CN1093107C - Gas-phase selective adsorption process for separating mixed dichlorobenzene - Google Patents
Gas-phase selective adsorption process for separating mixed dichlorobenzene Download PDFInfo
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- CN1093107C CN1093107C CN99113692A CN99113692A CN1093107C CN 1093107 C CN1093107 C CN 1093107C CN 99113692 A CN99113692 A CN 99113692A CN 99113692 A CN99113692 A CN 99113692A CN 1093107 C CN1093107 C CN 1093107C
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- dichlorobenzene
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Abstract
The present invention discloses a method for separating mixed dichlorobenzene from zeolite molecular sieves. The separation method of the prior art has the defects of high cost and high energy consumption. In the present invention, mixed dichlorobenzene passes through zeolite molecular sieve adsorption agents in a gas-phase condition, p-dichlorobenzene is selectively adsorbed by the adsorption agents, and residues of the adsorption are m-dichlorobenzene, o-dichlorobenzene and micro p-dichlorobenzene. The adsorbed p-dichlorobenzene is desorbed under a desorbing condition, and the zeolite molecular sieve adsorption agents are regenerated. The residues of the adsorption are rectified by a conventional rectification method, and m-dichlorobenzene whose purity is larger than 99.7% can be prepared.
Description
What the present invention relates to is the method for compartment dichlorobenzene from mixed dichlorobenzene, particularly uses the method for zeolite molecular sieve as solid adsorbent compartment dichlorobenzene.
As everyone knows, Meta Dichlorobenzene is important Organic Chemicals, and all multi-usages are arranged.The compartment dichlorobenzene has many methods from mixed dichlorobenzene, as extractive distillation method, sulfonation method and adsorption method of separation.Because adsorption method of separation has advantage pollution-free, that product purity is high, thereby development is very fast.As U.S. Pat 4,996,380, adopt this method exactly.This method is that the mixed dichlorobenzene liquid phase is passed through X or y-type zeolite adsorbent of molecular sieve, and wherein Meta Dichlorobenzene is adsorbed by selectivity, with desorbing agent the Meta Dichlorobenzene desorption that is adsorbed is come out then.This method has the advantage of general fractionation by adsorption, but the technological process more complicated, thereby investment is also bigger.In addition, owing to all contain desorbing agent in extractum and the suction excess, need to reclaim, thereby energy consumption is also higher with distillation.
The object of the present invention is to provide that a kind of technology is reasonable, equipment is simple, investment is low, can isolate the method for high-purity m-dichlorobenzene from mixed dichlorobenzene.
The present invention is achieved like this, with mixed liquor under adsorption conditions, by the adsorption bed of zeolite adsorbent is housed, the sorbent material in the adsorption bed selectively adsorbs santochlor with gas phase state, and inhaling excess is the mixture of Meta Dichlorobenzene, orthodichlorobenzene and micro-santochlor.The santochlor that is adsorbed, under desorption conditions, through desorbing agent desorption or decompression desorption, desorbing agent is water vapor, carbonic acid gas, nitrogen or less than C
4Lower carbon number hydrocarbons, inhale excess and make Meta Dichlorobenzene through rectifying.The boiling point of three kinds of dichlorobenzene isomers in the raw material of the present invention is: santochlor is 174.1 ℃, and Meta Dichlorobenzene is 173.0 ℃, 180.4 ℃ of (petrochemical complex basic data handbooks of orthodichlorobenzene, Lu Huanzhang etc. write, nineteen eighty-two, first version, Chemical Industry Press publishes and distributes).Selectively adsorbed the santochlor in the raw material owing to the present invention is sorbent used, Meta Dichlorobenzene and the orthodichlorobenzene boiling point inhaled in the excess differ 7.4 ℃, thereby can make the Meta Dichlorobenzene of high purity (more than 99.7%) easily with industrial general rectificating method.
Adsorption conditions of the present invention is: temperature is 180～230 ℃, pressure is normal pressure～0.5Mpa, air speed is 0.1～30/ o'clock (weight), desorption conditions is: use water vapor as desorbing agent, temperature is 180～230 ℃, pressure is normal pressure～2.0Mpa, air speed be 0.1～20/ o'clock (weight), agent water than 0.3～5.0, desorbing agent also can be carbonic acid gas, nitrogen or less than C
4Lower carbon number hydrocarbons.
The preferable absorption separation condition of the present invention is: adsorption temp is 180～200 ℃, adsorptive pressure is normal pressure～0.3Mpa, and the absorption air speed is 0.1～20/ o'clock (weight), and desorption temperature is 180～200 ℃, desorption pressure is normal pressure～1.0Mpa, and the desorption air speed is 0.1～10/ o'clock (weight).
The present invention is sorbent used to be MFI type zeolite adsorbent, and MFI type zeolite molecular sieve comprises ZSM-5 and silicon zeolite (Silicalite-1) zeolite molecular sieve.
The also available ferrierite of the present invention (Ferrierite), but be good with adhesive-free Silicalite-1 zeolite molecular sieve (seeing Chinese patent, patent No. ZL 94 112035.x).Because of this sorbent material has that loading capacity height, selectivity are good, thermostability and good, the no katalysis of chemical stability, desorption and advantages such as regenerability is good, long service life.
It is better that the present invention makes desorbing agent with water vapor, lower and suitable wide than other desorbing agent cost, got rid of the recycling step of desorbing agent in extractum and the suction excess.
The also available decompression desorption of the present invention replaces the desorbing agent desorption, and the pressure of decompression desorption is 0.001Mpa～0.07Mpa, and temperature is 160～230 ℃.
The present invention's preferable condition of desorption that reduces pressure is that the pressure of desorption is 0.001Mpa～0.07Mpa, and temperature is 160～200 ℃.
The present invention has very good effect at the mixed dichlorobenzene separation field, compares with existing technology, and pollution-free, advantages such as product purity is high, technology is reasonable, equipment is simple, less investment, the long easy industrialization of sorbent material life-span are arranged.
Embodiment:
It is as follows that the weight percent of four kinds of raw material A using among the embodiment, B, C, D is formed content:
| Raw material | Weight percent is formed (%) | ||
| Santochlor | Meta Dichlorobenzene | Orthodichlorobenzene | |
| A | 25.30 | 62.21 | 12.49 |
| B | 29.27 | 60.31 | 10.42 |
| C | 33.04 | 56.75 | 10.21 |
| D | 29.51 | 62.19 | 8.30 |
About 300 grams of MFI type zeolite molecular sieve are housed in the adsorption bed among the embodiment 1～6, feed adsorption bed after the feed vaporization, adsorbents adsorb behind the santochlor, obtain to contain the suction excess of Meta Dichlorobenzene, orthodichlorobenzene and micro-santochlor.With desorbing agent (water vapor or micromolecular hydro carbons or gas) or with decompression desorption method desorption, purge out middle distillate and make the santochlor desorption that adsorbs in the zeolite molecular sieve, obtain the mixture of middle distillate and extractum.Inhaling excess, middle distillate and extractum mixture analyzes with gas chromatograph.The suction excess makes purity with conventional precision fractional distillation and is higher than 99.7% Meta Dichlorobenzene.
Embodiment 1, raw material A 62.5 gram vaporization backs feed adsorption bed, Silicalite-1 adhesive-free sorbent material 322 grams are housed in the bed, 193 ℃ of adsorption temps, adsorptive pressure 0.10Mpa is during air speed 1.55/, obtain inhaling excess 15.1 grams, its weight percent consists of Meta Dichlorobenzene 83.50%, santochlor 0.09%, orthodichlorobenzene 16.41%.
Embodiment 2, after in embodiment 1, obtaining 15.1 gram suction excess, water vapor 290 grams during with 193 ℃ of temperature, pressure 0.25Mpa, air speed 1.40/ feed adsorption bed, make the santochlor desorption that adsorbs in the molecular sieve, collect middle distillate and extractum totally 47.2 grams, weight percent consists of Meta Dichlorobenzene 55.53%, santochlor 33.28%, orthodichlorobenzene 11.19%.
Embodiment 3, raw material B 54.3 gram vaporization backs feed adsorption bed, ZSM-5 (Si/Al=380) sorbent material 310 grams are housed in the bed, 188 ℃ of adsorption temps, adsorptive pressure 0.13Mpa is during air speed 1.60/, obtain inhaling excess 12.2 grams, its weight percent consists of Meta Dichlorobenzene 82.37%, santochlor 0.18%, orthodichlorobenzene 17.45%.
Embodiment 4, after in embodiment 3, obtaining 12.2 gram suction excess, adsorption bed is decompressed to 0.06Mpa, to be adsorbed in the santochlor desorption that adsorbs in the molecular sieve at 188 ℃, collect in the cold-trap totally 41.8 grams together with middle distillate, weight percent consists of Meta Dichlorobenzene 53.92%, santochlor 37.65%, orthodichlorobenzene 8.43%.
Embodiment 5, raw material C 57.7 gram vaporization backs feed adsorption bed, Silicalite-1 adhesive-free sorbent material 322 grams are housed in the bed, 185 ℃ of adsorption temps, adsorptive pressure 0.50Mpa is during air speed 1.20/, obtain inhaling excess 6.3 grams, its weight percent consists of Meta Dichlorobenzene 82.79%, santochlor 0.13%, orthodichlorobenzene 17.08%.
Water vapor 201 grams during then with 186 ℃ of temperature, pressure 0.20Mpa, air speed 0.30/ feed adsorption bed, make the santochlor desorption that adsorbs in the molecular sieve, collect middle distillate and extractum totally 51.0 grams, weight percent consists of Meta Dichlorobenzene 53.50%, santochlor 37.18%, orthodichlorobenzene 9.32%.
Embodiment 6, raw material D 50.7 gram vaporization backs feed adsorption bed, Silicalite-1 adhesive-free sorbent material 322 grams are housed in the bed, 218 ℃ of adsorption temps, adsorptive pressure 0.10Mpa is during air speed 1.81/, obtain inhaling excess 17.6 grams, its weight percent consists of Meta Dichlorobenzene 90.94%, santochlor 0.24%, orthodichlorobenzene 8.82%.
Water vapor 1550 grams during then with 220 ℃ of temperature, pressure 0.15Mpa, air speed 9.50/ feed adsorption bed, make the santochlor desorption that adsorbs in the molecular sieve, collect middle distillate and extractum totally 32.9 grams, weight percent consists of Meta Dichlorobenzene 46.86%, santochlor 45.09%, orthodichlorobenzene 8.05%.
Claims (6)
1, a kind of Gas Phase Adsorption is separated the method for mixed dichlorobenzene, it is characterized in that mixed dichlorobenzene passes through the MFI zeolite adsorbent with gas phase state, the adsorbents adsorb santochlor, the suction excess is the santochlor of Meta Dichlorobenzene, orthodichlorobenzene and trace, the santochlor that is adsorbed, through desorbing agent water vapor desorption, zeolite adsorbent obtains regeneration under desorption conditions, inhale excess and make pure Meta Dichlorobenzene through rectifying separation, actual conditions is:
(1) adsorption temp is 180 °～230 ℃, and pressure is normal pressure～0.5Mpa,
Air speed is 0.1～30/ o'clock (weight);
(2) desorption temperature is 180 ℃～230 ℃, and pressure is normal pressure～2.0pa,
Air speed is 0.1～20/ o'clock (weight), and agent water ratio is 3.0～5.0.
2, Gas Phase Adsorption according to claim 1 is separated the method for mixed dichlorobenzene, it is characterized in that absorption, desorption conditions are:
(1) adsorption temp is 180～200 ℃, and pressure is normal pressure～0.3Mpa,
Air speed 0.1～20/ o'clock (weight);
(2) desorption temperature is 180～200 ℃, and pressure is normal pressure～1.0Mpa,
Air speed is 0.1～10/ o'clock (weight).
3, Gas Phase Adsorption according to claim 1 is separated the method for mixed dichlorobenzene, it is characterized in that sorbent material is the Silicalite-1 zeolite adsorbent.
4, Gas Phase Adsorption according to claim 1 is separated the method for mixed dichlorobenzene, it is characterized in that sorbent material is an adhesive-free Silicalite-1 zeolite adsorbent.
5, Gas Phase Adsorption according to claim 1 is separated the method for mixed dichlorobenzene, it is characterized in that desorption is the decompression desorption, and pressure is 0.001Mpa～0.07Mpa, and temperature is 160～230 ℃.
6, Gas Phase Adsorption according to claim 1 is separated the method for mixed dichlorobenzene, it is characterized in that desorption is the decompression desorption, and condition is that pressure 0.01Mpa～0.07Mpa, temperature are 160～200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113692A CN1093107C (en) | 1999-05-10 | 1999-05-10 | Gas-phase selective adsorption process for separating mixed dichlorobenzene |
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| CN99113692A CN1093107C (en) | 1999-05-10 | 1999-05-10 | Gas-phase selective adsorption process for separating mixed dichlorobenzene |
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| CN1240783A CN1240783A (en) | 2000-01-12 |
| CN1093107C true CN1093107C (en) | 2002-10-23 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112225C (en) * | 2000-03-29 | 2003-06-25 | 北京燕山石油化工公司研究院 | Hydrophobic silicalite method for liquid-phase selective adsorption, separation and mixing of dichlorobenzene |
| CN101891586B (en) * | 2010-08-19 | 2012-12-26 | 江苏隆昌化工有限公司 | Process for extracting high-purity m-dichlorobenzene from solid waste chlorobenzene tar |
| CN107340346A (en) * | 2017-08-07 | 2017-11-10 | 安徽东至广信农化有限公司 | The quick determination method of micro dichloro-benzenes in a kind of chlorination benzaldehyde product |
| CN112452103A (en) * | 2020-11-24 | 2021-03-09 | 上海绿强新材料有限公司 | Method for extracting high-purity m-dichlorobenzene by using mixed adsorption bed |
| CN113754543B (en) * | 2021-09-06 | 2022-09-20 | 南京工业大学 | Method for separating high-boiling-point isomer by utilizing gas phase adsorption of hierarchical pore silicon molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996380A (en) * | 1989-11-08 | 1991-02-26 | Uop | Process for extracting meta-dichlorobenzene from isomer mixtures with mixed alkali metal exchanged X zeolite adsorbents |
| CN1017934B (en) * | 1988-12-19 | 1992-08-19 | 齐鲁石油化工研究院 | Rapid measuring method and apparatus for micro anti-active index |
| CN1105968A (en) * | 1993-09-10 | 1995-08-02 | 拜尔公司 | Method for separating m-dichlorobenzene from dichlorobenzene isomer mixture |
-
1999
- 1999-05-10 CN CN99113692A patent/CN1093107C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1017934B (en) * | 1988-12-19 | 1992-08-19 | 齐鲁石油化工研究院 | Rapid measuring method and apparatus for micro anti-active index |
| US4996380A (en) * | 1989-11-08 | 1991-02-26 | Uop | Process for extracting meta-dichlorobenzene from isomer mixtures with mixed alkali metal exchanged X zeolite adsorbents |
| CN1105968A (en) * | 1993-09-10 | 1995-08-02 | 拜尔公司 | Method for separating m-dichlorobenzene from dichlorobenzene isomer mixture |
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