对本发明的限制。需要特别说明的是，本领域技术人员对于本发明所有相类似的替换和改动都是显而易见的。因此，本发明的保护范围应由所附的权利要求限定。In summary, a method for separation and purification of electronic grade propylene glycol methyl ether acetate proposed by the present invention has been specifically described through the above preferred embodiments, but it should be recognized that the above description should not be considered as a limitation of the present invention. It should be noted that all similar substitutions and modifications of the present invention will be apparent to those skilled in the art. Therefore, the protection scope of the present invention should be defined by the appended claims.
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