CN103121908B - Method for separating mesitylene via extractive distillation - Google Patents
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000895 extractive distillation Methods 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 65
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 238000000605 extraction Methods 0.000 claims abstract description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- SSUBAQORPAUJGD-UHFFFAOYSA-N 1-methylpyrrolidin-2-one;pyrrolidin-2-one Chemical compound O=C1CCCN1.CN1CCCC1=O SSUBAQORPAUJGD-UHFFFAOYSA-N 0.000 abstract 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 1
- PKKGGWLTUCMSSD-UHFFFAOYSA-N 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=C(N)C(C)=C(S(O)(=O)=O)C(C)=C1N PKKGGWLTUCMSSD-UHFFFAOYSA-N 0.000 description 1
- ZLCSFXXPPANWQY-UHFFFAOYSA-N 3-ethyltoluene Chemical compound CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- NXHPIYRSMIFFBV-UHFFFAOYSA-N formaldehyde;1,3,5-trimethylbenzene Chemical compound O=C.CC1=CC(C)=CC(C)=C1 NXHPIYRSMIFFBV-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种萃取精馏分离均三甲苯的方法，所述方法采用的萃取精馏溶剂为N-甲基-2-吡咯烷酮、2-吡咯烷酮中的一种，优选为N-甲基-2-吡咯烷酮。采用本发明所述的方法具有分离工艺相对简单、操作能耗低、产品收率高的优点。该方法采用的萃取精馏溶剂对均三甲苯与邻甲基乙苯之间的分离效率高，使分离过程可在塔板数较少的萃取精馏塔上实现，而且该溶剂易于回收、化学热稳定好。
The invention discloses a method for extracting and rectifying to separate mesitylene. The extracting and rectifying solvent used in the method is one of N-methyl-2-pyrrolidone and 2-pyrrolidone, preferably N-methyl-2-pyrrolidone 2-pyrrolidone. Adopting the method of the invention has the advantages of relatively simple separation process, low operation energy consumption and high product yield. The extraction and rectification solvent adopted in the method has high separation efficiency between mesitylene and o-methylethylbenzene, so that the separation process can be realized on an extractive distillation column with fewer plates, and the solvent is easy to recycle, chemically Good thermal stability.
Description
技术领域 technical field
本发明涉及化工领域，进一步地说，是涉及一种萃取精馏分离均三甲苯的方法。The invention relates to the field of chemical industry, and more particularly relates to a method for separating mesitylene by extraction and rectification.
背景技术 Background technique
均三甲苯是一种宝贵的精细化工原料，经硝化、加氢还原，生产均三甲苯胺，再与1，4二羟基蒽醌缩合、磺化，则生成弱酸性普拉艳兰RAW；另一种染料是均三甲苯经磺化、硝化、还原，制成2，4-二氨基-均三甲苯-6-磺酸，再与溴氨酸缩合成兰色基，然后与乙氧基二氯均三嗪反应，最后生成活性艳兰K-3R及RAN，用于印花和轧染；此外均三甲苯胺与α-氯代丙酸甲酯缩合，可制成麦田除草剂，配成20％溶液使用。此外，以均三甲苯为原料可制成抗氧剂330，均苯三甲酸，2，4，6-三甲酚等多种化工产品及化工中间体，也可以用于合成三甲苯甲醛树脂，它的用途广，附加值很高。炼油厂重整装置二甲苯塔底油中均三甲苯10％左右。目前我国这部分重整碳九资源一直未进一步开发利用，以长岭炼油厂为例，目前该厂年产均三甲苯约0.7万吨，若将其分离提纯，不仅可使石油资源得到合理利用，也可增加企业的经济效益。Mesitylene is a valuable fine chemical raw material. After nitration and hydrogenation reduction, mesitidine is produced, and then condensed and sulfonated with 1,4 dihydroxyanthraquinone to generate weakly acidic purayan blue RAW; The first kind of dye is mesitylene through sulfonation, nitration and reduction to make 2,4-diamino-mesitylene-6-sulfonic acid, and then condensed with bromic acid to form a blue base, and then reacted with ethoxy dichloro The reaction of s-triazine produces reactive brilliant blue K-3R and RAN, which are used for printing and padding; in addition, condensed s-trimethylaniline and α-methyl chloropropionate can be made into a wheat field herbicide and formulated as a 20% solution use. In addition, using mesitylene as raw material can be used to make antioxidant 330, trimesic acid, 2,4,6-tricresol and other chemical products and chemical intermediates, and can also be used to synthesize mesitylene formaldehyde resin. It has a wide range of uses and high added value. There are about 10% mesitylene in the bottom oil of the xylene tower in the reforming unit of the refinery. At present, this part of reformed carbon nine resources in my country has not been further developed and utilized. Taking Changling Oil Refinery as an example, the plant currently produces about 7,000 tons of mesitylene per year. If it is separated and purified, it will not only make rational use of oil resources , can also increase the economic benefits of the enterprise.
由于碳九芳烃混合物中各组分的沸点十分接近，特别是均三甲苯和邻甲基乙苯沸点仅差约0.5℃，相对挥发度为1.009，用普通精馏分离难度较大，若以普通精馏方法对其分离，需要上千块理论板，因此实际上是无法实现的。Since the boiling points of the components in the mixture of carbon and nine aromatic hydrocarbons are very close, especially the difference between the boiling points of mesitylene and o-methylethylbenzene is only about 0.5°C, and the relative volatility is 1.009, it is difficult to separate them by ordinary rectification. The separation by rectification requires thousands of theoretical plates, so it is actually impossible to achieve.
迄今为止，人们开发了许多制备均三甲苯的方法，主要有偏三甲苯异构化法、萃取精馏法、分子筛吸附分离法、络合/分离法、烷基化-分离法等多种工艺，以上工艺所采用的原料均来源于碳九芳烃馏分。据报道，在上述的方法中，萃取精馏法产品收率较高，溶剂重复使用，不产生废物，可以综合利用C9芳烃资源，且没有环保问题，和其它方法相比具有多方面的优势，具有很高的商业价值。萃取精馏法基本原理是借助选择性溶剂的作用，改变均三甲苯和邻甲乙苯之间的相对挥发度，从而达到提纯均三甲苯的目的。因此，萃取精馏溶剂对均三甲苯与邻甲基乙苯分离效率在分离过程的技术经济指标中起着关健的作用。So far, people have developed many methods for preparing mesitylene, mainly including the isomerization method of mesitylene, extractive distillation method, molecular sieve adsorption separation method, complexation/separation method, alkylation-separation method and other processes , The raw materials used in the above processes are all derived from the C9 aromatics fraction. According to reports, among the above-mentioned methods, the extraction and rectification method has a higher product yield, the solvent is reused, no waste is generated, and C 9 aromatics resources can be comprehensively utilized, and there is no environmental protection problem. Compared with other methods, it has many advantages , has high commercial value. The basic principle of extractive distillation method is to change the relative volatility between mesitylene and o-methylethylbenzene with the help of selective solvent, so as to achieve the purpose of purifying mesitylene. Therefore, the extraction and rectification solvent plays a key role in the separation efficiency of mesitylene and o-methylethylbenzene in the technical and economic indicators of the separation process.
美国专利US 3220933披露了以邻苯二甲酸二甲酯作为萃取溶剂，对C9芳烃进行萃取蒸馏，由于该溶剂对均三甲苯和邻甲乙苯的分离效果不佳，仅能得到87％的均三甲苯，远远低于98％(均三甲苯一级品的纯度)。国内南京师范大学对该方法进行了进一步的研究(萃取精馏制取均三甲苯的实验研究.化工时刊.2000，5：18～20.)，由实验结果可知，当回流比为4，溶剂与原料进料物质的质量比为10时，萃取精馏塔理论板数N为102块的条件下，塔顶馏出液中的均三甲苯物质的质量分数可达0.92以上，并对该过程进行了模拟计算，模拟计算表明，当以N＝170，同等条件下塔顶馏出液中的均三甲苯物质的质量分数才可达98％以上，采用邻苯二甲酸二甲酯作为萃取溶剂制备高纯度的均三甲苯所需萃取精馏塔板数目要求过高(N＝170)，溶剂/原料比例过大。U.S. Patent No. 3,220,933 discloses using dimethyl phthalate as an extraction solvent to carry out extractive distillation of C9 aromatics. Because the solvent has a poor separation effect on mesitylene and o-methylethylbenzene, only 87% of mesitylene can be obtained. Trimethylbenzene, far below 98% (the purity of the first-grade mesitylene). Domestic Nanjing Normal University has carried out further research on this method (Experimental research on producing mesitylene by extraction and rectification. Chemical Times. 2000, 5: 18-20.), it can be known from the experimental results that when the reflux ratio is 4, When the mass ratio of solvent and raw material feed material was 10, under the condition that the theoretical plate number N of the extractive distillation column was 102, the mass fraction of the mesitylene substance in the tower overhead liquid could reach more than 0.92, and the The process has been simulated and calculated, and the simulated calculation shows that when N=170, the mass fraction of mesitylene in the overhead distillate under the same conditions can reach more than 98%, and dimethyl phthalate is used as the extraction method. The number of extraction and rectification trays required for the preparation of high-purity mesitylene from the solvent is too high (N=170), and the solvent/raw material ratio is too large.
中国专利CN1958538A公开了一种双溶剂萃取分离碳九芳烃的方法，包括将碳九芳烃混合物进行预分馏，截取含均三甲苯和邻甲乙苯的富集馏分；将含均三甲苯和邻甲乙苯的富集馏分引入双溶剂萃取精馏塔的中部，高沸点溶剂从所述双溶剂萃取精馏塔上部注入，低沸点溶剂从所述双溶剂萃取精馏塔下部注入，在两种溶剂协同萃取作用下，塔顶得到含均三甲苯和低沸点溶剂的混合馏分，塔底得到含部邻甲乙苯和高沸点溶剂的混合馏分；将塔顶和塔釜所得的两股混合馏分分别在溶剂回收塔中进行分离，将分离得到的均三甲苯和邻甲基乙苯产品排出系统，两种溶剂回收后重复使用。由于又引入了一种溶剂，必须对该溶剂进行分离和再利用，因而需增加一个低沸点溶剂分离塔。有设备一次性投资和流程相对复杂的缺点。另外，由于低沸点溶剂和均三甲苯和从塔顶排出，导致分离过程能耗增加。Chinese patent CN1958538A discloses a method for separating C9 aromatics through dual-solvent extraction, including pre-fractionating the mixture of C9 aromatics, intercepting the enriched fraction containing mesitylene and o-methylethylbenzene; The enriched fraction is introduced into the middle part of the dual-solvent extraction and rectification tower, and the high-boiling point solvent is injected from the upper part of the dual-solvent extraction and rectification tower, and the low-boiling point solvent is injected from the lower part of the dual-solvent extraction and rectification tower. Under the action, the top of the tower obtains a mixed fraction containing mesitylene and low-boiling solvent, and the bottom of the tower obtains a mixed fraction containing o-toluene and high-boiling solvent; Separation is carried out in the tower, and the separated mesitylene and o-methylethylbenzene products are discharged from the system, and the two solvents are recovered and reused. Since another solvent is introduced, the solvent must be separated and reused, so a low-boiling-point solvent separation tower needs to be added. There are disadvantages of one-time equipment investment and relatively complicated process. In addition, due to the low boiling point solvent and mesitylene being discharged from the top of the tower, the energy consumption of the separation process increases.
中国专利CN1513818A报道了一种精馏于萃取交错结合分离C9的工艺，采用N-甲酰吗啉作为萃取精馏溶剂，塔顶馏出液中，均三甲苯的含量可达98.5％以上，由于该溶剂对均三甲苯与邻甲基乙苯的分离效率较低，萃取精馏塔理论板数N多达123块，均三甲苯收率仅为84％。因此，为解决现有技术中的问题，提供了一种萃取精馏分离均三甲苯的方法，具有分离操作相对简单、操作能耗低、产品收率高及投资较低的萃取精馏分离均三甲苯的方法是十分必要的。Chinese patent CN1513818A reports a process of rectification combined with extraction and separation of C 9 , using N-formylmorpholine as the solvent for extraction and rectification, and the content of mesitylene in the overhead distillate can reach more than 98.5%. Due to the low separation efficiency of mesitylene and o-methylethylbenzene by this solvent, the number of theoretical plates N of the extractive distillation tower is as high as 123, and the yield of mesitylene is only 84%. Therefore, in order to solve the problems in the prior art, a method for extractive distillation and separation of mesitylene is provided, which has the advantages of relatively simple separation operation, low operating energy consumption, high product yield and low investment. The trimethylbenzene method is very necessary.
发明内容 Contents of the invention
为解决现有技术中的问题，本发明提供了一种萃取精馏分离均三甲苯的方法，具有分离工艺相对简单、操作能耗低、产品收率高的优点，该方法利用的萃取精馏溶剂对均三甲苯和邻甲基乙苯之间的分离效率高，使其分离过程容易在塔板数较少的萃取精馏塔上实现，而且该溶剂易于回收、化学热稳定好。In order to solve the problems in the prior art, the present invention provides a method for separating mesitylene by extractive distillation, which has the advantages of relatively simple separation process, low operating energy consumption, and high product yield. The solvent has high separation efficiency between mesitylene and o-methylethylbenzene, which makes the separation process easy to realize on an extractive distillation column with a small number of plates, and the solvent is easy to recover and has good chemical and thermal stability.
本发明的目的是提供一种萃取精馏分离均三甲苯的方法。The purpose of this invention is to provide a kind of method of extractive distillation separation mesitylene.
所述方法采用的萃取精馏溶剂为N-甲基-2-吡咯烷酮、2-吡咯烷酮中的一种，优选为N-甲基-2-吡咯烷酮。The extraction and rectification solvent used in the method is one of N-methyl-2-pyrrolidone and 2-pyrrolidone, preferably N-methyl-2-pyrrolidone.
本发明人经过深入的研究，筛选了大量用于萃取精馏分离均三甲苯的萃取精馏溶剂，惊奇的发现，含氮类化合物N-甲基-2-吡咯烷酮、2-吡咯烷酮可以显著地改变均三甲苯和邻甲乙苯之间的相对挥发度，而且和含有无机盐的溶剂组合物相比，具有不堵塞管道，操作简单的优点。After in-depth research, the inventor screened a large number of extraction and rectification solvents used for extraction and rectification to separate mesitylene, and surprisingly found that nitrogen-containing compounds N-methyl-2-pyrrolidone and 2-pyrrolidone can significantly change The relative volatility between mesitylene and o-methylethylbenzene, and compared with solvent compositions containing inorganic salts, has the advantages of not blocking pipelines and simple operation.
所述方法包括：The methods include:
(1)将经脱除轻组分的碳九芳烃混合物引入偏三甲苯塔，塔顶排出含均三甲苯和甲基乙苯的富集馏分，塔釜引出含有均三甲苯的物流；(1) The C9 aromatics mixture through removal of light components is introduced into the mesitylene tower, the tower top discharges the enriched fraction containing mesitylene and methylethylbenzene, and the tower still draws the stream containing mesitylene;
(2)将偏三甲苯塔塔顶排出含均三甲苯和甲基乙苯的富集馏分从萃取精馏塔的中部引入，所述的萃取精馏溶剂从塔顶引入，经过萃取精馏后，均三甲苯从萃取精馏塔的顶部排出，塔底排出含有邻甲乙苯和溶剂的物流；(2) The enriched cut containing mesitylene and methylethylbenzene discharged from the top of the trimethylene tower is introduced from the middle part of the extractive distillation tower, and the described extractive distillation solvent is introduced from the top of the tower, after extractive distillation , mesitylene is discharged from the top of the extractive distillation tower, and the stream containing o-methylethylbenzene and solvent is discharged from the bottom of the tower;
(3)将萃取精馏塔塔底排出含有邻甲乙苯和溶剂的物流，引入溶剂回收塔，含有邻甲乙苯得物流从溶剂回收塔顶排出，萃取精馏溶剂从溶剂回收塔底排出后循环利用。(3) The stream containing o-methylethylbenzene and solvent is discharged from the bottom of the extractive distillation tower and introduced into the solvent recovery tower. The stream containing o-methylethylbenzene is discharged from the top of the solvent recovery tower, and the extractive distillation solvent is discharged from the bottom of the solvent recovery tower and then circulated use.
其中，以重量计，所述的萃取精馏溶剂用量为所述的均三甲苯和甲基乙苯的富集馏分进料量的0.5-12倍，优选3-8倍；Wherein, by weight, the amount of the extractive distillation solvent is 0.5-12 times, preferably 3-8 times, the feed amount of the enriched fraction of mesitylene and methylethylbenzene;
(1)步中的脱除轻组分的碳九芳烃混合物的轻组分是指沸点小于均三甲苯的组份，主要是异丙苯，正丙苯，间、对甲基乙苯。(1)步中的脱除碳九芳烃混合物中轻组分的方法可采用现有技术中的精密精馏或萃取精馏技术。(1) The light component of the carbon nine aromatics mixture of removing light component in the step refers to the component that boiling point is less than mesitylene, mainly cumene, n-propylbenzene, m- and p-methylethylbenzene. (1) The method for removing light components in the carbon-nine aromatic hydrocarbon mixture in the step can adopt precision rectification or extractive distillation technology in the prior art.
操作条件可采用本领域内通常的操作条件，本发明中可优选：Operating conditions can adopt common operating conditions in this area, preferably among the present invention:
所述的偏三甲苯塔的理论塔板数为60-100，塔顶回流比为10-20，塔顶温度为150-170℃，塔底温度为170-200℃，塔顶压力为0.08-0.12MPa，塔底压力为0.09-0.14MPa.The theoretical plate number of the partial trimethylbenzene tower is 60-100, the reflux ratio at the top of the tower is 10-20, the temperature at the top of the tower is 150-170°C, the temperature at the bottom of the tower is 170-200°C, and the pressure at the top of the tower is 0.08-200°C. 0.12MPa, the tower bottom pressure is 0.09-0.14MPa.
所述的萃取精馏塔的理论塔板数为70-120，塔顶回流比为2-5，塔顶温度为150-170℃，塔底温度为190-220℃，塔顶压力为0.08-0.12MPa，塔底压力为0.09-0.14MPa.The theoretical plate number of the extractive distillation tower is 70-120, the top reflux ratio is 2-5, the top temperature is 150-170°C, the bottom temperature is 190-220°C, and the top pressure is 0.08- 0.12MPa, the tower bottom pressure is 0.09-0.14MPa.
所述的回收塔的理论塔板数为10-20，塔顶的回流比为1-3，塔顶温度为155-170℃，塔底温度为190-230℃，塔顶压力为0.08-0.12MPa，塔底压力为0.09-0.14MPa.The theoretical plate number of the recovery tower is 10-20, the reflux ratio at the top of the tower is 1-3, the temperature at the top of the tower is 155-170°C, the temperature at the bottom of the tower is 190-230°C, and the pressure at the top of the tower is 0.08-0.12 MPa, the pressure at the bottom of the tower is 0.09-0.14MPa.
所述的碳九芳烃混合物可优选来自铂重整塔底油、二甲苯异构化副产、催化裂化油或裂解石脑油，其中均三甲苯的含量为8重量％-50重量％，邻甲基乙苯的含量为5重量％-50重量％，偏三甲苯的含量为8重量％-60重量％。不同来源的碳九芳烃组成稍有不同，可根据实际情况调节流程和操作手段。The said C9 aromatics mixture can preferably come from platinum reforming tower bottom oil, xylene isomerization by-product, catalytic cracking oil or cracked naphtha, wherein the content of mesitylene is 8% by weight-50% by weight, ortho The content of methylethylbenzene is 5% by weight to 50% by weight, and the content of mesitylene is 8% by weight to 60% by weight. The composition of C9 aromatic hydrocarbons from different sources is slightly different, and the process and operation methods can be adjusted according to the actual situation.
本发明的方法具有以下优点：溶剂对均三甲苯和邻甲基乙苯之间的分离效率高，The method of the present invention has the following advantages: the separation efficiency between the solvent p-mesitylene and o-methylethylbenzene is high,
1，由于该方法采用的溶剂对均三甲苯和邻甲基乙苯的分离效率高，不仅使均三甲苯的分离可在塔板数较少的萃取精馏塔上实现，而且还降低了萃取精馏溶剂用量(降低了溶剂/均三甲苯和甲基乙苯的富集馏分的质量比)，可达到投资较少，生产过程能耗较低的目的。1. Because the solvent used in this method has a high separation efficiency for mesitylene and o-methylethylbenzene, not only the separation of mesitylene can be realized on an extractive distillation column with fewer plates, but also the extraction efficiency is reduced. The rectification solvent consumption (reducing the mass ratio of solvent/mesitylene and methylethylbenzene enrichment fraction) can achieve the purpose of less investment and lower energy consumption in the production process.
2，采用本发明的方法，得到的均三甲苯收率有明显的提高，因此提高了从碳九芳烃中获取均三甲苯产品的经济效益。2. By adopting the method of the present invention, the yield of mesitylene obtained is significantly improved, thus improving the economic benefits of obtaining mesitylene products from C9 aromatics.
附图说明 Description of drawings
图1：本发明所述的萃取精馏分离均三甲苯流程示意图Fig. 1: Schematic flow chart of extraction and rectification separation of mesitylene according to the present invention
附图标记说明Explanation of reference signs
设备类：T1偏三甲苯塔，T2萃取精馏塔，T3溶剂回收塔Equipment category: T1 partial trimethylbenzene tower, T2 extractive distillation tower, T3 solvent recovery tower
物流类：1脱除轻组分的碳九芳烃混合物，2均三甲苯和甲基乙苯的富集馏分，3偏三甲苯，4均三甲苯，5邻甲乙苯和溶剂，6主要含有邻甲乙苯的物流，7循环溶剂Logistics category: 1. C9 aromatic hydrocarbon mixture with light components removed, 2. Mesitylene and methyl ethylbenzene enriched fraction, 3. Trimethylbenzene, 4. Mesitylene, 5. O-methylethylbenzene and solvent, 6. Mainly containing ortho-trimethylbenzene Methylbenzene stream, 7 cycle solvents
具体实施方式 Detailed ways
下面结合实施例，进一步说明本发明。Below in conjunction with embodiment, further illustrate the present invention.
实施例：Example:
如图1所示，经脱除轻组分的碳九芳烃混合物1进入偏三甲苯塔T1的中下部，塔顶排出含均三甲苯和部甲基乙苯的富集馏分2，塔釜引出主要含有均三甲苯的物流3；从T1塔顶流出的含均三甲苯和部甲基乙苯的富集馏分2进入萃取精馏塔T2的中下部，循环溶剂7由上部进入萃取精馏塔T2，经过萃取精馏分离，塔顶馏出均三甲苯4，塔底排出主要含有邻甲乙苯和溶剂的物流5；从T2塔釜排出的主要含有邻甲乙苯和溶剂的物流5被引入溶剂回收塔，主要含有邻甲乙苯的物流6从溶剂回收塔顶排出，萃取精馏溶剂7从溶剂回收塔底排出后循环利用。As shown in Figure 1, the C9 aromatic hydrocarbon mixture 1 after removing the light components enters the middle and lower part of the trimethylbenzene tower T1, and the enriched fraction 2 containing mesitylene and partial methyl ethylbenzene is discharged from the top of the tower, and the tower bottom is drawn The stream 3 mainly containing mesitylene; the enriched fraction 2 containing mesitylene and partial methylethylbenzene flowing out from the top of T1 enters the middle and lower part of the extractive distillation tower T2, and the circulating solvent 7 enters the extractive distillation tower from the upper part T2, after extraction and rectification separation, mesitylene 4 is distilled from the top of the tower, and the stream 5 mainly containing o-methylethylbenzene and solvent is discharged from the bottom of the tower; the stream 5 mainly containing o-methylethylbenzene and solvent discharged from the T2 tower kettle is introduced into the solvent In the recovery tower, the stream 6 mainly containing o-methylethylbenzene is discharged from the top of the solvent recovery tower, and the extractive distillation solvent 7 is discharged from the bottom of the solvent recovery tower for recycling.
所用的萃取精馏溶剂为N-甲基-2-吡咯烷酮；The extraction and rectification solvent used is N-methyl-2-pyrrolidone;
实施例中所用的原料是脱除轻组分的碳九芳烃混合物，其中含35.10重量％的均三甲苯，其具体组分及含量见表1。The raw material used in the embodiment is a mixture of carbon and nine aromatic hydrocarbons with light components removed, which contains 35.10% by weight of mesitylene, and its specific components and contents are shown in Table 1.
表1 脱除轻组分的碳九芳烃混合物组成及沸点Table 1 Composition and boiling point of the mixture of C and nine aromatics for light component removal
产品的收率是通过下式计算的：The yield of product is calculated by the following formula:
具体的分离工艺条件、各物流说明、产品的收率及纯度见见表2、表3，表4。See Table 2, Table 3, and Table 4 for specific separation process conditions, each logistics description, yield and purity of the product.
表2 实施例的分离工艺条件The separation process condition of table 2 embodiment
表3 实施例的各物流说明Each logistics description of table 3 embodiment
表4 实施例的各产品收率及纯度Each product yield and purity of table 4 embodiment
对比例：Comparative example:
所用的原料是脱除轻组分的碳九芳烃混合物，其中含35.10重量％的均三甲苯，其具体组分及含量见表1。The raw material used is a mixture of carbon and nine aromatic hydrocarbons with light components removed, which contains 35.10% by weight of mesitylene, and its specific components and contents are shown in Table 1.
萃取精馏溶剂采用中国专CN1513818A利披露的N-甲酰吗啉。按图1所述的从碳九芳烃中富集均三甲苯的方法进行实施，具体的分离工艺条件、各物流说明、产品的收率及纯度见表5、表6，表7.The extracting and rectifying solvent adopts N-formylmorpholine disclosed in Chinese patent CN1513818A. Carry out the method for enriching mesitylene from carbon nine aromatic hydrocarbons described in Fig. 1, concrete separation process condition, each logistics explanation, the yield and the purity of product are shown in Table 5, Table 6, Table 7.
表5 对比例的分离工艺条件Table 5 Separation process conditions of comparative examples
表6 对比例的各物流说明Table 6 The logistics description of the comparative example
表7 对比例的各产品收率及纯度Each product yield and purity of table 7 comparative example
从表2、5可知，由于采用分离效率较高的萃取精馏溶剂，溶剂/原料(重量流量比)从10降低到7，从而降低了能耗；另外，从表4、7可知，由于采用分离效率较高的萃取精馏溶剂，产品均三甲苯收率从82.3％提高到93.2％，因此提高了从碳九芳烃中获取均三甲苯产品的经济效益。As can be seen from Tables 2 and 5, due to the use of the higher extractive distillation solvent of separation efficiency, the solvent/raw material (weight flow ratio) is reduced from 10 to 7, thereby reducing energy consumption; in addition, it can be seen from Tables 4 and 7 that due to the use The extraction and rectification solvent with high separation efficiency increases the yield of mesitylene from 82.3% to 93.2%, thus improving the economic benefits of obtaining mesitylene from C9 aromatics.
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| CN104591952A (en) * | 2014-12-25 | 2015-05-06 | 天津大学 | Method for refining mesitylene by virtue of differential pressure thermal coupling rectification |
| CN105837394B (en) * | 2016-04-05 | 2018-12-21 | 天津大学 | A kind of method of purification of high-purity 1,2,3-trimethylbenzene |
| CN109627140A (en) * | 2017-10-09 | 2019-04-16 | 中国石化扬子石油化工有限公司 | A kind of mesitylene extraction and rectification separation method |
| WO2020091391A1 (en) * | 2018-11-01 | 2020-05-07 | 주식회사 엘지화학 | Method for separating organic solvent from organic solvent-containing mixed solution |
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| CN114213208B (en) * | 2021-12-31 | 2024-01-30 | 黄河三角洲京博化工研究院有限公司 | Method for extracting, rectifying and purifying mesitylene by high-efficiency composite solvent |
| CN114292155B (en) * | 2021-12-31 | 2024-05-03 | 黄河三角洲京博化工研究院有限公司 | Method for purifying mesitylene through thermal coupling |
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