CN102382099B - Method for preparing thiophene through variable pressure azeotropic distillation - Google Patents
Method for preparing thiophene through variable pressure azeotropic distillation Download PDFInfo
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- CN102382099B CN102382099B CN 201110348713 CN201110348713A CN102382099B CN 102382099 B CN102382099 B CN 102382099B CN 201110348713 CN201110348713 CN 201110348713 CN 201110348713 A CN201110348713 A CN 201110348713A CN 102382099 B CN102382099 B CN 102382099B
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Abstract
The invention discloses a method for preparing thiophene through variable pressure azeotropic distillation. The method is carried out in a first distilling tower and a second distilling tower which are serially connected with each other, and comprises the following steps of (1) mixing crude thiophene extracted from coked crude benzene and an entrainer according to a weight ratio of 60-65: 35-40 to obtain an azeotrope; entering the first distilling tower firstly; distilling at a pressure of 0.08-0.12Mpa, obtaining a first azeotrope on the top of the tower at the temperature 65 to 75 DEC G according to the weight ratio of the thiophene to the entrainer of 65-68 : 32-35; and (2) sending the first azeotrope into the second distilling tower, distilling at a pressure of 0.4-0.5Mpa, and obtaining the finished product of thiophene at the bottom of the distilling tower at the temperature of 130 to 140 DEC G. The crude thiophene extracted from the coked crude benzene is effectively utilized; the economic benefit is good; the process flow is simple; pollution to environment is low; and a product with high purity can be obtained.
Description
Technical field
The present invention relates to the distilation technical field, relate in particular to a kind of low levels thiophene that extracts in the coking crude benzene and be the method for raw material transformation component distillation high-purity thiophene.
Background technology
Thiophene be a kind of colourless, foul smelling, can tear-gas liquid.Thiophene is natural to be present in the oil, and content is up to several percentage points, and the industrial sex change that is mainly used in the ethyl alcohols also can be used as solvent.Thiophene can replace benzene as the raw material of producing dyestuff and plastics in many occasions, but because thiophene character is comparatively active, general not as good by the produced product characteristics of benzene.The new purposes of thiophene-based heterogeneous ring compound constantly is developed, and Bell Laboratory is found can become the plastics with superconducting property after the thiophene polymerization, and cost is low, is expected to be widely used in the fields such as quantum computer and superelectron equipment.The molecular configuration that changes thiophen polymer improves superconducting temperature, can be made into various superconduction plastics, is applied to the high-tech areas such as Aeronautics and Astronautics, military project.
Thiophene is present in the crude benzol cut of coking generation, and most suitability for industrialized production is that thiophene is removed as the impurity in a kind of tar, and is approaching because of the boiling point of thiophene and benzene, is difficult to general fractionating process the two be separated.Present rectifying extracting method in the world mainly is hydrofining method and sulfuric acid treatment method, and the hydrofining method can obtain high-quality benzene, but Technology is complicated, and operational condition is harsh, and facility investment is large, and tooling cost is high, is difficult to apply on a small scale; Sulfuric acid process is seriously polluted, yield is low, aftertreatment is difficult, although technique is comparatively ripe, purifies the degree of depth inadequate, and this method is under an embargo in many developed countries; In addition also have solvent extration and freeze crystallization, but all be difficult to obtain highly purified product.In a lot of chemosynthesis take benzene as solvent, have a strong impact on quality product because there being micro-thiophene to exist, even scrap.
Therefore the recovery refining and thiophene of coking benzene is a technical barrier always, in hydrofining method and sulfuric acid treatment method, the thiophene destruction that all is decomposed in treating process is discharged in the environment at last, this has not only wasted limited resources, also environment has been caused serious pollution.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiency that prior art exists, provide a kind of good in economic efficiency, method that transformation component distillation that technical process is simple and environmental pollution is little, product purity is high is produced thiophene.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of transformation component distillation is produced the method for thiophene, and described producing in the first and second two distillation towers of mutual series connection carried out, and may further comprise the steps:
The thick thiophene that (1) will extract from coking crude benzene and entrainer form azeotrope with the weight ratio of 60-65: 35-40, at first enter the first distillation tower, under pressure 0.08-0.12Mpa, distill, tower top temperature 65-75 ℃, the weight ratio that cat head obtains thiophene and entrainer is the first azeotrope of 65-68: 32-35;
(2) described the first azeotrope is entered second column, under pressure 0.4-0.5Mpa, distill, column bottom temperature 130-140 ℃, obtain the finished product thiophene at the bottom of the tower.
As a kind of technical scheme, the weight ratio that the cat head of described second column obtains thiophene and entrainer is the second azeotrope of 55-58: 42-45.
As a kind of technical scheme, described entrainer is one or more in hexanaphthene, water, methylcyclohexane, methyl alcohol and the ethanol.
As a kind of technical scheme, described the first distillation tower column bottom temperature is 80-90 ℃.
As a kind of technical scheme, the tower top temperature of described second column is 100-110 ℃.
As a kind of technical scheme, the tower theoretical plate number is 120 in described the first distillation tower and the second column.
As a kind of technical scheme, be provided with wire packing in described the first distillation tower and the second column.
As a kind of technical scheme, the second azeotrope described in the step (2) is recycled.
As a kind of technical scheme, the purity of the finished product thiophene that obtains in the step (2) is more than 99.9wt%.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
The content of thiophene in coking crude benzene can reach 0.3-0.5%; generally all be to destroy to emit in coked crude benzene refining technique in the past; the low levels thiophene that the present invention extracts in the coking crude benzene is as raw material; improved in the past and in the technique thiophene had been destroyed the way of draining; saved the energy; protect environment, obtained simultaneously considerable economic benefit.
Entrainer is present in the overhead product behind the second column high pressure distillation among the present invention, and incoming stock tank reclaims and uses, and has avoided the subsequent disposal of entrainer, has saved the energy, discharges protection of the environment without waste.
The present invention adopts the transformation distillation mode of high pressure after the first low pressure, because so two distillation tower distillation pressure difference material azeotropic form different, the distillation pressure of the first distillation tower and second column raises successively, the content of thiophene also raises successively so, finally can obtain more highly purified thiophene, the thiophene purity that the present invention produces has reached the quality standard of the thiophene of chemical synthesis manufacturing more than 99.9wt%.
The present invention carries out in the first distillation tower and second column, be provided with wire packing in the tower, wire packing has advantages of that turndown ratio is large, scale effect is not clear easily, number of theoretical plate is high, flux is large, pressure decreased, low-load performance are good, can satisfy the requirement of high-accuracy distillation, for the rectifying separation of high purity product provides favourable condition.The first distillation tower and second column are connected mutually, and technique is continuous, and each material is distributing equilibrium and control convenience in tower, technical process is simple, having guaranteed the stability of thiophene quality, is iron and steel enterprise and coking oil enterprise carries out deep processing and utilization to byproduct better method, is worthy of popularization.
Description of drawings
Accompanying drawing is the process flow sheet of the embodiment of the invention;
Among the figure: 1. thiophene extraction column, 11. coking crude benzene imports, 12. thick thiophene outlets, 13. crude benzol high boiling material outlet, 2. the first distillation tower, 21. azeotrope imports, 22. the outlet of the first azeotrope, the outlet of 23. high boiling material, 24. wire packings, 3. second column, 31. first azeotrope imports, the outlet of 32. second azeotropes, 33. finished product thiophene outlet, 34. wire packing, 4. head tank, 5. entrainer.
Embodiment
Below in conjunction with drawings and Examples, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Coking crude benzene entered the thiophene extraction column 1 from coking crude benzene import 11 purify, thick thiophene outlet 12 obtains thick thiophene, and crude benzol high boiling material outlet 13 obtains the crude benzol high boiling material.Thick thiophene enters the first distillation tower 2 through azeotrope import 21, entrainer 5 also enters the first distillation tower 2, thick thiophene and entrainer form azeotrope, be provided with wire packing 24 in the first distillation tower 2, azeotrope is distilled, the first azeotrope outlet 22 obtains the first azeotrope, and high boiling material outlet 23 obtains high boiling material; The first azeotrope enters second column 3 through the first azeotrope import 31, is provided with wire packing 34 in the second column 3, distills, and the second azeotrope outlet 32 obtains the second azeotrope, and finished product thiophene outlet 33 obtains the finished product thiophene.
Embodiment 1
The thiophene that the content that will extract from coking crude benzene is lower and hexanaphthene enter the first distillation tower with 65: 35 ratio of mass ratio, control pressure 0.08Mpa, 65 ℃ of tower top temperatures, 80 ℃ of column bottom temperatures, the first azeotrope that comprises thiophene and hexanaphthene from overhead extraction, with this understanding, the azeotropic ratio of the thiophene of extraction and hexanaphthene is 68: 32, extraction high boiling material at the bottom of the tower.
The first azeotrope of 68: 32 thiophene and hexanaphthene is entered second column, control pressure is 0.4MPa, 100 ℃ of control tower top temperatures, 130 ℃ of column bottom temperatures, the second azeotrope that when overhead extraction pressure is 0.4MPa, comprises thiophene and hexanaphthene, the azeotropic ratio of thiophene and hexanaphthene is 58: 42, with the second azeotrope more incoming stock tank recycle, the highly purified thiophene of top extraction at the bottom of the tower, the thiophene purity that the present embodiment is produced sees Table 1.
Embodiment 2
The thiophene that the content that will extract from coking crude benzene is lower and hexanaphthene enter the first distillation tower with 63: 37 ratio of mass ratio, control pressure 0.1Mpa, 70 ℃ of tower top temperatures, 85 ℃ of column bottom temperatures, the first azeotrope that comprises thiophene and hexanaphthene from overhead extraction, with this understanding, the azeotropic ratio of the thiophene of extraction and hexanaphthene is 67: 33, extraction high boiling material at the bottom of the tower;
The first azeotrope of 67: 33 thiophene and hexanaphthene is entered second column, control pressure is 0.45MPa, 105 ℃ of control tower top temperatures, 135 ℃ of column bottom temperatures, the second azeotrope that when overhead extraction pressure is 0.45MPa, comprises thiophene and hexanaphthene, the azeotropic ratio of thiophene and hexanaphthene is 57: 43, with the second azeotrope more incoming stock tank recycle, the highly purified thiophene of top extraction at the bottom of the tower, the thiophene purity that the present embodiment is produced sees Table 1.
Embodiment 3
The thiophene that the content that will extract from coking crude benzene is lower and hexanaphthene enter the first distillation tower with 60: 40 ratio of mass ratio, control pressure 0.12Mpa, 75 ℃ of tower top temperatures, 90 ℃ of column bottom temperatures, the first azeotrope that comprises thiophene and hexanaphthene from overhead extraction, with this understanding, the azeotropic ratio of the thiophene of extraction and hexanaphthene is 65: 35, extraction high boiling material at the bottom of the tower;
The first azeotrope of 65: 35 thiophene and hexanaphthene is entered second column, control pressure is 0.5MPa, 110 ℃ of control tower top temperatures, 140 ℃ of column bottom temperatures, the second azeotrope of thiophene and hexanaphthene when being 0.5MPa from overhead extraction pressure, the azeotropic ratio of thiophene and hexanaphthene is 55: 45, with the second azeotrope more incoming stock tank recycle, the highly purified thiophene of top extraction at the bottom of the tower, the thiophene purity that the present embodiment is produced sees Table 1.
Embodiment 4
The thiophene that the content that will extract from coking crude benzene is lower and methylcyclohexane enter the first distillation tower with 65: 35 ratio of mass ratio, control pressure 0.08Mpa, 65 ℃ of tower top temperatures, 80 ℃ of column bottom temperatures, the first azeotrope that comprises thiophene and methylcyclohexane from overhead extraction, with this understanding, the azeotropic ratio of the thiophene of extraction and methylcyclohexane is 68: 32, extraction high boiling material at the bottom of the tower;
The first azeotrope of 68: 32 thiophene and methylcyclohexane is entered second column, control pressure is 0.4MPa, 100 ℃ of control tower top temperatures, 130 ℃ of column bottom temperatures, the second azeotrope that when overhead extraction pressure is 0.4MPa, comprises thiophene and methylcyclohexane, the azeotropic ratio of thiophene and methylcyclohexane is 58: 42, with the second azeotrope more incoming stock tank recycle, the highly purified thiophene of top extraction at the bottom of the tower, the thiophene purity that the present embodiment is produced sees Table 1.
Embodiment 5
The thiophene that the content that will extract from coking crude benzene is lower and ethanol enter the first distillation tower with 63: 37 ratio of mass ratio, control pressure 0.1Mpa, 70 ℃ of tower top temperatures, 85 ℃ of column bottom temperatures, the first azeotrope that comprises thiophene and ethanol from overhead extraction, with this understanding, the azeotropic ratio of the thiophene of extraction and ethanol is 67: 33, extraction high boiling material at the bottom of the tower;
The first azeotrope of 67: 33 thiophene and ethanol is entered second column, control pressure is 0.45MPa, 105 ℃ of control tower top temperatures, 135 ℃ of column bottom temperatures, the second azeotrope that when overhead extraction pressure is 0.45MPa, comprises thiophene and ethanol, the azeotropic ratio of thiophene and ethanol is 57: 43, with the second azeotrope more incoming stock tank recycle, the highly purified thiophene of top extraction at the bottom of the tower, the thiophene purity that the present embodiment is produced sees Table 1.
Embodiment 6
The thiophene that the content that will extract from coking crude benzene is lower and water enter the first distillation tower that has 120 blocks of theoretical trays and be provided with wire packing with 60: 40 ratio of mass ratio, control pressure 0.12Mpa, 75 ℃ of tower top temperatures, 90 ℃ of column bottom temperatures, the first azeotrope that comprises thiophene and water from overhead extraction, with this understanding, the azeotropic ratio of the thiophene of extraction and water is 65: 35, extraction high boiling material at the bottom of the tower;
The first azeotrope of 65: 35 thiophene and water is entered the second column that has 120 blocks of theoretical trays and be provided with wire packing, control pressure is 0.5MPa, 110 ℃ of control tower top temperatures, 140 ℃ of column bottom temperatures, the second azeotrope of thiophene and water when being 0.5MPa from overhead extraction pressure, the azeotropic ratio of thiophene and water is 55: 45, with the second azeotrope more incoming stock tank recycle, the highly purified thiophene of top extraction at the bottom of the tower, the thiophene purity that the present embodiment is produced sees Table 1.
Table 1
| Product | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Thiophene (wt%) | 99.93 | 99.96 | 99.95 | 99.94 | 99.96 | 99.95 |
Claims (8)
1. a transformation component distillation is produced the method for thiophene, it is characterized in that, described producing in the first and second two distillation towers of mutual series connection carried out, and may further comprise the steps:
The thick thiophene that (1) will extract from coking crude benzene and entrainer form azeotrope with the weight ratio of 60-65: 35-40, at first enter the first distillation tower, under pressure 0.08-0.12Mpa, distill, tower top temperature 65-75 ℃, the weight ratio that cat head obtains thiophene and entrainer is the first azeotrope of 65-68: 32-35;
(2) described the first azeotrope is entered second column, under pressure 0.4-0.5Mpa, distill, column bottom temperature 130-140 ℃, obtain the finished product thiophene at the bottom of the tower;
Described entrainer is one or more in hexanaphthene, water, methylcyclohexane, methyl alcohol and the ethanol.
2. a kind of transformation component distillation as claimed in claim 1 is produced the method for thiophene, it is characterized in that, the weight ratio that the cat head of described second column obtains thiophene and entrainer is the second azeotrope of 55-58: 42-45.
3. a kind of transformation component distillation as claimed in claim 1 is produced the method for thiophene, it is characterized in that: described the first distillation tower column bottom temperature is 80-90 ℃.
4. a kind of transformation component distillation as claimed in claim 1 is produced the method for thiophene, it is characterized in that: the tower top temperature of described second column is 100-110 ℃.
5. a kind of transformation component distillation as claimed in claim 1 is produced the method for thiophene, it is characterized in that: the tower theoretical plate number is 120 in described the first distillation tower and the described second column.
6. a kind of transformation component distillation as claimed in claim 5 is produced the method for thiophene, it is characterized in that: be provided with wire packing in described the first distillation tower and the second column.
7. a kind of transformation component distillation as claimed in claim 2 is produced the method for thiophene, it is characterized in that: the second azeotrope described in the step (2) is recycled.
8. a kind of transformation component distillation as claimed in claim 1 is produced the method for thiophene, it is characterized in that: the purity of the finished product thiophene that obtains in the step (2) is more than 99.9wt%.
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| CN103044319B (en) * | 2013-01-25 | 2014-09-24 | 山东元利科技股份有限公司 | Method for extracting 2-picoline and 3-picoline from coking crude benzene |
| CN103044318A (en) * | 2013-01-25 | 2013-04-17 | 山东元利科技股份有限公司 | Method for extracting pyridine from coked crude benzene |
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| CN1552682A (en) * | 2003-05-28 | 2004-12-08 | 北京石油化工学院 | Method for preparing purified petroleum benzine and concentrating thiofuran by cruden benzol |
| CN101219918A (en) * | 2007-01-08 | 2008-07-16 | 太原市侨友化工有限公司 | Method for refining carbonization crude benzole |
| CN101440083A (en) * | 2007-11-20 | 2009-05-27 | 河南大学 | Method for extracting thiophen from coking crude benzol |
| CN102001906A (en) * | 2007-01-08 | 2011-04-06 | 太原市侨友化工有限公司 | Coked crude benzene refining method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1552682A (en) * | 2003-05-28 | 2004-12-08 | 北京石油化工学院 | Method for preparing purified petroleum benzine and concentrating thiofuran by cruden benzol |
| CN101219918A (en) * | 2007-01-08 | 2008-07-16 | 太原市侨友化工有限公司 | Method for refining carbonization crude benzole |
| CN102001906A (en) * | 2007-01-08 | 2011-04-06 | 太原市侨友化工有限公司 | Coked crude benzene refining method |
| CN101440083A (en) * | 2007-11-20 | 2009-05-27 | 河南大学 | Method for extracting thiophen from coking crude benzol |
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| 张亮.萃取精馏法精制苯与回收噻吩.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2009,(第4期),第B016-89页. |
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