KR100501304B1 - Energy Efficient fractional distillation method and device of benzene, toluene and xylene from an effluent mixture of naphtha reforming process - Google Patents
Energy Efficient fractional distillation method and device of benzene, toluene and xylene from an effluent mixture of naphtha reforming process Download PDFInfo
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- KR100501304B1 KR100501304B1 KR10-2003-0023312A KR20030023312A KR100501304B1 KR 100501304 B1 KR100501304 B1 KR 100501304B1 KR 20030023312 A KR20030023312 A KR 20030023312A KR 100501304 B1 KR100501304 B1 KR 100501304B1
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 58
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000008096 xylene Substances 0.000 title claims abstract description 22
- 238000004508 fractional distillation Methods 0.000 title claims abstract description 19
- 238000002407 reforming Methods 0.000 title claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 81
- 238000009835 boiling Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 15
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000295 fuel oil Substances 0.000 abstract description 2
- 239000000306 component Substances 0.000 abstract 2
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- 239000013067 intermediate product Substances 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 1
- YQZBFMJOASEONC-UHFFFAOYSA-N 1-Methyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C YQZBFMJOASEONC-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47B—TABLES; DESKS; OFFICE FURNITURE; CABINETS; DRAWERS; GENERAL DETAILS OF FURNITURE
- A47B63/00—Cabinets, racks or shelf units, specially adapted for storing books, documents, forms, or the like
- A47B63/06—Cabinets, racks or shelf units, specially adapted for storing books, documents, forms, or the like with parts, e.g. trays, card containers, movable on pivots or on chains or belts
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47D—FURNITURE SPECIALLY ADAPTED FOR CHILDREN
- A47D3/00—Children's tables
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09B—EDUCATIONAL OR DEMONSTRATION APPLIANCES; APPLIANCES FOR TEACHING, OR COMMUNICATING WITH, THE BLIND, DEAF OR MUTE; MODELS; PLANETARIA; GLOBES; MAPS; DIAGRAMS
- G09B1/00—Manually or mechanically operated educational appliances using elements forming, or bearing, symbols, signs, pictures, or the like which are arranged or adapted to be arranged in one or more particular ways
- G09B1/02—Manually or mechanically operated educational appliances using elements forming, or bearing, symbols, signs, pictures, or the like which are arranged or adapted to be arranged in one or more particular ways and having a support carrying or adapted to carry the elements
- G09B1/04—Manually or mechanically operated educational appliances using elements forming, or bearing, symbols, signs, pictures, or the like which are arranged or adapted to be arranged in one or more particular ways and having a support carrying or adapted to carry the elements the elements each bearing a single symbol or a single combination of symbols
- G09B1/06—Manually or mechanically operated educational appliances using elements forming, or bearing, symbols, signs, pictures, or the like which are arranged or adapted to be arranged in one or more particular ways and having a support carrying or adapted to carry the elements the elements each bearing a single symbol or a single combination of symbols and being attachable to, or mounted on, the support
- G09B1/10—Manually or mechanically operated educational appliances using elements forming, or bearing, symbols, signs, pictures, or the like which are arranged or adapted to be arranged in one or more particular ways and having a support carrying or adapted to carry the elements the elements each bearing a single symbol or a single combination of symbols and being attachable to, or mounted on, the support by means of pins and holes
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- Business, Economics & Management (AREA)
- Physics & Mathematics (AREA)
- Educational Administration (AREA)
- Educational Technology (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 나프타 개질 공정에서 나오는 방향족 화합물을 성분별로 분리하는데 사용하는 증류 조작용 장치를 에너지 절감형으로 개선한 증류방법 및 장치에 관한 것으로, 본 발명의 분별 증류 방법 및 장치는 다성분 평형 증류 곡선에 맞는 분별 증류 방식인 확장형 열복합 증류탑을 사용하여 달성하는데, 이러한 증류탑은 석유 정유 공정, 나프타 개질반응 공정, 중질유 분해 공정들에서 얻은 여러 가지 혼합물에서 고비점 성분인 벤젠, 톨루엔, 자일렌을 분별 증류 공정에서 사용에너지를 현저히 감소하면서 분별 증류가 가능하게 한다.The present invention relates to a distillation method and apparatus for improving energy-saving distillation operation apparatus used to separate the aromatic compounds from the naphtha reforming step by component, the fractional distillation method and apparatus of the present invention is a multicomponent equilibrium distillation curve This is accomplished by using an extended thermal combined distillation column, a fractional distillation method suitable for the separation of high-boiling components, benzene, toluene and xylene, from various mixtures obtained from petroleum refinery, naphtha reforming and heavy oil cracking processes. Fractional distillation is possible while significantly reducing the energy used in the distillation process.
상기와 같이 구성되는 본 발명에 따른 확장형 열복합 증류방식은 탑 효율이 높기 때문에 확장형 열복합형 증류탑을 이용하여 분리조작을 하면 에너지 사용량을 절감할 수 있고 증류탑의 재비기와 냉각기로 사용하는 열교환기의 용량을 줄일 수 있어 열교환기의 설비비를 줄일 수 있다.Since the expansion type thermal combined distillation method according to the present invention configured as described above has a high tower efficiency, the separation operation using the expansion type thermal combined distillation column can reduce the energy consumption, and the heat exchanger used as the reboiler and cooler of the distillation column. The capacity can be reduced, reducing the equipment cost of the heat exchanger.
Description
본 발명은 확장형 열복합 증류식 분별증류 장치의 설계에 관한 것으로, 보다 자세하게는 석유정제 및 석유화학 공정에서 얻어진 방향족 혼합물로부터 성분별로 분리하는데 사용하는 증류조작용 장치를 에너지 절감형으로 개선한 증류방법 및 장치에 관한 것이다.The present invention relates to the design of an expansion type thermo-distillation fractional distillation unit, and more particularly, an energy-saving distillation method of a distillation vessel device used for separating components from aromatic mixtures obtained in petroleum refining and petrochemical processes. And to an apparatus.
종래, 석유 정유공정, 나프타 개질 공정, 중질유 분해 공정 등에서 나오는 가스 유분을 분리하는 방법은 이성분 증류탑과 유사하게 한 개의 탑에서 한가지 성분씩 분리하는 방법을 사용하고 있으며 그 구조는 도 1에 나타나 있는 바와 같다. 이러한 종래의 공정은 첫 번째 증류탑에서 가장 저비점인 벤젠을 분리하고 두 번째 증류탑에서 톨루엔 세 번째 증류탑에서 자일렌을 분리하는 3 탑 방식이다. 이와 같이, 현재의 석유화학공장에서 사용되고 있는 일반적인 분리방법으로서 3개의 재비기와 3개의 냉각기를 사용하기 때문에 에너지 소모가 많다는 단점이 있다.Conventionally, the method of separating gaseous oil from petroleum refining process, naphtha reforming process, heavy oil cracking process, etc. uses a method of separating one component from one column similarly to a two-component distillation column, the structure of which is shown in FIG. As shown. This conventional process is a three- tower method of separating the lowest boiling benzene in the first distillation column and xylene in the third distillation column toluene in the second distillation column. As such, since three reboilers and three coolers are used as a general separation method used in petrochemical plants, energy consumption is high.
상기와 같은 방향족 혼합물의 분별 증류법에 관해서는 몇몇 방법이 제안되어 있는데, 예를 들어 대한민국 특허등록 제 95390호(1981년 3월 26일 등록)는 새로운 증류방식에 대한 발명이 아니라 단지 폐열 회수의 방법을 제시한 것이다. 또 대한민국 특허등록 제 311429호(2001년 9월 26일 등록)는 수소화 변환반응기 유출물 스트림에서 생성물을 증류하여 분리하는 내용을 제시한 것으로 이 방법 또한 기존의 증류방식을 사용하여 분리하는 장치들의 새로운 배열만 포함한 내용으로 상기한 단점을 여전히 해결하지 못하고 있다.As for the fractional distillation of such aromatic mixtures, several methods have been proposed. For example, Korean Patent Registration No. 95390 (registered on March 26, 1981) is not an invention for a new distillation but merely a method for recovering waste heat. Will be presented. In addition, Korean Patent Registration No. 311429 (registered on September 26, 2001) proposed distillation of the product from the hydroconversion reactor effluent stream. Contents containing only arrays still do not solve the above drawbacks.
한편, 기존의 분별증류 방식은 한 개의 증류탑에서 한 개의 제품만을 생산하는 방식으로 모든 석유화학공장에서 사용하고 있으나 이러한 방식은 각 증류탑 마다 1개의 재비기와 1개의 냉각기를 독립적으로 사용하기 때문에 에너지 사용의 낭비가 크고 재비기와 냉각기용 열교환기의 용량이 크기 때문에 초기 설비비도 많이 소요되는 문제점이 있다.On the other hand, the conventional fractionation distillation method is used in all petrochemical plants to produce only one product in one distillation column, but this method uses one reboiler and one cooler independently for each distillation column. Since the waste is large and the capacity of the reheater and the cooler heat exchanger is large, there is a problem that the initial equipment cost is also large.
이에 본 발명자 등은 상기와 같이 분별 증류 방식에서 에너지 소비가 과다한 이유는 증류탑의 조성분포가 다성분 평형증류 조성곡선과 많은 차이를 가지기 때문이며, 종래의 분별증류 방식은 본질적으로 이러한 평형증류 조성곡선을 맞출 수 없다는 것을 인식하였다. 즉, 증류탑 내의 액의 조성분포가 평형증류 조성곡선과 유사하면 탑 내에서 스트림의 혼합이 최소가 되어 탑효율을 극대화할 수 있어 에너지 사용을 현저히 절감할 수 있으나, 종래의 방식은 이를 전혀 고려하고 있지 않아 사용 에너지의 소모가 크다는 종래의 요원한 문제점이 해결되지 않고 있었다.Therefore, the inventors of the present invention, the energy consumption in the fractional distillation method as described above is because the composition distribution of the distillation column has a lot of differences from the multi-component equilibrium distillation composition curve, the conventional fractional distillation method is essentially the equilibrium distillation composition curve I recognized that I could not fit. In other words, if the composition distribution of the liquid in the distillation column is similar to the equilibrium distillation composition curve, the mixing of the stream in the column is minimized to maximize the efficiency of the tower, which can significantly reduce the energy use. It is not solved the conventional problem of the long-term consumption of the use energy is not solved.
따라서, 본 발명자 등은 바로 이점을 인식하여 상기에 기재된 내용과 같은 문제점들을 해결하기 위하여 이미 특허 제10-2002-0056219호(2002년 9월 16일)를 출원한 바 있으며, 상기 출원이 나프타 개질반응기 유출 혼합물로부터 저비점 성분인 벤젠과 톨루엔의 2 성분 화합물과 고비점 혼합물만을 분별 증류하는 방법 및 장치에 관한 것이었으나 본 발명은 1개의 재비기와 1개의 냉각기만을 사용하여 상기에 기재된 내용과 같은 문제점들을 해결하면서도 확장형 열복합형 증류탑을 사용하여 개질반응기에서 나오는 방향족 화합물로부터 나프타 개질공정 유출 혼합물로부터 상기의 화합물들은 물론 자일렌 화합물도 동시에 분리해 낼 수 있는 연속 분별 증류방법 및 장치를 완성하게 되었다.Accordingly, the present inventors have already filed a patent No. 10-2002-0056219 (September 16, 2002) in order to solve the problems as described above, immediately recognizing the advantages, and the application has been modified naphtha Although the present invention relates to a method and apparatus for the fractional distillation of only two low boiling point components, such as benzene and toluene, and a high boiling point mixture from the reactor effluent mixture, the present invention addresses the problems described above using only one reboiler and one cooler. While solving the above problem, a continuous fractional distillation method and apparatus capable of simultaneously separating not only the above compounds but also xylene compounds from the naphtha reforming effluent mixture from the aromatics from the reforming reactor by using an extended thermal complex distillation column have been completed.
따라서, 본 발명의 목적은 나프타 개질공정에서 활용하여 저비점 성분인 벤젠, 톨루엔 및 자일렌을 각각 분리하는 증류공정에 활용함에 있어, 사용 에너지를 현저히 절감할 수 있는 증류 방법 및 그 장치를 제공하기 위한 것이다.Accordingly, an object of the present invention is to provide a distillation method and apparatus that can significantly reduce the energy used in the distillation process to separate the low boiling point components of benzene, toluene and xylene, respectively, in the naphtha reforming process. will be.
이러한 목적을 달성하기 위하여 본 발명에 따른 나프타 개질공정 유출 혼합물로부터 벤젠, 톨루엔, 자일렌의 연속 분별 증류방법 및 장치는 3개의 재비기와 3개의 냉각기를 사용하던 종래의 공정 대신 1개의 재비기와 1개의 냉각기만을 사용하는 공정을 채택함에 따라 에너지 소비를 현저히 절감할 수 있다는데 그 특징이 있다.In order to achieve this object, a continuous fractional distillation method and apparatus for benzene, toluene, and xylene from a naphtha reforming process effluent mixture according to the present invention have one reboiler and one instead of a conventional process using three reboilers and three coolers. Adopting a process that uses only a cooler can significantly reduce energy consumption.
더욱이, 본 발명은 증류공정에서 증류방식을 개선함으로서 증류단계의 사용에너지를 절감할 뿐 아니라, 증류설비를 단순화할 수 있게 함으로 증류장치의 설비비를 줄일 수 있는 증류 방법 및 그 장치를 제공하기 위한 것이다.In addition, the present invention is to provide a distillation method and apparatus that can reduce the equipment cost of the distillation apparatus by improving the distillation method in the distillation process to reduce the energy used in the distillation step, as well as simplify the distillation equipment. .
상기한 본 발명의 목적은 다성분 평형증류 곡선에 맞는 분별증류 방식을 이용한 확장형 열복합 증류탑을 사용하여 달성되는데, 이러한 증류탑은 석유정제 및 석유화학 공정의 나프타 개질 공정에 활용하여 비점에 따라 벤젠, 톨루엔 및 자일렌을 각각 분리하는 증류공정에서 사용 에너지를 현저히 감소하면서 분별증류가 가능하게 한다.The object of the present invention described above is achieved by using an expansion type thermal complex distillation column using a fractional distillation method that fits a multicomponent equilibrium distillation curve, and the distillation column is utilized in the naphtha reforming process of petroleum refining and petrochemical processes according to boiling point, In the distillation process that separates toluene and xylene respectively, fractional distillation is possible while significantly reducing the energy used.
상기와 같이 본 발명에 따른, 확장형 열복합 증류방식은 탑 효율이 높기 때문에 확장형 열복합형 증류탑을 이용하여 분리조작을 하면 에너지 사용량을 절감할 수 있고 증류탑의 재비기와 냉각기로 사용하는 열교환기의 용량을 줄일 수 있어 열교환기의 설비비를 줄일 수 있다.As described above, according to the present invention, the expansion type thermal complex distillation method has high tower efficiency, so that the separation operation using the expansion type thermal complex distillation column can reduce the energy consumption and the capacity of the heat exchanger used as a reboiler and a cooler of the distillation column. This can reduce the equipment cost of the heat exchanger.
본 발명의 구성을 보다 자세히 설명하면, 본 발명은 나프타 개질반응기에서 나오는 방향족 화합물의 혼합물에는 18가지의 성분이 혼합되어 있고 그 중 비점에 따라 벤젠, 톨루엔 및 자일렌을 각각 분리하여 제품으로 생산하는데 이 분리를 주탑에 재비기와 냉각기를 갖추지 않은 제 1 보조탑 및 제 2 보조탑을 설치한 확장형 열복합형 증류탑을 사용하여 분리하려고 한다. 방향족 화합물의 혼합물 성분의 수는 18가지이지만 각 성분의 비점과 함량에 따라 벤젠을 포함한 저비점 혼합물, 톨루엔을 포함한 제 1 중간비점 혼합물 , 자일렌을 포함한 제 2 중간비점 혼합물 및 나머지 고비점 혼합물의 4가지로 분류할 수 있다.When explaining the configuration of the present invention in more detail, the present invention is a mixture of aromatic compounds coming out of the naphtha reforming reactor 18 kinds are mixed, and the benzene, toluene and xylene are separated into each of them according to the boiling point to produce a product The separation is intended to be carried out using an expansion heat-comprising distillation column equipped with a first sub-column and a second sub-column without a scrubber and cooler in the main column. The number of mixture components of aromatic compounds is 18, but according to the boiling point and content of each component, 4 of the low boiling mixture containing benzene, the first intermediate boiling mixture containing toluene, the second intermediate boiling mixture containing xylene, and the remaining high boiling mixture 4 Can be classified into branches.
이를 위해 본 발명에 따른 증류방법은 도 2에 도시된 바와 같이 중앙에 위치한 주탑(Ⅰ)에 원료를 공급하고, 제 1 중간비점 혼합물중 액체는 주탑(Ⅰ)의 하부와 중간부 사이의 중간단에서 제 1 보조탑(Ⅱ)의 하단으로 이동되고, 증기는 주탑(Ⅰ)의 상부에 가까운 단에서 제 1 보조탑(Ⅱ)의 상단으로 이동되며, 제 2 중간비점 혼합물도 액체와 증기가 제 2 보조탑(Ⅲ)으로 이동하는 단의 위치가 제 1 중간비점 혼합물이 제 1 보조탑(Ⅱ)으로 이동하는 단의 위치보다 약간 아래에 위치한 단에서 액체와 증기가 각각 제 2 보조탑(Ⅲ)으로 이동하여 제 1 보조탑(Ⅱ)과 제 2 보조탑(Ⅲ)에서 각각 톨루엔과 자일렌을 생산하고, 벤젠과 고비점 혼합물은 주탑(Ⅰ)의 상부와 하부에서 각각 생산된다.To this end, the distillation method according to the present invention supplies the raw material to the main column (I) located at the center as shown in Figure 2, the liquid in the first intermediate boiling point mixture is the intermediate stage between the lower part and the middle of the main column (I) At the bottom of the first subsidiary tower (II), the vapor is moved from the stage near the top of the main tower (I) to the top of the first subsidiary tower (II), and the second intermediate boiling point mixture 2 In the stage where the stage moving to the subsidiary tower (III) is located slightly below the position of the stage where the first intermediate boiling point mixture moves to the first auxiliary tower (II), the liquid and vapor are respectively separated from the second auxiliary tower (III). ), Toluene and xylene are produced in the first subsidiary tower (II) and the second subsidiary tower (III), respectively, and benzene and high boiling point mixtures are produced in the upper and lower portions of the main tower (I), respectively.
이때 주탑(Ⅰ)과 두 개의 보조탑 사이는 증기와 액체가 서로 교환되기 때문에 두 개의 보조탑에서는 재비기와 냉각기를 필요로 하지 않는다. 이를 위해, 즉 상기와 같은 본 발명에 따른 증류의 조건을 만족하기 위해 본 발명에 따른 확장형 열복합형 증류탑은 탑의 상단에 냉각기, 탑의 하단에 재비기가 각각 설치된 주탑(Ⅰ)과 제 1 보조탑(Ⅱ), 제 2 보조탑(Ⅲ)으로 구성되며 탑의 단수, 세 탑의 연결위치, 원료 공급단, 중간제품 배출단의 결정을 위한 설계는 다음과 같이 되어야 한다. At this time, since the vapor and liquid are exchanged between the main tower (I) and the two auxiliary towers, the two auxiliary towers do not require a reboiler and a cooler. To this end, namely, in order to satisfy the conditions of the distillation according to the present invention as described above, the expansion type thermo-composite distillation column according to the present invention includes a main tower (I) and a first auxiliary unit having a cooler at the top of the tower and a reboiler at the bottom of the tower, respectively. It is composed of tower (II) and second subsidiary tower (III), and the design for determining the number of stages, the connection position of three towers, raw material supply stage and intermediate product discharge stage should be as follows.
첫째 전환류 조작에 의해 증류를 한다고 가정하면 최소의 증류단수를 계산하고 최소 증류단의 단수를 2배로 하여 실제 소요의 증류단수를 계산한다. 전환류 조작에서는 탑의 효율이 이상적이고 탑 내 조성분포가 평형관계 만으로 계산되기 때문이다. 주탑(Ⅰ)의 경우 원료의 조성을 이용하여 탑 상부의 조성분포를 계산하는데 우선 원료공급단의 액체조성이 원료의 조성과 같다고 하고 증기의 조성을 계산한다. 이 증기의 조성은 원료공급단보다 1단 위의 액체의 조성과 같으므로 다음 식 (1)과 같이 계산된다. First, assuming distillation by conversion flow operation, the minimum number of distillation stages is calculated and the actual required number of distillation stages is calculated by doubling the number of stages of the minimum distillation stage. This is because the efficiency of the tower is ideal in the divert flow operation and the composition distribution in the tower is calculated only by the equilibrium relationship. In the case of the main tower (I), the composition distribution of the top of the column is calculated using the composition of the raw material. First, the liquid composition of the raw material supply stage is the same as that of the raw material, and the composition of the steam is calculated. Since the composition of this steam is the same as that of the liquid one stage above the raw material supply stage, it is calculated as the following equation (1).
여기서 x는 액체조성이고 ??는 상대휘발도이며 하첨자 n은 단수를 나타내고 i는 성분을 나타낸다. 다시 증기의 조성과 액의 조성을 반복 계산하면 원료공급단의 상부탑 조성분포를 계산할 수 있다. 이렇게 하여 각각의 상부탑 조성을 각각 계산한다. 주탑(Ⅰ) 하부의 조성분포는 반대로 원료 투입단에서 부터 1단 아래의 단의 증기조성이 액체 원료의 조성과 같은 것으로 하여 차례차례 1단씩 내려가면서 식 (2)와 같이 계산한다.Where x is the liquid composition, and ?? Is the relative volatility, subscript n represents the singular and i represents the component. Again, by calculating the composition of the steam and the composition of the liquid repeatedly it is possible to calculate the top tower composition distribution of the raw material supply stage. In this way, each top tower composition is calculated separately. On the contrary, the composition distribution in the lower part of the main column (I) is calculated as shown in Eq.
제 1 보조탑(Ⅱ), 제 2 보조탑(Ⅲ)의 상부와 하부의 조성분포는 각각에서 생산되는 제품의 조성으로부터 주탑(Ⅰ)에서 계산한 것과 동일한 방법으로 계산하여 두고 각각의 끝은 주탑(Ⅰ)의 조성분포와 비교하여 연결부분의 조성이 유사한 곳으로 결정한다. 보조탑의 단수와 주탑의 연결단은 두 탑의 조성분포를 비교하여 계산하는데 두 탑의 조성분포를 나열하고 불순물의 양과 두 탑의 조성이 어느 정도 근접하는지를 고려하여 결정한다. 이렇게 결정된 보조탑의 상부조성의 단수와 하부조성의 단수를 합하면 보조탑의 전체 단수가 되고 주탑(Ⅰ)에서 원료의 공급단은 상부와 하부의 단수를 비교하여 결정된다. 또 주탑(Ⅰ)의 연결부위는 보조탑의 양쪽 끝 조성 각각과 이에 대응하는 위치를 찾아서 알아낸다. The composition distributions of the upper and lower portions of the first and second auxiliary towers (II) and (III) are calculated in the same way as those calculated in the main tower (I) from the composition of the products produced in each, and the ends of each of the main towers are The composition of the connection part is decided to be similar to the composition distribution of (I). The number of stages of the auxiliary tower and the connection stage of the main tower are calculated by comparing the composition distribution of the two towers. The composition distribution of the two towers is listed and determined by considering the amount of impurities and how close the composition of the two towers is. When the number of stages of the upper composition and the bottom composition of the auxiliary tower thus determined are added together, the total number of stages of the auxiliary tower becomes, and the supply stage of the raw material in the main tower (I) is determined by comparing the number of stages of the top and bottom. In addition, the connection part of the main tower (I) is found by finding the respective positions of the two ends of the auxiliary tower and their corresponding positions.
이렇게 계산된 단수는 최소 소요단으로 실제는 전환류 조작을 하지 않으므로 실제단수는 통상의 설계기준(J.D. Seader and E.J. Henley, "Separation Process Principles," p. 510, John Wiley & Sons, Inc., N. Y., 1998)에 따라 최소단의 2배로 하여 실제 소요단을 결정한다.The number of stages calculated in this way is the minimum required stage and does not actually perform the conversion flow operation. Therefore, the actual stage is a general design standard (JD Seader and EJ Henley, "Separation Process Principles," p. 510, John Wiley & Sons, Inc., NY , 1998) to determine the actual required stage by double the minimum stage.
표 1에 본 발명의 확장형 열복합 증류탑 단수 결정 결과를 정리하였다. 최소단으로부터 계산된 단수는 운전조건의 계산에서 약간 수정되었다. 주탑(Ⅰ)의 26번단은 원료가 공급되고 제 1 보조탑(Ⅱ) 18단에서 톨루엔이 생산되고 제 2 보조탑(Ⅲ)의 28단에서 자일렌이 생산되며, 제 1 보조탑(Ⅱ)은 주탑(Ⅰ)의 13번단과 상부와 연결되고 35번단은 제 1 보조탑(Ⅱ)의 하부와 연결되며, 제 2 보조탑(Ⅲ)은 주탑(Ⅰ)의 11번단과 상부가 연결되고 주탑(Ⅰ)의 39번단은 제 2 보조탑(Ⅲ)의 하부와 연결된다. 본 발명의 확장형 열복합 증류탑에는 재비기와 냉각기가 주탑(Ⅰ)에 만 설치되어 있는 것이 기존의 증류탑과 다른 점이다. Table 1 summarizes the results of the determination of the number of stages of the expansion type thermal complex distillation column of the present invention. The number of stages calculated from the minimum stage has been slightly modified in the calculation of the operating conditions. The 26th stage of the main tower (I) is supplied with raw materials, toluene is produced in the 18th stage of the first auxiliary tower (II), and xylene is produced in the 28th stage of the second auxiliary tower (III), and the first auxiliary tower (II) Is connected to the 13th stage and the upper part of the main tower (I), and the 35th stage is connected to the lower part of the first auxiliary tower (II), and the second auxiliary tower (III) is connected to the 11th stage and the upper part of the main tower (I). Step 39 in (I) is connected to the lower part of the second auxiliary tower (III). In the expansion type thermal complex distillation column of the present invention, the reboiler and the cooler are installed only in the main tower (I), which is different from the existing distillation column.
[표 1] 탑의 구조계산 결과 (단수는 탑상부에서부터 계산한 값임)[Table 1] Structural calculation results of the tower (single is calculated from the top of the tower)
나프타 개질반응공정으로부터 얻어진 제품에는 여러 가지의 성분이 혼합되어 있고 이를 각각의 용도별로 분리하여 제품으로 생산해 낸다. 본 발명의 장치는 이 분별증류에 사용되는 장치로써 장치에 공급되는 원료는 18가지 성분이 혼합되어 있고 그 조성은 표 2와 같다. The products obtained from the naphtha reforming process are mixed with various components and are separated into their respective applications and produced as products. The apparatus of the present invention is an apparatus used for this fractional distillation. The raw materials supplied to the apparatus are mixed with 18 components and the composition thereof is shown in Table 2.
표 2에는 원료의 조성과 함께 제품의 규격조성도 포함되어 있는데 이러한 제품을 생산하기 위해서는 장치의 운전조건을 계산하여야 한다. 운전조건을 계산하기 위하여 표 1과 같은 증류탑의 구조를 가진 확장형 열복합 증류탑에 여러 가지 운전조건을 사용하였을 때의 증류계산을 반복 실시하여 요구되는 제품을 생산하면서 에너지 사용이 가장 적은 조건을 찾아야 한다. 이러한 계산을 위해 본 발명에서는 상업용 계산 프로그램인 HYSYS를 사용하였으며 표 3의 운전조건에서 요구되는 제품이 얻어진다. Table 2 contains the composition of the product as well as the composition of the raw material. To produce these products, the operating conditions of the device must be calculated. In order to calculate the operating conditions, the distillation calculation when the various operating conditions are used in the expanded thermal combined column having the structure of the distillation column as shown in Table 1 should be repeated to find the condition that requires the least energy while producing the required product. . For this calculation, in the present invention, a commercial calculation program HYSYS was used, and a product required under the operating conditions of Table 3 was obtained.
[표 2] 원료와 제품의 조성(단위: kg-mol/h)[Table 2] Composition of Raw Materials and Products (Unit: kg-mol / h)
[표 3] 확장형 열복합 증류탑의 운전조건[Table 3] Operating conditions of the expansion type thermal complex distillation column
도 3는 본 발명의 확장형 열복합 증류탑을 사용하여 운전계산을 할 때의 장치를 도시한 것이다. 도면에서 왼쪽에 있는 탑이 톨루엔을 생산하는 제 1 보조탑이고 중간에 있는 탑이 주탑이며, 오른쪽에 있는 탑이 자일렌을 생산하는 제 2 보조탑이다. 세 탑의 단수와 연결단의 위치, 원료 공급단과 중간 제품 공급단의 위치는 표 1에 제시된 대로 설정하였다. 도면에서 Feed로 표시된 것이 원료이고 Bz로 표시된 것이 상부제품, Toluene로 표시된 것이 톨루엔, Xylene로 표시된 것이 자일렌, C9+로 표시된 것이 고비점 제품이다. 또 PD1은 제 1 보조탑에서 주탑으로 들어가는 증기이고 PD2는 주탑에서 제 1 보조탑으로 내려오는 액체이며 PB1은 제 1 보조탑에서 주탑으로 흐르는 액체이며 PB2는 주탑에서 제 1 보조탑으로 공급되는 증기의 흐름이다. PC1은 제 2 보조탑에서 주탑으로 흐르는 증기이고 PC2는 주탑에서 제 2 보조탑으로 흐르는 액체이며 PA1은 제 2 보조탑에서 주탑으로 흐르는 액체이고 PA2는 주탑에서 제 2 보조탑으로 공급되는 증기의 흐름이다. Cond Duty는 냉각기에서 제거되는 열흐름이고 Reboiler Duty는 재비기에 공급되는 열흐름이다.Figure 3 shows an apparatus when calculating the operation using the expanded thermal combined column of the present invention. In the drawing, the tower on the left is the first auxiliary tower for producing toluene, the tower in the middle is the main tower, and the tower on the right is the second auxiliary tower for producing xylene. The number of stages and the connection stages of the three towers, and the positions of the feed and intermediate product feed stages, were set as shown in Table 1. In the drawing, feed is the raw material, Bz is the upper product, Toluene is the toluene, Xylene is the xylene, C9 + is the high boiling point product. PD1 is the vapor entering the main column from the first sub-column, PD2 is the liquid flowing down from the main column to the first sub-column, PB1 is the liquid flowing from the first sub-column to the main column, and PB2 is the steam supplied from the main column to the first sub-column. Is the flow of. PC1 is the vapor flowing from the second column to the main column, PC2 is the liquid flowing from the main column to the second column, PA1 is the liquid flowing from the second column to the main column, and PA2 is the flow of steam supplied from the tower to the second column to be. Cond Duty is the heat flow removed from the chiller and Reboiler Duty is the heat flow supplied to the reboiler.
원료의 공급량을 표3에 제시된 대로 공급하고 원료의 조성이 표2에서와 같을 때 벤젠, 톨루엔, 자일렌 및 고비점 제품 각각의 조성은 표2에 제시된 대로 얻어 졌고 이 때의 생산량은 표 3에 나열된 바와 같다. 여기서 얻어진 증류탑 내에서의 각단의 액체 조성의 분포를 정의한 것이 도 4이다.When the feed amount of the raw material is supplied as shown in Table 3 and the composition of the raw material is as shown in Table 2, the composition of each of the benzene, toluene, xylene and high boiling point products is obtained as shown in Table 2, and the output is shown in Table 3 As listed. Fig. 4 defines the distribution of the liquid composition at each stage in the distillation column obtained here.
기존의 증류방식에 의한 운전조건을 본 발명의 장치와 비교하기 위하여 도 5와 같은 장치를 이용하여 계산한 결과 표 4와 같은 결과를 얻었다. 이 때의 각단에서의 조성분포는 도 6에 나타내었다. 도 5에서 Feed는 원료의 흐름이고 Bz Col은 벤젠생산의 증류탑으로 Bz Col OVHD는 벤젠탑의 상부 제품, Bz Col Btm은 벤젠탑의 하부흐름을 나타낸다. Tol Column 은 톨루엔 생산 증류탑이며 T-100은 자일렌 생산 증류탑이다. 마찬가지로 Tol OVHD는 톨루엔탑 상부제품을 Tol Btm은 톨루엔탑 하부제품을 나타내고 Xyl OVHD는 자일렌탑 상부제품을 Xyl Btm은 자일렌탑 하부제품을 나타낸다. Q-cond는 냉각기의 열흐름을 Q-Reb는 재비기의 열흐름을 각각 표시한다. In order to compare the operating conditions of the conventional distillation method with the apparatus of the present invention, the results shown in Table 4 were obtained using the apparatus shown in FIG. 5. The composition distribution in each stage at this time is shown in FIG. In Figure 5, Feed is the flow of raw materials and Bz Col is the distillation column of benzene production. Tol Column is a toluene distillation column and T-100 is a xylene distillation column. Similarly, Tol OVHD stands for Toluene Top Top, Tol Btm stands for Toluene Top Bottom, Xyl OVHD stands for Xylene Top Top, and Xyl Btm stands for Xylene Top Bottom. Q-cond indicates the heat flow of the cooler and Q-Reb indicates the heat flow of the reboiler.
[표 4] 기존 증류탑의 운전조건[Table 4] Operation conditions of the existing distillation column
이렇게 조작하여 얻은 제품의 조성은 표 2에 제시된 제품의 조성과 동일하였다. 본 발명에서 제시하는 것은 동일한 원료를 가공하여 동일한 제품을 생산하면서 기존의 증류방식에 비해 적은 에너지를 사용한다는 점이다. 이것은 표 3의 열 공급량과 표 4의 열공급량을 비교하면 알 수 있다.The composition of the product thus obtained was the same as that of the product shown in Table 2. The present invention is to process the same raw material to produce the same product while using less energy than the conventional distillation method. This can be seen by comparing the heat supply of Table 3 with that of Table 4.
원료를 도 5의 기존의 장치로 처리하였을 때 필요한 에너지의 양은 첫 번째 증류탑에서 21.4 GJ/h, 두 번째 증류탑에서 41.0 GJ/h, 세 번째 증류탑에서 21.4 GJ/h가 각각필요하나 본 발명의 장치를 사용할 경우 75.7 GJ/h가 필요하다. 즉 9.7%의 에너지 절감 효과를 얻을 수 있다. The amount of energy required when the raw material is treated with the conventional apparatus of FIG. 5 requires 21.4 GJ / h in the first distillation column, 41.0 GJ / h in the second distillation column, and 21.4 GJ / h in the third distillation column, respectively. Requires 75.7 GJ / h. That is, energy savings of 9.7% can be achieved.
상기와 같은 본 발명은 종래의 공정이 3개의 재비기와 3개의 냉각기를 사용하기 때문에 에너지 소모가 많은 단점을 보완하기 위해 본 발명의 구성에 따른 나프타 개질 공정에서 생산하는 방향족 화합물의 생산을 확장형 열복합 증류탑을 사용하는 공정은 주탑에만 1개의 재비기와 1개의 냉각기만을 설치하여 에너지 절감공정으로 대체하는 방안을 제시하였으며, 본 설계를 위하여 구조적 설계법을 활용하였다.The present invention as described above is to expand the production of the aromatic compound produced in the naphtha reforming process according to the configuration of the present invention in order to compensate for the drawback of the high energy consumption because the conventional process uses three reboiler and three coolers. In the distillation column, only one reboiler and one cooler were installed in the main column to replace the energy saving process, and the structural design method was used for this design.
제시된 설계방법으로 새로운 나프타 개질 공정을 구성할 수 있었으며 새로운 확장형 열복합 증류탑을 사용하면 기존의 탑 공정에 비해 에너지 절감효과를 얻을 수 있고 이는 증류설비를 단순화할 수 있게 함으로서 증류장치의 설비비를 줄일 수 있게 하는 유용한 발명이다.The proposed design method was able to construct a new naphtha reforming process, and the use of the new expansion heat-distillation column can provide energy savings compared to the existing tower process, which can simplify the distillation unit and reduce the cost of the distillation unit. It is a useful invention to make.
도 1은 종래의 증류 방법에 따른 증류장치를 개략적으로 나타낸 개략도이고1 is a schematic view showing a distillation apparatus according to a conventional distillation method
도 2는 본 발명의 증류 방법에 따른 증류장치를 개략적으로 나타낸 개략도이고,Figure 2 is a schematic diagram schematically showing a distillation apparatus according to the distillation method of the present invention,
도 3은 본 발명의 증류 방법에 따른 분별증류 공정의 배치도이고,3 is a layout view of a fractional distillation process according to the distillation method of the present invention,
도 4는 실제 단을 사용한 증류탑의 액체조성 분포를 나타내는 그래프이고,4 is a graph showing the liquid composition distribution of the distillation column using the actual stage,
도5는 종래의 증류 방법에 따른 분별증류 공정의 배치도이고,5 is a layout view of a fractional distillation process according to a conventional distillation method,
도6은 종래의 증류 방법에 따른 액체조성 분포를 나타내는 그래프이다.6 is a graph showing a liquid composition distribution according to a conventional distillation method.
*도면의 주요부분의 부호의 설명* Explanation of symbols in main part of drawing
Ⅰ : 주탑 Ⅱ : 제 1 보조탑 Ⅰ: main tower Ⅱ: first auxiliary tower
Ⅲ : 제 2 보조탑 ABCD, F : 원료 III: 2nd auxiliary tower ABCD, F: raw material
A : 벤젠 B : 톨루엔 A: Benzene B: Toluene
C : 자일렌 D : 고비점 제품 C: xylene D: high boiling point product
o : 주탑의 조성 +, x : 보조탑의 조성 o: Composition of main tower +, x: Composition of auxiliary tower
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| KR101674655B1 (en) | 2015-12-01 | 2016-11-09 | 동아대학교 산학협력단 | Benzene Removal Equipment and Removal Method in Gasoline Blend from Fluidized Catalytic Cracker Reformate |
| KR101674660B1 (en) | 2015-12-07 | 2016-11-09 | 동아대학교 산학협력단 | Aromatic compounds separation equipment and separation method with reduced extraction load |
| KR102070421B1 (en) | 2019-10-08 | 2020-01-28 | 부경대학교 산학협력단 | Aromatic compounds separation equipment and separation method with high separation efficiency by extractive distillation |
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| US7910070B2 (en) | 2008-12-09 | 2011-03-22 | Uop Llc | Process for reducing benzene concentration in reformate |
| KR101340881B1 (en) * | 2011-12-30 | 2013-12-13 | 이기영 | Distilation method of the fake gasoline |
| KR101340884B1 (en) * | 2011-12-30 | 2013-12-13 | 이기영 | Distilation method of the fake gasoline |
| CN111362772B (en) * | 2020-02-13 | 2022-10-04 | 东营威联化学有限公司 | Device for producing dimethylbenzene by using straight-run naphtha method |
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| KR101674660B1 (en) | 2015-12-07 | 2016-11-09 | 동아대학교 산학협력단 | Aromatic compounds separation equipment and separation method with reduced extraction load |
| KR102070421B1 (en) | 2019-10-08 | 2020-01-28 | 부경대학교 산학협력단 | Aromatic compounds separation equipment and separation method with high separation efficiency by extractive distillation |
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