CN100393677C - Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar - Google Patents
Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar Download PDFInfo
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- CN100393677C CN100393677C CNB2005100141937A CN200510014193A CN100393677C CN 100393677 C CN100393677 C CN 100393677C CN B2005100141937 A CNB2005100141937 A CN B2005100141937A CN 200510014193 A CN200510014193 A CN 200510014193A CN 100393677 C CN100393677 C CN 100393677C
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- methylnaphthalene
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Abstract
The present invention discloses a method for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar. The method uses a device comprising an alkanization polymerization reactor and three rectifying towers connected in series. The present invention comprises the process that raw materials having the total methylnaphthalene content which is not lower than 60 % are added into the alkylation polymerization reactor, the catalyst and the alkylating agent of solid acid or liquid acid or mixed acid are also added in the alkylation polymerization reactor, and alkylation polymerization reaction is carried out at a temperature from 70 DEG C to 90 DEG C and from 95 DEG C to 115 DEG C. The materials after alkanization polymerization are added to a rectifying tower 1 for separation, and light distillate is eliminated by a tower top. The materials without the light distillate are added to a rectifying tower 2 for separation, and the tower top obtains 2-methylnaphthalene having a content which is not less than 95 %. The materials without the 2-methylnaphthalene are added to a rectifying tower 3 for separation, and the tower top obtains 1-methylnaphthalene having a content which is not less than 95 %. The present invention has the advantages that the same equipment can be used for washing oil in coal tar as well as washing oil in pyrolysis tar, and the purity of the 1-methylnaphthalene and the 2-methylnaphthalene is not less than 95 %.
Description
Technical field
The present invention relates to a kind of method of from tar, extracting 1-methylnaphthalene and 2-methylnaphthalene, be specially adapted to from the petroleum cracking by-product coke oil wash oil that contains the methylnaphthalene composition or coal tar wash oil, extract high purity 1-methylnaphthalene and 2-methylnaphthalene.
Background technology
Extract 1-methylnaphthalene and 2-methylnaphthalene from coal tar wash oil is the main method of producing 1-methylnaphthalene and 2-methylnaphthalene always.In recent years along with industry to the increasing sharply of 1-methylnaphthalene and 2-methylnaphthalene demand, also be subjected to increasing attention from the 1-methylnaphthalene in petroleum cracking by-product tar source and the extraction of 2-methylnaphthalene.
1-methylnaphthalene and 2-methylnaphthalene boiling point only differ 3 ℃, use the method separation 1-methylnaphthalene and the 2-methylnaphthalene of conventional rectification very difficult.The raw material that in addition contains 1-methylnaphthalene and 2-methylnaphthalene is the byproduct of coal tar refining or petroleum cracking, composition is very complicated, wherein some composition boiling point and 1-methylnaphthalene and 2-methylnaphthalene are very approaching, also some composition and 1-methylnaphthalene and 2-methylnaphthalene form azeotrope, so only utilize the conventional rectification method may not obtain purity greater than 90% 1-methylnaphthalene and 2-methylnaphthalene product.In order effectively to address these problems, the past extract from coal tar wash oil methylnaphthalene technological design many schemes.But owing to be subjected to the restriction of equipment level and state of the art at that time, used scheme all seems, and operation is too loaded down with trivial details, and extraction efficiency is not high yet.Particularly,, also there is not industrialized report so far because its material composition and coal tar wash oil have a great difference for extracting methylnaphthalene from petroleum cracking by-product coke oil wash oil.
For example, handle the raw material that comes from coal tar, consider and wherein contain a large amount of quinoline and indoles, designed the technology that removes quinoline and indoles.Generally remove quinoline with pickling, after hydro-oxidation potassium removed indoles, 1-methylnaphthalene and 2-methylnaphthalene were extracted in rectifying again.Perhaps adopt the method for azeotropic distillation, add entrainer in raw material, azeotropic distillation removes quinoline, indoles and other composition simultaneously.And the raw material from petroleum cracking by-product coke oil wash oil is handled in the laboratory, because it is few wherein to contain quinoline and indoles amount, does not generally extract quinoline and indoles, but adopts the method for azeotropic distillation to extract 1-methylnaphthalene and 2-methylnaphthalene.Because pickling process produces a large amount of acid-bearing wastewaters, hydro-oxidation potassium operation produces a large amount of solid slags, does not meet chemical environment close friend's developing direction.Though azeotropic distillation does not have severe contamination, the recycling of expensive entrainer has increased the cost of product greatly.
All there is the cost height to some extent in above-mentioned production method, or pollutes greatly, or operates miscellaneous shortcoming.Particularly to produce highly purified 1-methylnaphthalene and 2-methylnaphthalene, also need to increase the operation of highly energy-consumings such as freezing and crystallizing, equipment, the more loaded down with trivial details complexity of operation.
Summary of the invention
At the existing shortcomings and deficiencies of past technology, the object of the present invention is to provide a kind of method of from tar, extracting 1-first-Ji naphthalene and 2-methylnaphthalene, this method is utilized same set of production unit, both can handle petroleum cracking by-product coke oil wash oil raw material, also the coal tar wash oil raw material can be handled, all highly purified product can be obtained.
The present invention is realized by following technical proposals.Employing comprises the device of an alkanisation polymerization reactor and three placed in-line rectifying tower, the method of 1-methylnaphthalene and 2-methylnaphthalene is extracted in realization from the petroleum cracking by-product coke oil wash oil that contains the methylnaphthalene composition or coal tar wash oil, it is characterized in that comprising following process:
1, to derive from coal tar or petroleum tar, contain methylnaphthalene, naphthalene, tetramethyl-benzene, quinoline, indoles, biphenyl, ancient wine vessel, and total methylnaphthalene content is not less than 60% raw material, add the alkanisation polymerization reactor, and press 0.1%～8% of material quantity weight adds solid acid or liquid acid or their mixing acid in this reactor catalyzer, be warming up to 70 ℃～90 ℃ 0.5%～5.0% adding alkylating agents then by material quantity weight, system was 70 ℃～90 ℃ alkanisation polyreactions 0.5 hour～2 hours, improve temperature to 95 ℃～115 ℃ then, continued the alkanisation polyreaction 1 hour～3 hours.
2, the material after the alkanisation polymerization is added rectifying tower 1 from rectifying tower 1 middle part, this rectifying tower is that 0.06MPa～0.08MPa, column bottom temperature are that 220 ℃～240 ℃ and tower top temperature are to operate under 180 ℃～200 ℃ the condition at pressure, is comprised the lighting end of naphthalene, tetramethyl-benzene by its removed overhead.
3, extraction at the bottom of material that rectifying tower 1 has removed lighting end is by this Tata, add rectifying tower 2 from rectifying tower 2 middle parts, this rectifying tower is 0.05MPa～0.07MPa at pressure, column bottom temperature is 220 ℃～240 ℃, tower top temperature is to operate under 180 ℃～200 ℃ the condition, obtains content by its top of tower and is not less than 95% 2-methylnaphthalene.
4, extraction at the bottom of material that rectifying tower 2 removes the 2-methylnaphthalene is by this Tata, add rectifying tower 3 from rectifying tower 3 middle parts, this rectifying tower is that 0.04MPa～0.06MPa, column bottom temperature are that 220 ℃～240 ℃ and tower top temperature are to operate under 180 ℃～200 ℃ the condition at pressure.Obtain content by its top of tower and be not less than 95% 1-methylnaphthalene.Discharge the heavy constituent that comprise biphenyl, ancient wine vessel and polymerization alkylation product at the bottom of the tower.
Above-mentioned solid acid is SO
4 2-/ Fe
2O
3, SO
4 2-/ ZrO
2, SO
4 2-/ ZrO
2-SiO
2, SO
4 2-/ TiO
2-La
2O
3, SiO
2-ZrO
2Or Zeo-karb.
Above-mentioned liquid acid is sulfuric acid, phosphoric acid or hydrochloric acid.
Above-mentioned alkylating agent is a kind of in iso-butylene, methyl tertiary butyl ether, the trimethyl carbinol, the propylene or several.
The invention has the advantages that, utilize same set of production unit, both can handle petroleum cracking by-product coke oil wash oil raw material, also can handle the coal tar wash oil raw material, the 1-methylnaphthalene of extraction and 2-methylnaphthalene purity are not less than 95%.Technology is simple, realizes automated operation easily.
Description of drawings
Fig. 1 is device of the present invention and schematic flow sheet.
Among Fig. 1: the 1st, alkanisation polymerization reactor, the 2nd, rectifying tower 1,3rd, rectifying tower 2,4th, rectifying tower 3.
Embodiment
Accompanying drawing 11 is described below in conjunction with the accompanying drawings for extracting 1-methylnaphthalene and 2-methylnaphthalene schematic representation of apparatus:
The coal tar wash oil that contains total methylnaphthalene 61% is pumped in raw material tank the alkanisation polymerization reactor, adds the solid acid SO of raw material weight 6% in the alkanisation polymerization reactor
4 2-/ ZrO
2Catalyzer is warmed up to 75 ℃, feeds iso-butylene in 1 hour, the feeding amount of control iso-butylene is 1% of a raw material weight, stop to feed iso-butylene, be warmed up to 100 ℃, continue reaction 1.5 hours, emit material, remove by filter catalyzer, feed liquid enters rectifying tower 1, working pressure 0.08MPa, 233 ± 3 ℃ of column bottom temperatures, 195 ± 3 ℃ of tower top temperatures.At the cat head extraction boiling point of rectifying tower 1 light constituent less than the 2-methylnaphthalene, light constituent mainly contains naphthalene, tetramethyl-benzene etc.The bottoms material enters rectifying tower 2, working pressure 0.06MPa, 225 ± 3 ℃ of column bottom temperatures, 182 ± 3 ℃ of tower top temperatures are not less than 95% 2-methylnaphthalene at the cat head extraction content of rectifying tower 2, the bottoms material enters rectifying tower 3, working pressure 0.04MPa, 238 ± 3 ℃ of column bottom temperatures, 195 ± 3 ℃ of tower top temperatures, at the cat head extraction 1-of rectifying tower 3 methylnaphthalene product, wherein 1-methylnaphthalene content is not less than 95%; The bottoms material is mainly to contain the heavy constituent that connect benzene, ancient wine vessel and polymerization alkylation product etc., enters the heavy constituent storage tank.
1 be described below in conjunction with the accompanying drawings:
The petroleum tar washing oil that contains total methylnaphthalene 73%, in raw material tank, be pumped into the alkanisation polymerization reactor, the vitriol oil that in the alkanisation polymerization reactor, adds raw material weight 0.5%, be warmed up to 85 ℃, fed methyl tertiary butyl ether in 1 hour, the feeding amount of control methyl tertiary butyl ether is 3% of a raw material weight, stop to feed methyl tertiary butyl ether, be warmed up to 110 ℃, continue reaction 2.5 hours, add Ca (OH)
2Material is emitted in neutralization, removes by filter sediment, feed liquid enters rectifying tower 1, and at the cat head extraction boiling point of rectifying tower 1 light constituent less than the 2-methylnaphthalene, the bottoms material enters middle trough 1, working pressure 0.08MPa, 233 ± 3 ℃ of column bottom temperatures, 195 ± 3 ℃ of tower top temperatures.At the cat head extraction boiling point of rectifying tower 1 light constituent less than the 2-methylnaphthalene, light constituent mainly contains naphthalene, tetramethyl-benzene etc.The bottoms material enters rectifying tower 2, working pressure 0.06MPa, 225 ± 3 ℃ of column bottom temperatures, 182 ± 3 ℃ of tower top temperatures are not less than 95% 2-methylnaphthalene at the cat head extraction content of rectifying tower 2, the bottoms material enters rectifying tower 3, working pressure 0.04MPa, 238 ± 3 ℃ of column bottom temperatures, 195 ± 3 ℃ of tower top temperatures, at the cat head extraction 1-of rectifying tower 3 methylnaphthalene product, wherein 1-methylnaphthalene content is not less than 95%; The bottoms material is mainly to contain the heavy constituent that connect benzene, ancient wine vessel and polymerization alkylation product etc., enters the heavy constituent storage tank.
Claims (4)
1. method of from tar, extracting 1-methylnaphthalene and 2-methylnaphthalene, this method adopts the device that comprises an alkanisation polymerization reactor and three placed in-line rectifying tower, 1-methylnaphthalene and 2-methylnaphthalene are extracted in realization from the petroleum cracking by-product coke oil wash oil that contains the methylnaphthalene composition or coal tar wash oil, it is characterized in that comprising following process:
1) will derive from coal tar or petroleum tar, contain methylnaphthalene, naphthalene, tetramethyl-benzene, quinoline, indoles, biphenyl, ancient wine vessel, and total methylnaphthalene content is not less than 60% raw material, add the alkanisation polymerization reactor, and press 0.1%～8% of material quantity weight adds solid acid or liquid acid or their mixing acid in this reactor catalyzer, be warming up to 70 ℃～90 ℃ 0.5%～5.0% adding alkylating agents then by material quantity weight, system was 70 ℃～90 ℃ alkanisation polyreactions 0.5 hour～2 hours, improve temperature to 95 ℃～115 ℃ then, continued the alkanisation polyreaction 1 hour～3 hours;
2) material after the alkanisation polymerization is added rectifying tower (1) from rectifying tower (1) middle part, this rectifying tower is that 0.06MPa～0.08MPa, column bottom temperature are that 220 ℃～240 ℃ and tower top temperature are to operate under 180 ℃～200 ℃ the condition at pressure, is comprised the lighting end of naphthalene, tetramethyl-benzene by its removed overhead;
3) extraction at the bottom of material that rectifying tower (1) has removed lighting end is by this Tata, add rectifying tower (2) from rectifying tower (2) middle part, this rectifying tower is that 0.05MPa～0.07MPa, column bottom temperature are that 220 ℃～240 ℃ and tower top temperature are to operate under 180 ℃～200 ℃ the condition at pressure, obtains content by its top of tower and is not less than 95% 2-methylnaphthalene;
4) extraction at the bottom of material that rectifying tower (2) removes the 2-methylnaphthalene is by this Tata, add rectifying tower (3) from rectifying tower (3) middle part, this rectifying tower is that 0.04MPa～0.06MPa, column bottom temperature are to operate under the condition of 180 ℃～200 ℃ of 220 ℃～240 ℃ and tower top temperatures at pressure, obtains content by its top of tower and is not less than 95% 1-methylnaphthalene; Discharge the heavy constituent that comprise biphenyl, ancient wine vessel and polymerization alkylation product at the bottom of the tower.
2. by the described method of claim 1, it is characterized in that: solid acid is SO
4 2-/ Fe
2O
3, SO
4 2-/ ZrO
2, SO
4 2-/ZrO
2-SiO
2, SO
4 2-/ TiO
2-La
2O
3, SiO
2-ZrO
2Or Zeo-karb.
3. by the described method of claim 1, it is characterized in that: liquid acid is sulfuric acid, phosphoric acid or hydrochloric acid.
4. by the described method of claim 1, it is characterized in that: alkylating agent is a kind of in iso-butylene, methyl tertiary butyl ether, the trimethyl carbinol, the propylene or several.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100141937A CN100393677C (en) | 2005-06-30 | 2005-06-30 | Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar |
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|---|---|---|---|
| CNB2005100141937A CN100393677C (en) | 2005-06-30 | 2005-06-30 | Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar |
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| CN1721380A CN1721380A (en) | 2006-01-18 |
| CN100393677C true CN100393677C (en) | 2008-06-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053355A (en) * | 2018-09-29 | 2018-12-21 | 上海化工研究院有限公司 | A kind of method of continuous rectification biphenyl purification |
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|---|---|---|---|---|
| CN101270028B (en) * | 2007-03-23 | 2012-01-11 | 宝山钢铁股份有限公司 | purification process of alpha-methylnaphthalene |
| CN102078699B (en) * | 2009-12-01 | 2013-06-05 | 宝舜科技股份有限公司 | Direct distillation technology for 2-methylnaphthalene |
| CN102134500B (en) * | 2011-02-17 | 2013-05-15 | 广东新华粤石化股份有限公司 | Method for extracting naphthalene, 1-methylnaphthalene and 2-methylnaphthalene from ethylene tar |
| CN106336338A (en) * | 2015-07-09 | 2017-01-18 | 上海宝钢化工有限公司 | Method for removing quinoline in DMNO-3 |
| CN105646342B (en) * | 2015-12-08 | 2018-12-11 | 长春工业大学 | A kind of method of quinoline in extraction and separation quinoline-biphenyl-naphthalene mixtures |
| CN108586183B (en) * | 2018-04-17 | 2020-10-23 | 鹏辰新材料科技股份有限公司 | Supercritical technology-based method for separating and purifying high-purity alpha-methylnaphthalene |
| CN114225453A (en) * | 2021-11-26 | 2022-03-25 | 安徽金禾实业股份有限公司 | Device and method for extracting furfuryl alcohol by rectification in maltol production |
| CN115044392B (en) * | 2022-06-06 | 2023-08-01 | 中建安装集团有限公司 | Process and device for improving comprehensive utilization additional value of ethylene cracking inferior tar |
| CN115073257B (en) * | 2022-08-03 | 2023-10-27 | 连云港鹏辰特种新材料有限公司 | Method for separating and purifying 1-methylnaphthalene from methylnaphthalene enrichment mother liquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02202592A (en) * | 1989-01-31 | 1990-08-10 | Nkk Corp | Separation and recovery of 2-methylnaphthalene |
| JPH0585959A (en) * | 1991-09-27 | 1993-04-06 | Osaka Gas Co Ltd | Production of methylnaphthalene |
| CN1122320A (en) * | 1994-11-02 | 1996-05-15 | 武汉钢铁(集团)公司 | Method and apparatus for extracting alpha-methyl naphthalene and beta-methylnaphthalene |
-
2005
- 2005-06-30 CN CNB2005100141937A patent/CN100393677C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02202592A (en) * | 1989-01-31 | 1990-08-10 | Nkk Corp | Separation and recovery of 2-methylnaphthalene |
| JPH0585959A (en) * | 1991-09-27 | 1993-04-06 | Osaka Gas Co Ltd | Production of methylnaphthalene |
| CN1122320A (en) * | 1994-11-02 | 1996-05-15 | 武汉钢铁(集团)公司 | Method and apparatus for extracting alpha-methyl naphthalene and beta-methylnaphthalene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053355A (en) * | 2018-09-29 | 2018-12-21 | 上海化工研究院有限公司 | A kind of method of continuous rectification biphenyl purification |
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Assignee: Qilong Chemical Co., Ltd., Shandong Assignor: Tianjin University Contract fulfillment period: 2008.6.15 to 2013.6.14 contract change Contract record no.: 2009120000033 Denomination of invention: Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar Granted publication date: 20080611 License type: Exclusive license Record date: 2009.4.29 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.6.15 TO 2013.6.14; CHANGE OF CONTRACT Name of requester: SHANDONG QILONG CHEMICAL CO., LTD. Effective date: 20090429 |
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