CN102451619B - Y-shaped molecular sieve film and removal method for moisture in dichloromethane - Google Patents
Y-shaped molecular sieve film and removal method for moisture in dichloromethane Download PDFInfo
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- CN102451619B CN102451619B CN2010105140306A CN201010514030A CN102451619B CN 102451619 B CN102451619 B CN 102451619B CN 2010105140306 A CN2010105140306 A CN 2010105140306A CN 201010514030 A CN201010514030 A CN 201010514030A CN 102451619 B CN102451619 B CN 102451619B
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Abstract
The present invention discloses a Y-shaped molecular sieve film and a removal method for moisture in dichloromethane. With the present invention, the Y-shaped molecular sieve film is the Y-shaped molecular sieve film loaded on a support body, and is prepared by the following steps, wherein the steps comprise: carrying out cupric chloride modification for Y-shaped molecular sieve crystal seed with the particle size of 10-40 nm; pre-planting the modified crystal seed on the support the body; then adopting Y-shaped molecular sieve gel as a raw material to carry out hydrothermal synthesis to obtain the Y-shaped molecular sieve film. The removal method for the moisture in the dichloromethane comprises that: the dichloromethane discharged from a rectification tower is condensed by a condenser, and then the condensed dichloromethane enters a penetration tank provided with the Y-shaped molecular sieve film of the present invention by a supporting tank to carry out dewatering. With adopting the dichloromethane dewatering method by the Y-shaped molecular sieve film of the present invention, the dichloromethane reagent with the water content less than or equal to 0.04% is obtained, and the recovery rate of the dichloromethane can be 85.0-96.8%.
Description
Technical field
The invention belongs to the chemistry field that dewaters, relate in particular to a kind of y-type zeolite membrane and reclaim the removal methods of moisture in carrene.
Background technology
When using solvent, from economic loss, environmental pollution, the fire hazard of solvent, the aspects such as impair one's health, all illustrate solvent recovery, refining and to re-use be fully necessary.Solvent has contained more impurity after once using, re-use the not impact of some impurity on solvent, but some impurity brings larger harmful effect can for operations such as re-using some special chemical reactions of carrying out, recrystallization, extraction, washing, at this moment, impurity must be removed.The solvent recovery purpose is exactly to remove the impurity that impact is produced, and realizes the solvent recycling, reduces costs protection of the environment.Method for recovering solvents has condensation method, compression method, absorption process, absorption method and the way of distillation.In general solvent recovery, water is the impurity that content is maximum, so the recovery of solvent is nearly all first to dewater, removes and then other impurity.But water and many organic solvents have certain mutual solubility, by simple distillation, dewater after acquiring a certain degree and just are difficult to continue to reduce again the moisture of solvent.
In synthetic reaction, often use carrene to make solvent, for cost-saving, carrene need to reclaim use repeatedly usually.And usually contain 5%～20% moisture (weight content, as follows) from the carrene that reclaims mother liquor.this will directly affect synthetic reaction, for example, the carrene that uses in medicine intermediate 7-ACA (7-amino-cephalosporanic acid) production process is exactly this situation, carrene water content after synthetic reaction require to reclaim is necessary≤and 0.04%, but in the time of 25 ℃, water dissolves content in carrene be 0.17% (wt), usually the mode of dewatering that adopts is the way of distillation, the modes such as seasoning, and its water content of carrene that reclaims out with the azeotropic distillation evaporation is generally at 0.2% (wt), if this carrene is directly used in synthetic reaction, the yield of 7-ACA 23% left and right that will descend, production is caused and has a strong impact on.Existing carrene water-eliminating method be use the A type molecular sieve adsorbing and removing (as the pharmaceutical engineering design, 2001,22:15～17 " molecular sieve adsorption dewater the application in carrene reclaims "; Heilungkiang medicine, 2001,14:190～191 " application of 4A type molecular sieve in the carrene remanufacture " introduced).In CN101450890A, utilize the physical property of carrene, adopt freezing mode that the water in carrene is removed, this separation method only can make water content in carrene be down to below 0.5%, is difficult to reach the requirement of synthetic reaction.Although molecular screen membrane can remove the moisture in carrene, the undercapacity of common A molecular screen membrane, be unwell to the dehydration of carrene, and the dehydrating effect of common Y type molecular film needs further to improve.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of y-type zeolite membrane and with this y-type zeolite membrane, remove the method for moisture in carrene, the method dehydrating effect is good, and the water content in carrene is reduced to below 0.04%.
Y-type zeolite membrane of the present invention is load y-type zeolite membrane on supporter, Y type molecular film is that particle size is that the Y zeolite crystal seed of 10～40nm is after the copper chloride modification, plant in advance on supporter, then take the Y zeolite gel as raw water thermal synthesis y-type zeolite membrane.
In the present invention, the supporter of y-type zeolite membrane can be the suitable supporter in this area, as earthenware, mullite pipe, stainless steel tube etc., on supporter, has suitable pore passage structure.Supporter, before planting in advance the Y zeolite crystal seed, preferably passes through pretreatment.A kind of concrete preprocess method is: by supporter concentration, be that 5～15mol/L NaOH aqueous solution is processed 0.5～12h under 25～150 ℃, then use the deionized water supersound washing to neutral, oven dry under 100～150 ℃.
In the present invention, the copper chloride modifying process of nano Y-shaped molecular sieve crystal seed is: the Y zeolite crystal seed is immersed in the dichloride copper solution, carries out ion-exchange; Then centrifugation, washing; Last roasting.Dichloride copper solution concentration is at 0.05～10mol/L, Q/Y (ml/g)=10: 1～40: 1, and Q is the dichloride copper solution, in ml, Y is Y zeolite, in g.Ion-exchange temperature is 20～50 ℃, and ion-exchange time is 1～5h.Then with distilled water washing 3～6 times.Finally at 200～400 ℃ of lower roasting 1～3h.
In the present invention, the process that the Y zeolite crystal seed is planted on supporter in advance is: be dispersed in ethanol crystal seed is ultrasonic, the content of crystal seed in solution is 5wt%～20wt%, supporter is put into to the modified molecular screen seed-solution and flood 1～10min, take out airing, repeat then oven dry under 100～150 ℃ 3～6 times.
In the present invention, the process take the Y zeolite gel as raw water thermal synthesis y-type zeolite membrane as: He Gui source, aluminium source is added in distilled water and stirs successively, and mixing time is 30～60min, makes gel.The mol ratio of each component is 10～20 Na
2O: Al
2O
3: 8～20 SiO
2: 600～1000 H
2O.Described aluminium source is sodium aluminate, aluminium colloidal sol, and aluminum sulfate, be preferably sodium aluminate.Described silicon source is Ludox, waterglass, and silicic acid, be preferably Ludox.The supporter of having planted in advance the Modified Zeolite Y crystal seed is positioned in molecular sieve gel, at 70～100 ℃ of lower crystallization 8～36h, obtains y-type zeolite membrane.
In carrene of the present invention, the removal methods of moisture comprises following content: at first will be from rectifying column carrene out through condenser condenses, and then through accepting tank, enter in the osmotic cell that y-type zeolite membrane of the present invention is housed and dewater.
In carrene of the present invention, in the removal methods of moisture, there is control valve the osmotic cell below, can control fluid flow, and osmotic cell is connected to condenser and vavuum pump.Osmotic cell both sides pressure reduction is 10～150KPa.Carrene after processing finally by y-type zeolite membrane flow in finished pot naturally.Osmotic cell and finished pot keep certain difference in height, can smooth and easy outflow to guarantee carrene.So just obtain the carrene reagent of water content≤0.04%.And the carrene rate of recovery can reach 85.0%～96.8%.
Key in processing procedure of the present invention is: (1) adopts the Y zeolite crystal seed of Copper Ion Exchange modification to prepare y-type zeolite membrane, and it is high that the y-type zeolite membrane for preparing by modification has a silica alumina ratio, Heat stability is good, and Stability Analysis of Structures, extend access times.(2) prepare the Y zeolite crystal seed of film crystal grain used less, the y-type zeolite membrane of preparation is finer and close, and dehydrating effect is better, and improves the carrene rate of recovery.
The accompanying drawing explanation
Fig. 1 carrene dewatering process FB(flow block).
The specific embodiment
A kind of concrete operation method of the present invention below is described.
Embodiment 1
(1) earthenware pretreatment
The preparation 10mol/LNaOH aqueous solution, put into this NaOH aqueous solution by earthenware, under 70 ℃, processes 4h.Then use the deionized water supersound washing to neutral, then 120 ℃ of lower dry for standby.
(2) Y zeolite crystal seed modification
Compound concentration is the dichloride copper solution of 0.8mol/L, and the Y zeolite crystal seed is put into and wherein carried out ion-exchange, and exchange temperature is 50 ℃, and be 2h swap time.Dichloride copper solution/Y zeolite crystal seed (ml/g)=20: 1.Then centrifugation, with distilled water washing 5 times.Finally under 260 ℃, add thermal bake-out 2h.
(3) on earthenware, plant in advance the Modified Zeolite Y crystal seed
Choose the Y zeolite seed particles that is of a size of 20nm, be dispersed in ethanol crystal seed is ultrasonic, the content of crystal seed in solution is 10wt%, earthenware after processing is put into to the modified molecular screen seed-solution and flood 4min, take out airing, repeat 5 times, then oven dry under 150 ℃.
(4) preparation Y zeolite gel
Sodium aluminate and Ludox are added in distilled water and stir successively, and mixing time is 60min, makes gel.The each component mol ratio is 10 Na
2O: Al
2O
3: 15 SiO
2: 800 H
2O.
(5) hydrothermal crystallizing
The earthenware of having planted in advance the Modified Zeolite Y crystal seed is positioned in the Y zeolite gel, at 100 ℃ of lower hydrothermal crystallizing 12h.Then be cooled to room temperature.
(6) washing
Earthenware after the taking-up crystallization, be washed with distilled water to neutrality.
(7) dehydration
Will be from accepting tank carrene 2000ml out through the osmotic cell dehydration of Modified Zeolite Y film is housed, osmotic cell both sides pressure reduction is 100KPa, the carrene flow velocity is 15ml/min.Parallel processing three times.
Carrene water content after the Modified Zeolite Y film is processed is in Table 1.
Embodiment 2
With reference to process and the condition of embodiment 1, the change part is that in step (2) Y zeolite crystal seed modification, compound concentration is the dichloride copper solution of 1.0mol/L, carries out ion-exchange.Exchange temperature is 40 ℃, and be 3h swap time.Dichloride copper solution/Y zeolite crystal seed (ml/g)=10: 1.
Embodiment 3
With reference to process and the condition of embodiment 1, the change part is that in step (4) preparation Y zeolite gel, each component mol ratio is 12 Na
2O: Al
2O
3: 18 SiO
2: 900 H
2O.(5) hydrothermal crystallization process is at 80 ℃ of lower hydrothermal crystallizing 20h.Then be cooled to room temperature.
Comparative example
Adopt the method identical with embodiment 1, just the Y zeolite crystal seed is without modification.The results are shown in Table 1.
Table 1 embodiment and comparative example result (percentage by weight)
Claims (8)
1. y-type zeolite membrane, for load y-type zeolite membrane on supporter, it is characterized in that: y-type zeolite membrane is that particle size is that the Y zeolite crystal seed of 10～40nm is after the copper chloride modification, plant in advance on supporter, then take the y-type zeolite membrane of Y zeolite gel as the raw water thermal synthesis; The copper chloride modifying process of nano Y-shaped molecular sieve crystal seed is: the Y zeolite crystal seed is immersed in the dichloride copper solution, carries out ion-exchange; Then centrifugation, washing; Last roasting; Wherein dichloride copper solution concentration is 0.05～1.0mol/L, Q/Y (ml/g)=10: 1～40: 1, and Q is the dichloride copper solution, in ml, Y is Y zeolite, in g; Ion-exchange temperature is 20～50 ℃, and ion-exchange time is 1～5h; Then with distilled water washing 3～6 times; Finally at 200～400 ℃ of lower roasting 1～3h.
2. according to y-type zeolite membrane claimed in claim 1, it is characterized in that: the supporter of y-type zeolite membrane is earthenware, mullite pipe or stainless steel tube.
3. according to the described y-type zeolite membrane of claim 1 or 2, it is characterized in that: supporter is before planting in advance the Y zeolite crystal seed, through pretreatment, preprocess method is: by supporter concentration, be that 5～15mol/LNaOH aqueous solution is processed 0.5～12h under 25～150 ℃, then use the deionized water supersound washing to neutral, oven dry under 100～150 ℃.
4. according to y-type zeolite membrane claimed in claim 1, it is characterized in that: the process that the Y zeolite crystal seed is planted on supporter in advance is, be dispersed in ethanol crystal seed is ultrasonic, the content of crystal seed in solution is 5wt%～20wt%, supporter is put into to the modified molecular screen seed-solution and flood 1～10min, take out airing, repeat 3～6 times, then oven dry under 100～150 ℃.
5. according to y-type zeolite membrane claimed in claim 1, it is characterized in that: the process take the Y zeolite gel as raw water thermal synthesis y-type zeolite membrane as, He Gui source, aluminium source is added in distilled water and stirs successively, mixing time is 30～60min, make gel, the mol ratio of each component is 10～20Na
2O: Al
2O
3: 8～20SiO
2: 600～1000H
2O; The supporter of having planted in advance the Modified Zeolite Y crystal seed is positioned in molecular sieve gel, at 70～100 ℃ of lower crystallization 8～36h, obtains y-type zeolite membrane.
6. according to y-type zeolite membrane claimed in claim 5, it is characterized in that: the aluminium source is sodium aluminate, aluminium colloidal sol or aluminum sulfate, and the silicon source is Ludox, waterglass or silicic acid.
7. the removal methods of moisture in a carrene, comprise following content: at first will be from rectifying column carrene out through condenser condenses, then through accepting tank, enter in the osmotic cell that y-type zeolite membrane is housed and dewater, it is characterized in that: y-type zeolite membrane is the described y-type zeolite membrane of the arbitrary claim of claim 1 to 6.
8. in accordance with the method for claim 7, it is characterized in that: osmotic cell both sides pressure reduction is 10～150KPa, obtains the carrene reagent of water content≤0.04%.
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| CN102908880A (en) * | 2012-10-24 | 2013-02-06 | 大连理工大学 | Pre-dewatering method for reducing load of high-water-content methyl chloride drying apparatus |
| CN103551179A (en) * | 2013-11-07 | 2014-02-05 | 扬州大学 | Preparation method of cancrinite molecular sieve membrane catalyst |
| CN104529006B (en) * | 2014-12-30 | 2016-06-22 | 苏州市晶协高新电子材料有限公司 | A kind of device reducing dichloromethane waste liquid acidity and moisture |
| CN104857742B (en) * | 2015-05-28 | 2017-05-31 | 重庆理工大学 | A kind of water-eliminating method of dichloromethane |
| CN107855004A (en) * | 2016-09-22 | 2018-03-30 | 中国石油化工股份有限公司 | The method dried using membrane module to chlorated liquid in the chlorination reaction of benzene |
| US11052346B2 (en) * | 2018-05-23 | 2021-07-06 | Molecule Works Inc. | Device and method for separation of water from mixtures |
| CN114057541B (en) * | 2021-12-09 | 2023-08-15 | 河南省化工研究所有限责任公司 | Refining recovery method for dehydrating waste dichloromethane through supergravity coupling membrane |
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