CN1317471A - Coked benzene-thiophenium co-separating process - Google Patents
Coked benzene-thiophenium co-separating process Download PDFInfo
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- CN1317471A CN1317471A CN 01112849 CN01112849A CN1317471A CN 1317471 A CN1317471 A CN 1317471A CN 01112849 CN01112849 CN 01112849 CN 01112849 A CN01112849 A CN 01112849A CN 1317471 A CN1317471 A CN 1317471A
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- benzene
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- thiophenium
- coking benzene
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Abstract
A coked benzene-thiophenium co-separation process features that the strong or superstrong solid acid catalyst is filled into rectifying tower, auxiliaries are added to coked benzene as raw material, and the physical difference between thiophenium in the form of easily biodegradable thiphernium derivative and benzene is increased by rectifying reaction, resulting in obtaining high-quality benzene and thiophernium derivative within short time. Its advantages include simplified process and energy consumption, no pollution to water and less corrosion to equipment.
Description
The present invention relates to the purification techniques of coking benzene, be specifically related to the separation method of benzene and thiophene mixture.
As everyone knows, benzene is important chemical material, has purposes very widely, and it one of mainly comes is the coking benzene that obtains behind the coal Pintsch process.Industrial often is that raw material carries out chemical process with benzene, and in the coking benzene that behind the coal Pintsch process, obtains because of also existing thiophene sulfides matter, influence is to the deep processing of coking benzene, thiophene also is a kind of purposes chemical substance very widely simultaneously, be the important source material or the additive of medicine, agricultural chemicals, material and food, higher use value is arranged, therefore, must fully utilize.
According to the physico-chemical property of benzene and thiophene, traditional method is the sulfuric acid scrubbing method for refining, but this method pollution is big, will be eliminated gradually; Also can adopt the shortening method, but this method investment is big, can not reclaim thiophene; And freeze crystallization, extraction fractional distillation degree of purification are low, and absorption method exists problems such as processing power is little.
Patent EP, 275885,1988 and SU, 1705270,1992 adopt the X type of modifications with Y zeolite benzene-thiophene to be carried out selective adsorption separates, have energy consumption low, make with extra care degree height, advantage such as easy and simple to handle, but because of adsorptive capacity is little, and there is the effective regeneration problem of sorbent material, so poor practicability.
Therefore, the coal tar industry urgently wish to seek a kind of treatment capacity big, refining effect good, can clean the coked benzene-thiophenium co-separating process of production.
The purpose of invention is to disclose a kind of collaborative separation method of coking benzene-thiophene mixture, and the existing in prior technology treatment capacity is little, refining effect is poor, environmental pollution is serious to overcome, can not reclaim the defective of thiophene resource simultaneously.
The technical conceive of invention:
Thiophene is least active in the five-membered ring, is heated to 850 ℃ usually and does not also decompose.The present invention is filled in catalyzer in the reaction fractionating tower with the fixed bed form, in the coking benzene raw material, add auxiliary material, pass through reactive distillation, make thiophene wherein draw back poor properties apart from (boiling point) with the thiophene derivant form of readily biodegradable and benzene, that is: separate by reactive distillation, when obtaining high-quality benzene (superfine benzene standard), also obtain the thiophene derivant that can further utilize.
According to above-mentioned design, the contriver has proposed to realize the technical scheme of the object of the invention by a large amount of tests, and this scheme comprises the steps:
Coking benzene and auxiliary material are placed the reactive distillation Tata still of having filled solid strong acid or super acidic catalyst, the heating total reflux is 1～6 hour under normal pressure or decompression, 60～120 ℃ of temperature of reaction, extract benzene, toluene and dimethylbenzene cut respectively at cat head then, then can obtain thiophene derivant at the bottom of the still, through pre-treatment (be adjusted to Institute of Micro-biology suitable pH) and lipase or Alcaligenes effect, can become pesticides additive agent or have the electronics starting material of electroluminescent properties.
Auxiliary material also can add reaction fractionating tower with the method for continuous dropping.
Said auxiliary material is in bionical synthetic waste edible oil fat, firpene, vinylbenzene or the phosphorus protonic acid one or more of can be used for of easy bio-transformation.
Said solid strong acid or super acidic catalyst are a kind of in polystyrene sulfonic acid resin, chlorsulfonic acid resin or the perfluorosulfonic acid resin.
The weight ratio of coking benzene and auxiliary material is: 100: 1～10, be advisable with 100: 1～7.
The packing height of catalyst levels in reaction fractionating tower is the structured packing height of 1～20 theoretical stage, with 1～10 good, irrelevant substantially with the coking benzene treatment capacity.
For the auxiliary material that makes interpolation more economical rationally, and be further purified the coking benzene that cat head obtains, can be with two reaction fractionating tower series connection, the coking benzene that first tower is obtained carries out refinement treatment again, then can obtain high-quality (superfine) coking benzene, coking toluene and coking xylene.
By above-mentioned disclosed technical scheme as seen, the most outstanding advantage of the present invention is: adopt solid strong acid or super acidic catalyst and auxiliary material, under normal decompression, in the less reaction times, obtain high-quality (superfine) coking benzene, coking toluene and coking xylene by reactive distillation.Make the work simplification of ortho-sulfuric acid separation and purification, saved the facility investment and the energy, and avoided conventional sulfuric acid (washing) method for refining in coke-oven plant to add the water pollution problems that the water termination reaction is produced, make the treating process serialization of coking benzene.And the corrodibility to equipment is less.
Embodiment 1～2
In a band standard ground-in there-necked flask, put into coking benzene 300 grams, add waste edible oil fat 10 grams simultaneously, and install band ground-in thermometer and prolong, give heater heats with variable-voltage transformer, under the polystyrene sulfonic acid resin fixed-bed catalytic, back flow reaction is 2.5 hours under the normal pressure, extracts coking benzene, coking toluene respectively, the result is as follows for coking xylene cut (triphen yield＞88%):
Total thiophene content/mg.L
-1The total decreasing ratio % of thiophene
Embodiment 1 2,460 41.4
Embodiment 2 2,200 47.6
Can obtain the thiophene derivant easily separated, the treated pesticides additive agent that can be used as at the bottom of the tower simultaneously by lipase.
Embodiment 3
In a band standard ground-in there-necked flask, put into coking benzene 600 grams, and install band ground-in thermometer and prolong, under chlorsulfonic acid resin fixed-bed catalytic, adopt continuous processing to add system 10 gram auxiliary material vinylbenzene and 25 gram phosphorus protonic acids, it in pressure 480mmHg and temperature reaction 6 hours under 60 ℃ the condition, cut coking benzene, coking toluene, coking xylene cut (triphen yield＞90%) respectively, the result is as follows:
Total thiophene content/mg.L
-1The total decreasing ratio % of thiophene
830 80.2
Can obtain the thiophene derivant of easily being degraded, the treated starting material that become at the bottom of the tower simultaneously with electroluminescent properties by Alcaligenes.
Embodiment 4
In the device of similar embodiment 3, adding is by coking benzene 200 grams of embodiment 3 gained, under the perfluorosulfonic acid resin fixed-bed catalytic, add vinylbenzene 8 grams, back flow reaction is after 2 hours under the normal pressure, thiophene content in the coking benzene is 0.018mg/100L, in like manner can make with extra care coking toluene and coking xylene; Total triphen yield＞88%.
Claims (6)
1. a coked benzene-thiophenium co-separating process is characterized in that, comprises the steps:
Coking benzene and auxiliary material are placed the reactive distillation Tata still of having filled solid strong acid or super acidic catalyst, the heating total reflux is 1～6 hour under normal pressure or decompression, 60～120 ℃ of temperature of reaction extract benzene, toluene and dimethylbenzene cut respectively at cat head then, then can obtain thiophene derivant at the bottom of the still;
Said auxiliary material is one or more in waste edible oil fat, firpene, vinylbenzene or the phosphorus protonic acid.
2. the method for claim 1 is characterized in that, said solid strong acid or super acidic catalyst are a kind of in polystyrene sulfonic acid resin, chlorsulfonic acid resin or the perfluorosulfonic acid resin.
3. the method for claim 1 is characterized in that, the weight ratio of coking benzene and auxiliary material is: 100: 1～10.
4. method as claimed in claim 3 is characterized in that, the weight ratio of coking benzene and auxiliary material is: 100: 1～7.
5. the method for claim 1 is characterized in that auxiliary material adds reaction fractionating tower with the method with continuous dropping.
6. as the arbitrary described method of claim 1～5, it is characterized in that, the coking benzene that is obtained is carried out refinement treatment with identical method again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011128496A CN1137073C (en) | 2001-05-10 | 2001-05-10 | Coked benzene-thiophenium Co-separating process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011128496A CN1137073C (en) | 2001-05-10 | 2001-05-10 | Coked benzene-thiophenium Co-separating process |
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| Publication Number | Publication Date |
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| CN1317471A true CN1317471A (en) | 2001-10-17 |
| CN1137073C CN1137073C (en) | 2004-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011128496A Expired - Fee Related CN1137073C (en) | 2001-05-10 | 2001-05-10 | Coked benzene-thiophenium Co-separating process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336789C (en) * | 2005-12-31 | 2007-09-12 | 石家庄焦化集团有限责任公司 | Process and apparatus for producing reagent benzene by coking benzene |
| CN100376518C (en) * | 2005-12-31 | 2008-03-26 | 石家庄焦化集团有限责任公司 | Process and apparatus for producing reagent methylbenzene by coking toluene |
| CN100591647C (en) * | 2007-05-29 | 2010-02-24 | 王武谦 | Coking benzene desulfurization process method for co-production of refined benzene and nitrobenzene |
| CN101440083B (en) * | 2007-11-20 | 2012-04-25 | 河南大学 | Method for extracting thiophen from coking crude benzol |
| CN101691321B (en) * | 2009-10-13 | 2012-11-21 | 太原理工大学 | Method for removing unsaturated hydrocarbon and thiophene from coking benzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319918C (en) * | 2005-05-09 | 2007-06-06 | 天津大学 | Method for refining environmental protection type carbonized benzene |
-
2001
- 2001-05-10 CN CNB011128496A patent/CN1137073C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336789C (en) * | 2005-12-31 | 2007-09-12 | 石家庄焦化集团有限责任公司 | Process and apparatus for producing reagent benzene by coking benzene |
| CN100376518C (en) * | 2005-12-31 | 2008-03-26 | 石家庄焦化集团有限责任公司 | Process and apparatus for producing reagent methylbenzene by coking toluene |
| CN100591647C (en) * | 2007-05-29 | 2010-02-24 | 王武谦 | Coking benzene desulfurization process method for co-production of refined benzene and nitrobenzene |
| CN101440083B (en) * | 2007-11-20 | 2012-04-25 | 河南大学 | Method for extracting thiophen from coking crude benzol |
| CN101691321B (en) * | 2009-10-13 | 2012-11-21 | 太原理工大学 | Method for removing unsaturated hydrocarbon and thiophene from coking benzene |
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| CN1137073C (en) | 2004-02-04 |
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