CN1749226A - Complex phase adsorption separating method on hydrophobic silicon zeolite for benzene di-substituted isomer - Google Patents
Complex phase adsorption separating method on hydrophobic silicon zeolite for benzene di-substituted isomer Download PDFInfo
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- CN1749226A CN1749226A CN 200510028921 CN200510028921A CN1749226A CN 1749226 A CN1749226 A CN 1749226A CN 200510028921 CN200510028921 CN 200510028921 CN 200510028921 A CN200510028921 A CN 200510028921A CN 1749226 A CN1749226 A CN 1749226A
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Abstract
The present invention belongs to the field of isomer adsorption and separation technology, and is especially complex phase adsorption and separation method of benzene disubstituted isomer on hydrophobic silicon zeolite. The method includes passing separated mixed benzene disubstituted isomer liquid through the adsorbent bed layer at the temperature lower than the boiling point of the isomer, passing the gaseous desorbent through the adsorbent bed layer at the same temperature to desorb, and performing the next step of adsorption/desorption, so as to realize the continuous adsorption/desorption operation of liquid/gas complex phase. The adsorbent is MFI type hydrophobic silicon zeolite. The present invention has high adsorption and separation efficiency, simple technological process and easy scale production.
Description
Technical field
The invention belongs to isomer adsorption separation technology field, be specifically related to a kind of benzene di-substituted (containing dinitrobenzene, toluene(mono)chloride, dimethylbenzene, dichlorobenzene etc.) isomer complex phase absorption/desorption separation method on hydrophobic silicalite of novelty.This method has the prospect of extensively answering on the organic isomer of fractionation by adsorption.
Background of invention
Usually, benzene di-substituted have three kinds of isomers-contrapositions (P), a position (M), ortho position (O).With dinitrobenzene, toluene(mono)chloride, dimethylbenzene, dichlorobenzene four classes are example, boiling point of its three kinds of isomerss (b.p.) and fusing point (m.p.) see the following form:
| Dimethylbenzene | Toluene(mono)chloride | Dichlorobenzene | Dinitrobenzene | |||||||||
| O | M | P | O | M | P | O | M | P | O | M | P | |
| b.p. | 144 | 139.3 | 138.4 | 159.1 | 161 | 162 | 180-183 | 173 | 174 | 319 | 300 | 299 |
| m.p. | -25 | -47.4 | 13.2 | -35.1 | -48 | 7.5 | -16.7 | -24.8 | 53 | 118 | 90 | 174 |
Data presentation, three kinds of isometry bulk melting points of all kinds of isomer differ bigger, might separate by Steppecd crystallization.But this method often is subjected to generating easily between three kinds of isomerss the restriction of eutectic mixture, is difficult for obtaining highly purified single product.And in three kinds of isomerss, the two boiling-point difference of O-and M-and P-position is bigger, and the boiling point of M-and P-position only differs less than 1 degree.Therefore, with the method for common rectifying, the O-position isomer that separable acquisition purity is higher, and be difficult to the M-position is separated with the P-position with rectificating method.
Chinese patent (ZL 99 1 13692.6) " a kind of gas phase selects to separate the method for mixed dichlorobenzene ") (petrochemical complex 2001,30 (3), 178) propose, the isomer steam-like, mixture passes through hydrophobic silicon zeolite adsorbent without cohesive agent, remove the P position in the dichlorobenzene isomer steam, the mixture of the M of acquisition and O position slips with essence and separates single M of acquisition and O isomer.Adsorbing saturated sorbent material water vapour is the desorbing agent desorption, realizes the continuous operation of absorption/desorption.
It is the corrosion of desorbing agent to cut down the consumption of energy and to alleviate equipment that Chinese patent (ZL 00120892.6) " a kind of gas phase is selected the method for fractionation by adsorption mixed dichlorobenzene " proposes to replace water vapour with organic steam such as chlorobenzenes.Above-mentioned sepn process is vapour/vapour-suction/desorption process.
Chinese patent (the ZL 95 1 12773.X) method of compartment dimethylbenzene and o-Xylol " a kind of from Mixed XYLENE and ethylbenzene " proposes, the steam-like isomer mixture passes through hydrophobic silicon zeolite adsorbent without cohesive agent, remove the P position in the xylene isomer steam, the M that obtains and the mixture of O position obtain single M and O isomer with rectifying separation again.Adsorbing saturated sorbent material water vapour is the desorbing agent desorption, realizes the continuous operation of absorption/desorption.
Obviously, the energy consumption mass consumption of vapour/vapour-suction/desorption process is in the vaporization of separated material and desorbing agent.In addition, at the vaporization temperature height, the unsettled organism of vaporescence is used vapour/vapour-suction/desorption process and is separated also improper for some.
Chinese patent (ZL 00 1 11893.5) " a kind of " (Separation and purification tech with hydrophobic silicalite liquid phase selection fractionation by adsorption dichlorobenzene blended method.2001,24,3,507; Petrochemical complex 2001,30 (2), 121) isolating novel method in liquid phase is proposed, use organism, as chlorobenzene, toluene, p-Xylol, benzene etc. are desorbing agent, realize the fractionation by adsorption of dichlorobenzene isomer in the liquid phase, can significantly cut down the consumption of energy.Its principle is in dichlorobenzene isomer/desorbing agent system, M/P on the binder free silicon sorbent material, and there is very high separation factor the M/O position, can realize the fractionation by adsorption in the liquid phase.
Chinese patent (ZL 99108761.5) " a kind of method of selecting the fractionation by adsorption p-Xylol with hydrophobic silicalite " (Microporous ﹠amp; Mesoporous materials, 2000,39 (1-2), 149; Petrochemical complex, 2001,30 (1), 20) isolating novel method in liquid phase is proposed, use organism, as chlorobenzene, toluene, p-Diethylbenzene, benzene etc. are desorbing agent, realize the fractionation by adsorption of xylene isomer in the liquid phase, can significantly cut down the consumption of energy.Its principle is in xylene isomer/desorbing agent system, M/P on the binder free silicon sorbent material, and there is very high separation factor the M/O position, can realize the fractionation by adsorption in the liquid phase.
But in liquid phase, realize successive liquid/liquid-absorption/desorption manipulation, normally adopt expensive complicated simulation moving-bed equipment and technology to realize.This is for dichlorobenzene, the isomer of dinitrobenzene and toluene(mono)chloride etc., and the only hundreds of products productions to thousands of tons of/year of its market demand are not reasonable.
Summary of the invention
The present invention be directed to the new benzene di-substituted isomer adsorption separating method of the shortcoming proposition of above-mentioned separation method.
The benzene di-substituted isomer form and aspect adsorption separating method that the present invention proposes, be with separated benzene mixed di-substituted isomer liquid, be lower than this below isomer boiling temperature by adsorbent bed, the gaseous state desorbing agent under uniform temp by adsorbent bed carry out desorption after, carry out next step absorption/desorption again, realize the operation of liquid/gas complex phase absorption/desorption continuous operation.Concrete steps are as follows:
Liquid phase benzene di-substituted isomer mixture (A material) is being lower than under this isomer boiling temperature 10-100 degree by adsorbent bed, and at this moment, the P-position is adsorbed, and the mixture of O-position and M-position is suction excess oil (B material); Before adsorption bed is saturated by the P-position, stop charging, switch N immediately
2Blow in carrying out, with the isomer mixture in the stripping dead space; Then with the gaseous state desorbing agent under uniform temp by the adsorbent bed desorption that carries out, make P-position (C material) desorption that is adsorbed; After adsorption bed is finished first round absorption/desorption, enter second and take turns same operation.
Inhale excess oil (B material) and can pass through rectifying tower, separate with the O-position M-position that boiling point is differed 5-7 ℃ by the column plate separate effect.
In the aforesaid method, sorbent material adopts MFI type zeolite (ZSM-5), especially use high silicon or all-silica MFI type hydrophobic silicalite, it is the Silicalite-1 zeolite, the absorption air speed is 0.5-4.0, the gaseous state desorbing agent can be gases such as nitrogen, hydrogen, carbonic acid gas, liquefied petroleum gas (LPG), is organic steam such as benzene, toluene, sherwood oil, chlorobenzene, ethylbenzene perhaps, and the desorption air speed is 0.5-5.0.Here so-called air speed is meant that 1000 gram sorbent materials per hour pass through the amount (liter) of liquid or gas.
Used its structure aperture of MFI type hydrophobic silicon zeolite adsorbent (Chinese patent ZL 94 1 12035.X) of the present invention is a nano level, binder free, to three kinds of isomers-contrapositions (P) being arranged by benzene di-substituted, between the position (M), there is very high adsorption selectivity P position in the ortho position (O), no acidic and base catalysis center, no strong adsorption center, the easy desorption of the benzene di-substituted molecule in P position that is adsorbed, and can not cause the coking charing because of chemical transformation takes place in katalysis on the molecular sieve surface, stop up the duct, make the sorbent material inactivation.The inventive method, fractionation by adsorption efficient height, and also technology is simple, is easy to accomplish scale production.
Embodiment
It is as follows that the weight percent of the A raw material that uses among the embodiment is formed content:
| Raw material | Weight percent is formed (%) | ||
| Right | Between | Adjacent | |
| Dimethylbenzene | 15 | 60 | 25 |
| Toluene(mono)chloride | 18 | 56 | 26 |
| Dichlorobenzene | 17 | 55 | 28 |
| Oil of mirbane | 13 | 54 | 33 |
About 300 grams of MFI type zeolite molecular sieve are housed in the adsorption bed among the embodiment, raw material heating back is by adsorption bed, adsorbents adsorb the contraposition disubstituted benzenes, obtain to contain a disubstituted benzenes, adjacent disubstituted benzenes and trace suction excess to disubstituted benzenes, to absorption saturated after, switch N
2The A raw material of stripping sorbent material dead space.Then, purge out the mixture of middle runnings and extractum with desorbing agent (nitrogen, hydrogen, carbonic acid gas, gases such as liquefied petroleum gas (LPG), benzene, toluene, sherwood oil, chlorobenzene, ethylbenzene, organic steam such as oil of mirbane) or with the desorption method desorption that reduces pressure.Inhaling excess, middle distillate and extractum mixture analyzes with liquid chromatograph.Inhale excess oil with the precision fractional distillation of routine make purity be higher than 99.7% between disubstituted benzenes.
Embodiment 1, raw material dimethylbenzene raw material 65 gram heating backs feed adsorption bed, MFI type silicon zeolite adsorbent 300 grams are housed in the bed, 120 ℃ of adsorption temps, adsorptive pressure 0.10MPa is during air speed 1/, obtain inhaling excess oil 18 grams, its weight percent consists of m-xylene 65.0%, p-Xylol 0.6%, o-Xylol 34.4%.The back gets middle runnings with nitrogen purging, and pressure is 0.15MPa, and toluene 250 grams of air speed 1.5 feed adsorbent, collects middle runnings and extractum totally 47 grams, and weight percent consists of m-xylene 58.1%, p-Xylol 20.5%, o-Xylol 21.4%.
Embodiment 2, raw material toluene(mono)chloride 57 gram heating backs feed adsorption bed, MFI type silicon zeolite adsorbent 300 grams are housed in the bed, 130 ℃ of adsorption temps, adsorptive pressure 0.10MPa is during air speed 1/, obtain inhaling excess oil 16 grams, its weight percent consists of m-chlorotoluene 64.0%, parachlorotoluene 0.5%, ortho-chlorotolu'ene 35.5%.The back gets middle runnings with nitrogen purging, and pressure is 0.15MPa, and Benzene Chloride 250 grams of air speed 1.5 feed adsorbent, collects middle runnings and extractum totally 41 grams, and weight percent consists of m-chlorotoluene 53.3%, parachlorotoluene 24.4%, ortho-chlorotolu'ene 22.3%.
Embodiment 3, raw material dichlorobenzene 70 gram heating backs feed adsorption bed, MFI type silicon zeolite adsorbent 300 grams are housed in the bed, 160 ℃ of adsorption temps, adsorptive pressure 0.10MPa is during air speed 1/, obtain inhaling excess oil 15 grams, its weight percent consists of Meta Dichlorobenzene 66.0%, to toluene dichloride 0.8%, and orthodichlorobenzene 32.2%.The back gets middle runnings with nitrogen purging, and pressure is 0.15MPa, and Benzene Chloride 250 grams of air speed 1.5 feed adsorbent, collects middle runnings and extractum totally 55 grams, and weight percent consists of Meta Dichlorobenzene 52.0%, santochlor 26.7%, orthodichlorobenzene 21.3%.
Embodiment 4, raw material dinitrobenzene 62 gram heating backs feed adsorption bed, MFI type silicon zeolite adsorbent 300 grams are housed in the bed, 280 ℃ of adsorption temps, adsorptive pressure 0.15MPa, air speed 1, obtain inhaling excess oil 10 grams, its weight percent consists of Meta-dinitrobenzene 60.0%, paradinitrobenzene 0.9%, o-dinitrobenzene 39.1%.The back gets middle runnings with nitrogen purging, and pressure is 0.15MPa, and oil of mirbane 250 grams of air speed 1.5 feed adsorbent, collect middle runnings and extractum totally 52 grams, weight percent consists of Meta-dinitrobenzene 52.8%, paradinitrobenzene 15.4%, o-dinitrobenzene 31.8%.
Claims (5)
1, a kind of benzene mixed di-substituted isomer complex phase adsorption separating method, it is characterized in that concrete steps are: with liquid phase benzene di-substituted isomer mixture, be lower than under this isomer boiling temperature 10-100 degree by adsorbent bed, at this moment, the P-position is adsorbed, and the mixture of O-position and M-position is for inhaling excess oil; Before adsorption bed is saturated by the P-position, stop charging, switch N immediately
2Blow in carrying out, with the isomer mixture in the stripping dead space, then with the gaseous state desorbing agent under uniform temp by the adsorbent bed desorption that carries out, make the P-position desorption that is adsorbed; After adsorption bed is finished first round absorption/desorption, enter second wheel operation; Inhale excess oil through rectifying tower, separate with the O-position M-position that boiling point is differed 5-7 ℃ by the column plate separate effect.
2, method according to claim 1 is characterized in that sorbent material adopts MFI type zeolite.
3, method according to claim 1, it is characterized in that adsorbing air speed is 0.5-4.0.
4, method according to claim 1 is characterized in that described gaseous state desorbing agent is nitrogen, hydrogen, carbonic acid gas or liquefied petroleum gas (LPG) gas, or the organic steam of benzene, toluene, sherwood oil, chlorobenzene, p-Xylol or ethylbenzene.
5, method according to claim 1 is characterized in that the desorbing agent air speed is 0.5-5.0.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153438A (en) * | 2011-03-04 | 2011-08-17 | 苏州久泰集团公司 | Method for producing high-purity petroleum m-xylene |
| CN104275154A (en) * | 2014-10-16 | 2015-01-14 | 东南大学 | Composite material capable of separating mixed xylene and preparation method of composite material capable of separating mixed xylene |
| CN106237652A (en) * | 2015-06-11 | 2016-12-21 | 上海复榆新材料科技有限公司 | Molecular sieve is utilized to be selectively adsorbing and separating method as adsorbent |
| CN114805080A (en) * | 2022-06-10 | 2022-07-29 | 福建技术师范学院 | Method for continuously separating 3-chloro-4-fluoronitrobenzene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705909A (en) * | 1986-02-27 | 1987-11-10 | Mobil Oil Corporation | Process for the separation of para-xylene |
| CN1095818C (en) * | 1999-07-17 | 2002-12-11 | 北京燕山石油化工公司研究院 | Process for separating p-xylene with hydrophobic silicic zeolite by selective adsorption |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153438A (en) * | 2011-03-04 | 2011-08-17 | 苏州久泰集团公司 | Method for producing high-purity petroleum m-xylene |
| CN104275154A (en) * | 2014-10-16 | 2015-01-14 | 东南大学 | Composite material capable of separating mixed xylene and preparation method of composite material capable of separating mixed xylene |
| CN104275154B (en) * | 2014-10-16 | 2016-06-01 | 东南大学 | A kind of matrix material and its preparation method that can be separated Mixed XYLENE |
| CN106237652A (en) * | 2015-06-11 | 2016-12-21 | 上海复榆新材料科技有限公司 | Molecular sieve is utilized to be selectively adsorbing and separating method as adsorbent |
| CN106237652B (en) * | 2015-06-11 | 2019-09-20 | 上海复榆新材料科技有限公司 | Method is selectively adsorbing and separating using molecular sieve as adsorbent |
| CN114805080A (en) * | 2022-06-10 | 2022-07-29 | 福建技术师范学院 | Method for continuously separating 3-chloro-4-fluoronitrobenzene |
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