CN1112226C - Gas-phase selective adsorption process for separating dichlorobenzene from mixture - Google Patents
Gas-phase selective adsorption process for separating dichlorobenzene from mixture Download PDFInfo
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- CN1112226C CN1112226C CN 00120892 CN00120892A CN1112226C CN 1112226 C CN1112226 C CN 1112226C CN 00120892 CN00120892 CN 00120892 CN 00120892 A CN00120892 A CN 00120892A CN 1112226 C CN1112226 C CN 1112226C
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Abstract
The present invention discloses a method for separating mixed dichlorobenzene by gas-phase selective adsorption. The present invention adopts MFI type zeolite (Silicalite-1) molecular sieves as adsorption agents, benzene, mono-substituted alkylbenzene, p-disubstituted alkylbenzene, mono-substituted halogeno benzene or the mixture of the benzene, the mono-substituted alkylbenzene, the p-disubstituted alkylbenzene and the mono-substituted halogeno benzene is used as a desorbing agent, mixed dichlorobenzene passes through the zeolite molecular sieves which are used as adsorption agents in a gas-phase state, p-dichlorobenzene is selectively adsorbed by the adsorption agents, residues after the absorption are m-dichlorobenzene, o-dichlorobenzene and a little amount of p-dichlorobenzene, the adsorbed p-dichlorobenzene is desorbed under a desorption condition, the residues after the absorption are rectified by a conventional rectification method, and m-dichlorobenzene whose purity is higher than 99.7% can be prepared. The water content of the adsorption agents of the present invention does not need controlling, and the adsorption agents can be regenerated.
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 A4,996,380, 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, this sorbent material is the hydrophilic sorbent material, needs strict control sorbent material water content in the use, sorbent material competence exertion optimal separation usefulness.Make sorbent material immerse a large amount of moisture content or heavy oil kind as careless manipulation, adsorbent activity descends even loses activity fully, must change sorbent material.
The applicant has also applied for the method (CN1240783A) of a gas phase selection fractionation by adsorption mixed dichlorobenzene, be characterized in making sorbent material, making desorbing agent with water vapor with MFI type zeolite molecular sieve, fractionation by adsorption mixed dichlorobenzene under gas phase condition, further discover: in the muriate system, at high temperature muriate contacts the corrodibility of equipment bigger for a long time with water vapor.This just impels the contriver to remove to find new desorbing agent addressing this problem, but because specific desorbing agent is difficult to prediction to the influence of the adsorption selectivity of particular type sorbent material, makes this work become very difficult.The contriver finds through further investigation: when making sorbent material with MFI type zeolite molecular sieve, from benzene, single substituted alkyl benzene, two substituted alkyl benzene and single the replacement the halogeno-benzene are chosen one or more desorbing agents, can be from mixed dichlorobenzene the compartment dichlorobenzene.
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.
Another object of the present invention is to provide a kind of with MFI type zeolite molecular sieve make sorbent material, with benzene, single substituted alkyl benzene, two substituted alkyl benzene and single the replacement are chosen one or more compounds and are made the method that desorbing agent gas phase from mixed dichlorobenzene is selected the fractionation by adsorption Meta Dichlorobenzene in the halogeno-benzene.This method is sorbent used need not controlled water-content and can regenerate.
To achieve the above object of the invention, the present invention adopts following technical scheme: a kind of Gas Phase Adsorption is separated the method for mixed dichlorobenzene, comprise mixed dichlorobenzene is passed through MFI type 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, under desorption conditions through the desorbing agent desorption, 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, and air speed is 0.1～30/ o'clock (weight);
(2) desorption temperature is 180 ℃～230 ℃, and pressure is normal pressure～2.0Mpa, and air speed is 0.1～20/ o'clock (weight), and desorbing agent is from benzene, single substituted alkyl benzene, gets two
Substituted alkyl benzene and single the replacement in the halogeno-benzene, chosen one or more.
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).
Use method of the present invention, 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 the desorbing agent desorption, desorbing agent is benzene, single substituted aroma hydrocarbon, fragrant hydrocarbon of di-substituted aryl or list is replaced halogeno-benzene etc.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 orthodichlorobenzenes (Wei Wende edits for organic chemical industry's complete works, the 3rd volume, and the Ministry of Chemical Industry's scientific information research 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.
The used sorbent material of the present invention is a MFI type zeolite adsorbent, MFI type zeolite molecular sieve comprises ZSM-5 and MFI type hydrophobic Silicone Zeolite Molecular Sieve (ZSM-5 type hydrophobic Silicone Zeolite Molecular Sieve or Silicalite-1), be preferably the Silicalite-1 zeolite adsorbent, be more preferably adhesive-free Silicalite-1 zeolite molecular sieve, feature of this sorbent material and preparation method thereof is seen Chinese patent CN1105906A.This sorbent material has very high water, thermostability, anti-strong acid and weakly alkaline chemical etching.Because do not contain aluminium substantially in the framework of molecular sieve, hydrophobicity is very high, water regain is very little, need not control the water-content of sorbent material during use.In addition, if because careless manipulation makes the adsorbent of molecular sieve poisoning and deactivation, only need simple calcination activation can make sorbent material recover active fully, the activating and regenerating condition was: at 300-800 ℃ of following roasting 1-5 hour.
Desorbing agent involved in the present invention comprises following four compounds: benzene, single substituted alkyl benzene, to two substituted alkyl benzene and single halogeno-benzene that replaces.
In the present invention, benzene is a good desorbing agent, and the substituting group carbochain of single substituted alkyl benzene is 1～12 carbon atom, is 1～4 carbon atom preferably, and more preferably methylbenzene, ethylbenzene, n-propylbenzene are taken all factors into consideration, and toluene is the preferential sorbent material of selecting.Simultaneously, the mixture of two or more formations in the above-claimed cpd also can be used as desorbing agent and uses, according to practical situation, and the also available inertia component dilution of desorbing agent, as 1,1,3,5-triisopropylbenzene etc.
Another kind of desorbing agent is contraposition two substituted alkyl benzene, and two substituting group carbochain length of contraposition can be any, but is advisable with short carbochain, is 1～10 as carbonatoms, preferred 1～4.Preferable contraposition two substituted alkyl benzene are p-diethylbenzenes, to methyl-propyl benzene, to ethyl methyl benzene etc., best contraposition two substituted alkyl benzene are p-diethylbenzenes, equally, the mixture that is made of this class desorbing agent compound or also can be used as desorbing agent with mixture that single substituted alkyl benzene class desorbing agent constitutes, desorbing agent also can dilute with the inertia component.
In the present invention, single replacement halogeno-benzene is the good desorbing agent of a class, is preferably chlorobenzene, bromobenzene or iodobenzene, most preferably chlorobenzene.
The adsorption separation process of Meta Dichlorobenzene of the present invention can carry out with intermittence or successive mode.
The present invention has very good effect at the mixed dichlorobenzene separation field, compares with existing technology, and the present invention is a sorbent material with MFI type zeolite molecular sieve; From benzene, single substituted alkyl benzene, two substituted alkyl benzene and single the replacement are chosen one or more the halogeno-benzene and are made desorbing agent, the separable Meta Dichlorobenzene that goes out in the mixed dichlorobenzene, products obtained therefrom purity height, and have the long easy industrialization of sorbent material life-span, adsorption/desorption separating technology to advantages such as equipment non-corrosivenesss.
Further specify the present invention below in conjunction with embodiment, but do not limit to its scope.
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, and (this test is sorbent used to be the Industrial products that do not have stick hydrophobic silicalite (Silicalite-1) by the MFI type that patented technology (CN1105906A) is produced.Sieve was got 10-20 purpose particle during use, 550 ℃ of activation two hours), feed adsorption bed after the feed vaporization, adsorbents adsorb behind the santochlor, obtain to contain the suction excess of Meta Dichlorobenzene and orthodichlorobenzene.Purge out middle distillate and make the santochlor desorption that adsorbs in the zeolite molecular sieve with desorbing agent, 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 58.6 gram vaporization backs feed adsorption bed, Silicalite-1 adhesive-free sorbent material 322 grams are housed in the bed, 191 ℃ of adsorption temps, adsorptive pressure 0.10Mpa, during air speed 1.5l/ (weight), obtain inhaling excess 14.1 grams, its weight percent consists of Meta Dichlorobenzene 80.48%, santochlor 0.11%, orthodichlorobenzene 19.41%.
Embodiment 2
After in embodiment 1, obtaining 14.1 gram suction excess, mono chloro benzene 278 grams of (weight) feed adsorption bed during with 191 ℃ of temperature, pressure 0.25Mpa, air speed 1.36/, make the santochlor desorption that adsorbs in the molecular sieve, collect middle distillate and extractum totally 44.1 grams (having removed desorbing agent), weight percent consists of Meta Dichlorobenzene 56.48%, santochlor 33.26%, orthodichlorobenzene 10.26%.
Embodiment 3
Raw material B 50.5 gram vaporization backs feed adsorption bed, Silicalite-1 sorbent material 310 grams are housed in the bed, 189 ℃ of adsorption temps, adsorptive pressure 0.13Mpa, during air speed 1.63/ (weight), obtain inhaling excess 12.1 grams, its weight percent consists of Meta Dichlorobenzene 87.49%, santochlor 0.20%, orthodichlorobenzene 12.31%.
Embodiment 4
After in embodiment 3, obtaining 12.1 gram suction excess, toluene 280 grams of (weight) feed adsorption bed during with 193 ℃ of temperature, pressure 0.25Mpa, air speed 1.41/, the santochlor desorption that adsorbs in the molecular sieve will be adsorbed in, middle distillate and emersion object be totally 38.1 grams (having removed desorbing agent), weight percent consists of Meta Dichlorobenzene 51.62%, santochlor 38.52%, orthodichlorobenzene 9.86%.
Embodiment 5
Raw material C 55.5 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, during air speed 1.28/ (weight), obtain inhaling excess 10.3 grams, its weight percent consists of Meta Dichlorobenzene 81.66%, santochlor 0.16%, orthodichlorobenzene 18.18%.
Mono chloro benzene 211 grams of (weight) feed adsorption bed during then with 185 ℃ of temperature, pressure 0.20Mpa, air speed 0.30/, make the santochlor desorption that adsorbs in the molecular sieve, collect middle distillate and extractum totally 44.9 grams (having removed desorbing agent), weight percent consists of Meta Dichlorobenzene 51.06%, santochlor 40.58%, orthodichlorobenzene 8.36%.
Embodiment 6
Raw material D 60.7 gram vaporization backs feed adsorption bed, Silicalite-1 adhesive-free sorbent material 322 grams are housed in the bed, 211 ℃ of adsorption temps, adsorptive pressure 0.10Mpa, during air speed 1.7l/ (weight), obtain inhaling excess 12.9 grams, its weight percent consists of Meta Dichlorobenzene 92.06%, santochlor 0.08%, orthodichlorobenzene 7.86%.
P-Diethylbenzene 1550 grams of (weight) feed adsorption bed during then with 211 ℃ of temperature, pressure 0.15Mpa, air speed 8.50/, make the santochlor desorption that adsorbs in the molecular sieve, collect middle distillate and extractum totally 47.5 grams (having removed desorbing agent), weight percent consists of Meta Dichlorobenzene 53.99%, santochlor 37.58%, orthodichlorobenzene 8.43%.
Claims (10)
1. a Gas Phase Adsorption is separated the method for mixed dichlorobenzene, comprise mixed dichlorobenzene is passed through MFI type 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 the desorbing agent desorption, inhale excess and make pure Meta Dichlorobenzene through rectifying separation under desorption conditions, actual conditions is:
(1) adsorption temp is 180 °～230 ℃, and pressure is normal pressure～0.5Mpa, and air speed is 0.1～30/ o'clock (weight);
(2) desorption temperature is 180 ℃～230 ℃, and pressure is normal pressure～2.0Mpa, and air speed is 0.1～20/ o'clock (weight), it is characterized in that desorbing agent is from benzene, single substituted alkyl benzene, two substituted alkyl benzene and single the replacement the halogeno-benzene are chosen one or more.
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, and 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 3 is separated the method for mixed dichlorobenzene, it is characterized in that sorbent material is an adhesive-free Silicalite-1 zeolite adsorbent.
5. according to the method for each described Gas Phase Adsorption separation mixed dichlorobenzene of claim 1～4, when it is characterized in that desorbing agent is the monoalkyl substituted benzene, the substituting group carbon chain lengths is not more than 4.
6. Gas Phase Adsorption according to claim 5 is separated the method for mixed dichlorobenzene, it is characterized in that desorbing agent is a toluene.
7. the method for separating mixed dichlorobenzene according to each described Gas Phase Adsorption of claim 1～4 is characterized in that desorbing agent is during to two substituted alkyl benzene, and disubstituted carbon chain lengths is not more than 4.
8. Gas Phase Adsorption according to claim 7 is separated the method for mixed dichlorobenzene, it is characterized in that desorbing agent is a p-diethylbenzene.
9. according to the method for each described Gas Phase Adsorption separation mixed dichlorobenzene of claim 1～4, when it is characterized in that desorbing agent is list replacement halogeno-benzene, halogen atom is selected from chlorine, bromine or iodine.
10. Gas Phase Adsorption according to claim 9 is separated the method for mixed dichlorobenzene, it is characterized in that desorbing agent is a chlorobenzene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00120892 CN1112226C (en) | 2000-08-16 | 2000-08-16 | Gas-phase selective adsorption process for separating dichlorobenzene from mixture |
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| CN 00120892 CN1112226C (en) | 2000-08-16 | 2000-08-16 | Gas-phase selective adsorption process for separating dichlorobenzene from mixture |
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| CN1112226C true CN1112226C (en) | 2003-06-25 |
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| CN102924225B (en) * | 2012-11-20 | 2015-01-07 | 江苏超跃化学有限公司 | Method for selectively absorbing and separating mixed toluene dichloride |
| CN111545166B (en) * | 2020-05-18 | 2022-12-13 | 江苏扬农化工集团有限公司 | Preparation method of adsorbent for separating and mixing dichlorobenzene, adsorbent prepared by preparation method and application of adsorbent |
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