CN1061640C - Method for preparing industrial phenanthrene - Google Patents
Method for preparing industrial phenanthrene Download PDFInfo
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- CN1061640C CN1061640C CN97118122A CN97118122A CN1061640C CN 1061640 C CN1061640 C CN 1061640C CN 97118122 A CN97118122 A CN 97118122A CN 97118122 A CN97118122 A CN 97118122A CN 1061640 C CN1061640 C CN 1061640C
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 15
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000000998 batch distillation Methods 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 4
- 230000006837 decompression Effects 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000006229 carbon black Substances 0.000 abstract description 2
- 239000000295 fuel oil Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000002893 slag Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- -1 isopropylaniline sulfamate Chemical compound 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本发明属于焦化产品深加工领域，特别是一种工业菲的制取方法。随着科学技术的发展，工业菲的应用领域越来越广阔，可以用于生产苯酐，也可以氧化成联苯二甲酸(DNA)，用于制造合成树脂、合成纤维等；可以氧化成菲醌，用于生产农药、染料等，也可以用于生产阻燃纤维、光电显影剂等。但是要求这种工业菲有较高的纯度。提高菲的纯度有多种方法：The invention belongs to the field of deep processing of coking products, in particular to a method for preparing industrial phenanthrene. With the development of science and technology, the application field of industrial phenanthrene has become more and more extensive. It can be used to produce phthalic anhydride, and can also be oxidized into biphenyl dicarboxylic acid (DNA), used to make synthetic resins, synthetic fibers, etc.; it can be oxidized into phenanthrenequinone , used in the production of pesticides, dyes, etc., and can also be used in the production of flame-retardant fibers, photoelectric developers, etc. However, this industrial phenanthrene is required to have a higher purity. There are several ways to increase the purity of phenanthrene:
一是利用脱晶蒽油(含菲20％)为原料，用精馏法得到含菲80％左右的馏分，在溶剂中重结晶得含菲90％的工业菲(见《КОКИХИМИя》1983，No1，p27～30)。One is to use decrystallized anthracene oil (containing 20% phenanthrene) as a raw material, obtain a fraction containing about 80% phenanthrene by rectification, and recrystallize in a solvent to obtain industrial phenanthrene containing 90% phenanthrene (see "КОКИХИМИя", 1983, No1 , p27-30).
二是用含菲20～30％的粗蒽为原料，利用CC14保护，浓硫酸洗涤，得到90％的工业菲(《КОКИХИМИя》1987，No4)。The second is to use crude anthracene containing 20-30% phenanthrene as raw material, protect it with CC14, and wash it with concentrated sulfuric acid to obtain 90% industrial phenanthrene ("КОКИХИМИя" 1987, No4).
三是用沸石吸收法，如日本专利JP09067276公开那种从菲蒽混合物中分离出菲的二步法，第一步是将混合物与含有碱金属或碱土金属的x型或y型沸石相接触，有选择地将菲吸附到沸石上，第二步是用苯和／或低烷基苯与吸附有菲的沸石相接触，从沸石中解吸出菲，再将苯和菲分离。专利RU2043324也公开了一种类似的方法。The third is to use zeolite absorption method, such as Japanese Patent JP09067276 discloses the two-step method of separating phenanthrene from the phenanthrene mixture, the first step is to contact the mixture with x-type or y-type zeolite containing alkali metal or alkaline earth metal, The phenanthrene is selectively adsorbed on the zeolite, and the second step is to use benzene and/or lower alkylbenzene to contact the phenanthrene adsorbed on the zeolite, desorb the phenanthrene from the zeolite, and then separate the benzene and phenanthrene. Patent RU2043324 also discloses a similar method.
四是采用所谓逆流法(SU1293166)，使蒽菲混合物与逆向流动的吸收剂混合液相接触，此混合液由异丙基苯氨基磺酸盐和10～14C石腊烃(重量比为1～4∶1，温度为80～85℃)，从提取塔顶上收集起来的残液为含有菲的石腊溶液冷却后形成菲晶体再用过滤法分离出来，在提取塔底部收集起的提取液为溶解在N异丙基苯氨基磺酸盐中的蒽所组成，冷却后分离出蒽，用这种方法所提取的菲的纯度可达95％，蒽的纯度可达98％。以上种种方法各有优缺点，适用于不同的原材料条件。The fourth is to use the so-called countercurrent method (SU1293166) to contact the anthracene mixture with the countercurrent flow of the absorbent mixture, which is composed of isopropylaniline sulfamate and 10 to 14C paraffin (weight ratio of 1 to 4:1, temperature is 80～85 ℃), the raffinate collected from the top of the extraction tower is the paraffin wax solution containing phenanthrene after cooling to form phenanthrene crystals and then separated by filtration, and the extract collected at the bottom of the extraction tower It is composed of anthracene dissolved in N-isopropylaniline sulfamate, and anthracene is separated after cooling. The purity of phenanthrene extracted by this method can reach 95%, and the purity of anthracene can reach 98%. The above methods have their own advantages and disadvantages, and are suitable for different raw material conditions.
本发明的目的是提供一种利用减压蒸馏得到的菲馏分，放入反应器中，加入添加剂和溶剂，重结晶后进行抽滤得到含菲量达到95％以上的工业菲取制方法。The purpose of this invention is to provide a kind of phenanthrene cut that utilizes vacuum distillation to obtain, put into reactor, add additive and solvent, carry out suction filtration after recrystallization and obtain the industrial phenanthrene extraction method that content reaches more than 95%.
本发明的另一个目的是提供一种利用含菲95％的工业菲制取菲含量达到98％以上的工业菲制取方法。Another object of the present invention is to provide a method for producing industrial phenanthrene with a content of more than 98% from industrial phenanthrene containing 95% phenanthrene.
按照本发明的工业菲制取方法，是同样以含菲为15～20％的蒽油为原料，利用减压间歇蒸馏法得到含菲70～80％的馏分，然后使此馏分和添加剂、溶剂进行反应、重结晶、抽滤得到含菲95％以上的工业菲，其工艺制度为：According to the industrial phenanthrene preparation method of the present invention, the anthracene oil containing 15-20% of phenanthrene is also used as raw material, and a fraction containing 70-80% of phenanthrene is obtained by vacuum intermittent distillation, and then the fraction and additives and solvents are used Carry out reaction, recrystallization, suction filtration to obtain the industrial phenanthrene containing more than 95% phenanthrene, and its technological system is:
1)将所述的馏分加到反应釜中在70～150℃的温度下使之溶化；1) adding the fraction into the reactor to melt it at a temperature of 70-150°C;
2)加入作为添加剂的顺丁烯二酸酐，搅拌均匀；2) Add maleic anhydride as an additive and stir evenly;
3)加入溶剂再进行搅拌均匀；3) add solvent and then stir evenly;
4)将搅拌均匀的反应物送进结晶器中进行5～20小时结晶；4) Send the uniformly stirred reactant into a crystallizer for crystallization for 5 to 20 hours;
5)将结晶后的混合物送到抽滤机中进行9～20小时抽滤，所得滤饼即为含菲95％以上的工业菲；5) Send the crystallized mixture to a suction filter for 9 to 20 hours of suction filtration, and the resulting filter cake is industrial phenanthrene containing more than 95% phenanthrene;
6)加入反应釜中各组份的重量比为∶馏分∶顺丁烯二酸酐∶溶剂=1∶0．08～0．15∶2～4。6) The weight ratio of each component added to the reactor is: fraction: maleic anhydride: solvent = 1: 0.08-0.15: 2-4.
1)～5)项所需的时间取决于所处的馏分的重量，即所处的馏分越多，所需的时间越长。从滤液中再生回收的溶剂可重复使用。提高工业纯度的关键是要将菲馏分中的蒽除去。众所周知，蒽和菲的沸点非常接近，只差2℃，用蒸馏方法很难将两者完全分离，蒽又比菲更难溶解在溶剂中。因此，去除蒽就是提高工业菲纯度的关键环节。使蒽与添加剂结合成蒽的加成物，溶解在溶剂中，加以去除是一种理想的方法，也是本发明的要点。The time required for items 1) to 5) depends on the weight of the cuts, that is, the more cuts there are, the longer the time required. The solvent recovered from the regeneration of the filtrate can be reused. The key to improving the industrial purity is to remove the anthracene in the phenanthrene fraction. As we all know, the boiling points of anthracene and phenanthrene are very close, with a difference of only 2°C. It is difficult to completely separate the two by distillation, and anthracene is more difficult to dissolve in solvents than phenanthrene. Therefore, the removal of anthracene is the key link to improve the purity of industrial phenanthrene. Combining anthracene with additives to form anthracene adducts, dissolving them in solvents and removing them is an ideal method, which is also the gist of the present invention.
本发明选用的添加剂为顺丁二酸酐，但是本发明的添加剂并不局限于此，只要能和蒽化合成能溶于溶剂中而又不和菲发生反应的物质均可用作为添加剂，均属于本发明的范围。The additive used in the present invention is maleic anhydride, but the additive of the present invention is not limited thereto, as long as it can be synthesized with anthracene and can be dissolved in a solvent and does not react with phenanthrene, it can be used as an additive, and all belong to this invention. the scope of the invention.
按照本发明的工业菲制取方法，所述的溶剂可选用乙醇或甲醇，也可选用性能相同或相近的其它溶剂。According to the industrial phenanthrene preparation method of the present invention, the solvent may be ethanol or methanol, or other solvents with the same or similar properties.
如果想要得到纯度更高(例如98％以上)的工业菲，可以将95％的工业菲放进反应釜中只加入适量溶剂，在70～80℃温度下进行搅拌后再进行重结晶，抽滤即可。If you want to obtain industrial phenanthrene with higher purity (for example, more than 98%), you can put 95% industrial phenanthrene into the reaction kettle and only add an appropriate amount of solvent, and then carry out recrystallization after stirring at a temperature of 70-80°C. Just filter.
本发明具有如下特点：The present invention has following characteristics:
1)原料脱晶蒽油价廉、易得，而且产量较大，年产可达3～4万吨或更大。1) The raw material decrystallized anthracene oil is cheap and easy to obtain, and the output is relatively large, with an annual output of 30,000 to 40,000 tons or more.
2)所使用的添加剂用量较少。2) The amount of additive used is less.
3)所使用的溶剂容易得到，容易回收利用。3) The used solvent is easy to obtain and easy to recycle.
4)蒸馏残渣可用作炭黑油或燃料油；预蒸馏物质可作重质洗油用。4) Distillation residue can be used as carbon black oil or fuel oil; pre-distilled material can be used as heavy washing oil.
实施例：Example:
1、当减压蒸馏所得馏分含菲为76．90％，含蒽为13．25％时，各组分的重量比为馏分∶顺丁烯二酸酐∶溶剂(乙醇)=1∶0．15∶2．5，熔化搅拌温度为140℃。1. When the fraction obtained by vacuum distillation contains 76.90% phenanthrene and 13.25% anthracene, the weight ratio of each component is fraction: maleic anhydride: solvent (ethanol)=1:0.15 : 2.5, the melting and stirring temperature is 140°C.
2．当减压蒸馏所得到的馏分含菲为80．2％含蒽为7．8％时各组分重量比为∶馏分∶顺丁烯二酸酐∶溶剂(乙醇)=1∶0．1∶3，熔融反应温度为150℃。目前高纯度工业菲的市场前景看好，按照本发明的方法制取高纯度工业菲，经济效益可观。2. When the fraction obtained by vacuum distillation contains 80.2% phenanthrene and 7.8% anthracene, the weight ratio of each component is: fraction: maleic anhydride: solvent (ethanol)=1: 0.1: 3 , The melting reaction temperature is 150°C. At present, the market prospect of high-purity industrial phenanthrene is promising, and the preparation of high-purity industrial phenanthrene according to the method of the present invention has considerable economic benefits.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118122A CN1061640C (en) | 1997-09-19 | 1997-09-19 | Method for preparing industrial phenanthrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118122A CN1061640C (en) | 1997-09-19 | 1997-09-19 | Method for preparing industrial phenanthrene |
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| CN1212250A CN1212250A (en) | 1999-03-31 |
| CN1061640C true CN1061640C (en) | 2001-02-07 |
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| CN97118122A Expired - Fee Related CN1061640C (en) | 1997-09-19 | 1997-09-19 | Method for preparing industrial phenanthrene |
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| CN104447184A (en) * | 2014-10-28 | 2015-03-25 | 常州大学 | Method for synthesizing 2-chloro-benzo [9,10] phenanthrene |
| CN104447190A (en) * | 2014-10-28 | 2015-03-25 | 常州大学 | Synthetic method of 2-fluorotriphenylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1293166A1 (en) * | 1985-06-26 | 1987-02-28 | Уральский политехнический институт им.С.М.Кирова | Method of separating anthracene-phenanthrene mixture |
| CN1121103A (en) * | 1994-10-18 | 1996-04-24 | 北京市燃气煤化工研究所 | Method of refining anthracene, phenanthrene and carbazole |
| JPH0967276A (en) * | 1995-08-28 | 1997-03-11 | Nkk Corp | How to separate phenanthrene |
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1997
- 1997-09-19 CN CN97118122A patent/CN1061640C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1293166A1 (en) * | 1985-06-26 | 1987-02-28 | Уральский политехнический институт им.С.М.Кирова | Method of separating anthracene-phenanthrene mixture |
| CN1121103A (en) * | 1994-10-18 | 1996-04-24 | 北京市燃气煤化工研究所 | Method of refining anthracene, phenanthrene and carbazole |
| JPH0967276A (en) * | 1995-08-28 | 1997-03-11 | Nkk Corp | How to separate phenanthrene |
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