CN105985475A - Diluted hydrochloric acid concentration anion membrane - Google Patents
Diluted hydrochloric acid concentration anion membrane Download PDFInfo
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- CN105985475A CN105985475A CN201510078453.0A CN201510078453A CN105985475A CN 105985475 A CN105985475 A CN 105985475A CN 201510078453 A CN201510078453 A CN 201510078453A CN 105985475 A CN105985475 A CN 105985475A
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Abstract
The invention relates to a diluted hydrochloric acid concentration anion membrane. The compact anion membrane is formed through polymerization crosslinking of an isobutene monomer, a 2-trifluoromethyl t-pentenol monomer and an isobutenyl quaternary ammonium salt monomer. The ion capacity reaches 0.7-2.4mmol/g, and the H<+> dialysis coefficient is 0.0014-0.0065m/h. The membrane has very small apertures and very high membrane ion capacity, so the membrane can effectively block reverse osmosis of H<+> from a high concentration zone to a low concentration zone, and has strong diluted hydrochloric acid concentration ability. The anion membrane contains no phenyl rings, ester groups or ether bonds, has a benzyl structure, has very strong oxidation resistance, and is very durable even diluted hydrochloric acid contains a tiny amount of chlorine.
Description
Technical field:
The present invention is a kind of technical method that dilute hydrochloric acid carries out efficient concentration, is that discarded dilute hydrochloric acid is become the field of Environment Protection technology into the utilization of resources of giving up.
Background technology:
How content 5-15%wt dilute hydrochloric acid concentration is concentrated hydrochloric acid by low cost？It it is the difficult problems of environment protection treating field face.Hydrochloric acid is chemical industry and system
Mordant that medicine field is conventional and raw material, also can discharge substantial amounts of low concentration waste hydrochloric acid in these production processes simultaneously.Owing to hydrochloric acid would generally be formed
Maximum azeotrope thing, azeotropic composition containing hydrogen chloride 20.24% (mass fraction), cannot obtain, by the method for conventional distillation, the hydrochloric acid solution that concentration is higher.
And the extensive dilute hydrochloric acid process technique of domestic and international application comparative maturity mainly has conventional desorption method, pressure differential method and catalyst method etc. at present.Conventional desorbing
Method is only applicable to the desorption process of the concentration hydrochloric acid higher than 20.24%, it is impossible to for the concentration of lower concentration hydrochloric acid, distillation energy consumption is the biggest.
Chinese patent CN200410017364 describes a kind of dilute waste hydrochloric acid semi-continuous extraction and distills the method producing concentrated hydrochloric acid, needs with molar concentration
Be 25.0～32.3% sulphuric acid make extractant, vapo(u)rizing temperature is 95 DEG C～110 DEG C, and still temperature is 155 DEG C～200 DEG C.The semicontinuous addition of dilute waste hydrochloric acid
Boiling aqueous sulfuric acid in and make aqueous sulfuric acid be in fluidized state all the time, carry out normal pressure or decompression extractive distillation.This method energy consumption is too big,
Dilute hydrochloric acid concentrated cost is high, and equipment corrosion is serious, and operating environment is extremely severe, can produce again Waste Sulfuric Acid and residual dilute hydrochloric acid, substantially not have
Practical value.
Anionic membrane energy selectivity passes through chloride ion, thus can low cost effective concentration dilute hydrochloric acid on electrodialysis plant.But anion both domestic and external
Film uses styryl structures or methacrylate cross-linked polymeric to form mostly, or doping polymerizable organosilicon monomer, cross-links shape by siloxane bond
Become anionic membrane.
Phenylethylene is polymerized the anionic membrane of monomer crosslinked formation, and due to the existence of phenyl ring rigid structure, fenestra is more than 10nm, and ion exchange capacity is less than
0.8mmol/g, and phenyl ring a position is easily oxidized fracture.Because fenestra is big, water is easy to from high concentration region reverse osmosis to low concentration region, HCl
Along with water together reverse osmosis, substantially there is no dilute hydrochloric acid concentration ability.And siloxane bond can form fine and close crosslinking, but siloxanes is built fearness acid and is afraid of alkali, PH
Strong acid or the PH alkali more than 9 less than 2 just can make siliconoxygen bond rupture, and fenestra increases rapidly or penetrates.Owing to dilute hydrochloric acid is the strong acid that PH is less than 1,
The anionic membrane of silicone-containing does not has dilute hydrochloric acid concentration ability yet.
CN201410102732 describes a kind of many silicon cross-linking agent and the special anionic membrane of diffusion dialysis thereof, uses allyl bromide, bromoallylene and vinylsiloxane to gather
Synthesis coating solution, after crosslinking film forming, comes quaterisation, ion exchange capacity 0.3-0.65mmol/g, H with trimethylamine aqueous solution+Dialysis coefficent
For 0.011-0.036m/h, separation is 30.3-47.4.Owing to being quaterisation after film forming, the fenestra micropore trimethylamine less than 1-2nm without
Method enters, and therefore ion exchange capacity is the lowest, is distributed the most uneven, there is the fenestra road not having ion electric potential in a large number, H+Dialysis coefficent is very big,
It is easily broken off making fenestra significantly increase under strong acid plus siliconoxygen bond, substantially there is no dilute hydrochloric acid concentrating capacity.
The CN201180061830 of GE introduces acid and blocks anionic membrane, a kind of ionic membrane that can reclaim acid from inorganic salt, uses
4-vinyl chloride synthesizes membrane polymer quaternary ammonium salt, and this benzyl quaternary ammonium salt structure is weak to chlorine oxidation, when dilute hydrochloric acid exists trace chlorine,
This film can be degraded by rapid oxidation within 1-3 week, it is impossible to is continuing with.
Sum up existing ionic membrane documents and materials, due to the various defects of existing anionic membrane, it is impossible to carry out low cost with anionic membrane and concentrate dilute hydrochloric acid.
Main anionic membrane defect is as follows:
(1) fenestra is the biggest: the ionic membrane aperture of existing polymerization is generally higher than 10nm, it is impossible to stop that water penetration crosses ionic membrane, H+Along with water
From high concentration region reverse osmosis to low concentration region, there is no concentration ability.
(2) membrane material is very easy to oxidation: benzyl chloride structure or the polymer of styryl structures, phenyl ring a position carbochain is easy to by chlorine oxidation
Fracture, service life is the shortest, does not has practical value.If forming polymer by ester bond or ehter bond, these keys are under strong acid
Being easy to hydrolytic cleavage, the service life of film is very limited.
(3) ion capacity is the lowest: typically at 0.3-0.7mmol/g, causes HCl via not having the duct of ion electric potential, and reverse osmosis is to low concentration
District, is greatly reduced dilute hydrochloric acid concentration ability.
(4) heat-resisting ability: containing the ionic membrane of siliconoxygen bond crosslinking, at 50-70 degree and PH under the strong acid less than 1, siliconoxygen bond, ester bond or ether
Key can rupture rapidly, makes ionic membrane quickly lose concentrating capacity.
For the anionic membrane problem of above all concentration dilute hydrochloric acid, the present invention provides a kind of without phenyl ring, without siliconoxygen bond, macroion capacity
With the anionic membrane of stable fine and close fenestra, make dilute hydrochloric acid concentration can stablize longtime running effectively.
Summary of the invention:
The present invention provide a kind of can the anionic membrane of effective concentration dilute hydrochloric acid, use isobutene., the cross-linking agent of formula A molecular structure, formula B or formula C
Isobutenyl quaternary ammonium salt polymerization monomer, by polymerization crosslinking, synthesis fenestra is fine and close and anionic membrane that ion exchange capacity is the highest.
H+Infiltration, mainly high concentration region concentrated hydrochloric acid H+Along with water diffuses and penetrate into low concentration region from fenestra road；Therefore ionic membrane concentration dilute hydrochloric acid energy
The power of power, it is important to the most effectively stop H+Scattering and permeating？
Wherein: formula B is isobutenyl-N-methylmorpholine ammonium chloride, formula C is isobutenyl trimethyl ammonium chloride.
Effectively to stop H+Scattering and permeating, anionic membrane has to pass through fine and close crosslinking, membrane aperture is controlled at 0.8-1.5nm, and fenestra is the least, water
The resistance of scattering and permeating is the biggest, and scattering and permeating speed is the slowest.If not containing siliconoxygen bond, ester bond or ehter bond, membrane aperture just can be stably held in
The fine and close cross-linked state of 0.8-1.5nm；Meanwhile, anionic membrane keeps uniform macroion capacity, it is to avoid existing in anionic membrane does not has ion electric potential
Fenestra road, stop H+Via not having the fenestra road of ion electric potential, diffusion is to low concentration region.
In order to overcome the defect of the easy oxidation scission of anionic membrane benzyl structure, make ionic membrane in an oxidizing environment can longtime running, the polymerization of the present invention
Monomer all uses isobutene. or isobutenyl derivant, main polymer chain does not exist the secondary carbon hydrogen of easily oxidation, makes ionic membrane oxidative resistance compare benzyl
Based structures significantly strengthens.
The preparation technology of anionic membrane of the present invention, needs, through being polymerized for the first time, be acidified and second time polymerization, just to prepare high densification and cross-link and high
The anionic membrane of ion capacity.
Polymerization for the first time: in autoclave, the isobutenyl quaternary ammonium salt adding the cross-linking agent of formula A compound, formula B compound or formula C compound gathers
Closing monomer, add solvent and azo-initiator, be passed through the isobutene. of rated capacity after sealing, heating in water bath to material is maintained at 60-100 degree,
Decomposition of initiator goes out free radical and causes material polymerization, obtains linear long-chain oligomer film solution.
Acidifying: add phosphoric acid, methylphosphonic acid or p-methyl benzenesulfonic acid etc. in above-mentioned linear long-chain oligomer film solution, be heated to 50-90 degree and carry out
Acidification reaction, removes most solvent, obtains the acidifying solution of the linear long-chain oligomer film solution of thickness.
Second time polymerization: add the azo-initiator dissolved with a small amount of solvent in above-mentioned acidifying solution, stir, be subsequently poured into 0.5-1.0mm
Deep die cavity levelling, cover plate for sealing post-heating to 60-100 degree, cause second time polymerization, cross-linked polymeric becomes fine and close anionic membrane.
The present invention causes the initiator of polymerization to use azo type free radical initiator, such as azodiisobutyronitrile, AMBN, azo two different heptan
Nitrile or azo-bis-iso-dimethyl etc..The addition of initiator is the 0.2-1.0% of total formulation weight.
The first time polymerization of the present invention, the mol ratio of isobutene., formula A compound and formula B compound is 10: 0.2～2: 0.5～2；When formula C of employing
During compound, the mol ratio of isobutene., formula A compound and formula C compound is 10: 0.2～2: 0.5～2.
By the fine and close cross-linked anion membrane of second time polymerization preparation, fenestra can reach 0.8-1.5nm, and ion exchange capacity is up to 0.7-2.4mmol/g,
H+Dialysis coefficent is greatly reduced as 0.0014-0.0065m/h, exceeds well over the most common homogeneous-phase anion film.
In order to improve film mechanical strength, when second time polymerization, gauze can be strengthened by Acidulent film solution impregnation and form thin liquid layer, after polymerization, form yarn
The anionic membrane that net strengthens.General selection PTFE gauze or glass fibre gauze.
Detailed description of the invention:
In order to be more fully understood that the anionic membrane of the present invention synthesizes, introduce some embodiments and describe in detail, but the invention is not restricted to these embodiments following.
Embodiment 1:
In 1500ml autoclave add 31g formula A compound (0.2mol), 75g formula C compound (0.5mol), 5g AMBN and
400g dehydrated alcohol, after sealing, adds 280g isobutene. (5mol), the autoclave that 60 degree of heating in water bath are stirred continuously, causes the freedom of material
Base is polymerized, and exothermic heat of reaction causes material to heat up, and in controlling autoclave, temperature is less than 80 DEG C, and after 6-7 hour, temperature of charge drops to bath temperature, instead
Should terminate, after being cooled to room temperature, pour out the linear long-chain oligomer film solution 775g of polymerization for the first time.
Adding 85%wt phosphoric acid 30g in above-mentioned solution, be heated to reflux 2-3 hour, acidifying terminates.Then distillation removing major part ethanol, obtains
The oligomer film solution acidifying solution 536g of thickness.
2g AMBN addition 20g dehydrated alcohol is configured to initiator solution, is subsequently adding in above-mentioned acidifying solution and stirs, pour into deep
Impregnating PTFE gauze in the die cavity of 1mm, form the thin liquid layer of 0.6-0.8mm, after covering cover plate for sealing, heating is maintained at 60 degree of initiations and was polymerized
At night, second time polymerization obtains the anionic membrane of fine and close crosslinking.The anionic membrane data of test are as follows:
Ion exchange capacity is 1.3mmol/g, H+Dialysis coefficent is 0.0038m/h, has the sour blocking ability of excellence.
Embodiment 2:
31g formula A compound (0.2mol), 75g formula C compound (0.5mol), 5g azo diisoamyl is added in 1500ml autoclave
Nitrile and 400g dehydrated alcohol, after sealing, add 338g isobutene. (6mol), the autoclave that 60 degree of heating in water bath are stirred continuously, cause material
Radical polymerization, exothermic heat of reaction causes material to heat up, and in controlling autoclave, temperature is less than 80 DEG C, and after 6-7 hour, temperature of charge drops to bath temperature,
Reaction terminates, and after being cooled to room temperature, pours out the linear long-chain oligomer film solution 834g of polymerization for the first time.
Adding 85%wt phosphoric acid 30g in above-mentioned solution, be heated to reflux 2-3 hour, acidifying terminates.Then distillation removing major part ethanol, obtains
The oligomer film solution acidifying solution 572g of thickness.
2g AMBN addition 20g dehydrated alcohol is configured to initiator solution, is subsequently adding in above-mentioned acidifying solution and stirs, pour into deep
Impregnating PTFE gauze in the die cavity of 1mm, form the thin liquid layer of 0.6-0.8mm, after covering cover plate for sealing, heating is maintained at 60 degree of initiations and was polymerized
At night, second time polymerization obtains the anionic membrane of fine and close crosslinking.The anionic membrane data of test are as follows:.
Ion exchange capacity is 1.1mmol/g, H+Dialysis coefficent is 0.0049m/h, has the sour blocking ability of excellence.
Embodiment 3:
1500ml autoclave adds 31g formula A compound (0.2mol), 86g formula B compound (0.5mol), 5g azo two different heptan
Nitrile and 400g dehydrated alcohol, after sealing, add 281g isobutene. (5mol), the autoclave that 60 degree of heating in water bath are stirred continuously, cause material
Radical polymerization, exothermic heat of reaction causes material to heat up, and in controlling autoclave, temperature is less than 80 DEG C, and after 6-7 hour, temperature of charge drops to bath temperature,
Reaction terminates, and after being cooled to room temperature, pours out the linear long-chain oligomer film solution 787g of polymerization for the first time.
Adding methylphosphonic acid 20g in above-mentioned solution, be heated to reflux 2-3 hour, acidifying terminates.Then distillation removing major part ethanol, is glued
Thick oligomer film solution acidifying solution 530g.
2g 2,2'-Azobis(2,4-dimethylvaleronitrile) addition 20g dehydrated alcohol is configured to initiator solution, is subsequently adding in above-mentioned acidifying solution and stirs, pour into deep
Impregnating PTFE gauze in the die cavity of 1mm, form the thin liquid layer of 0.6-0.8mm, after covering cover plate for sealing, heating is maintained at 60 degree of initiations and was polymerized
At night, second time polymerization obtains the anionic membrane of fine and close crosslinking.The anionic membrane data of test are as follows:
Ion exchange capacity is 1.2mmol/g, H+Dialysis coefficent is 0.0065m/h, has the sour blocking ability of excellence.But than formula C compounds property
The most inferior.
Embodiment 4:
31g formula A compound (0.2mol), 75g formula C compound (0.5mol), 5g azo diisoamyl is added in 1500ml autoclave
Nitrile and 400g dehydrated alcohol, after sealing, add 226g isobutene. (4mol), the autoclave that 60 degree of heating in water bath are stirred continuously, cause material
Radical polymerization, exothermic heat of reaction causes material to heat up, and in controlling autoclave, temperature is less than 80 DEG C, and after 6-7 hour, temperature of charge drops to bath temperature,
Reaction terminates, and after being cooled to room temperature, pours out the linear long-chain oligomer film solution 716g of polymerization for the first time.
Adding methylphosphonic acid 20g in above-mentioned solution, be heated to reflux 2-3 hour, acidifying terminates.Then distillation removing major part ethanol, is glued
Thick oligomer film solution acidifying solution 488g.
2g AMBN addition 20g dehydrated alcohol is configured to initiator solution, is subsequently adding in above-mentioned acidifying solution and stirs, pour into deep
Impregnating PTFE gauze in the die cavity of 1mm, form the thin liquid layer of 0.6-0.8mm, after covering cover plate for sealing, heating is maintained at 60 degree of initiations and was polymerized
At night, second time polymerization obtains the anionic membrane of fine and close crosslinking.The anionic membrane data of test are as follows:
Ion exchange capacity is 1.4mmol/g, H+Dialysis coefficent is 0.0027m/h, has the sour blocking ability of excellence.
Embodiment 5:
In 1500ml autoclave add 31g formula A compound (0.2mol), 86g formula B compound (0.5mol), 5g AMBN and
400g dehydrated alcohol, after sealing, adds 228g isobutene. (4mol), the autoclave that 60 degree of heating in water bath are stirred continuously, causes the freedom of material
Base is polymerized, and exothermic heat of reaction causes material to heat up, and in controlling autoclave, temperature is less than 80 DEG C, and after 6-7 hour, temperature of charge drops to bath temperature, instead
Should terminate, after being cooled to room temperature, pour out the linear long-chain oligomer film solution 734g of polymerization for the first time.
Adding 85%wt phosphoric acid 30g in above-mentioned solution, be heated to reflux 2-3 hour, acidifying terminates.Then distillation removing major part ethanol, obtains
The oligomer film solution acidifying solution 496g of thickness.
2g azo isobutyl cyanide addition 20g dehydrated alcohol is configured to initiator solution, is subsequently adding in above-mentioned acidifying solution and stirs, pour deep 1mm into
Die cavity in impregnate PTFE gauze, formed 0.6-0.8mm thin liquid layer, after covering cover plate for sealing, heating be maintained at 60 degree cause polymerization overnight,
Second time polymerization obtains the anionic membrane of fine and close crosslinking.The anionic membrane data of test are as follows:
Ion exchange capacity is 1.3mmol/g, H+Dialysis coefficent is 0.0042m/h, has the sour blocking ability of excellence.
Claims (9)
1. an anionic membrane for concentration dilute hydrochloric acid, it is mainly characterized by including following raw material:
(1) using formula A fluorochemical is polymeric cross-linker, by the oligomer film solution crosslinking film forming of line style long-chain.
(2) use isobutene. as polymerization monomer.
(3) formula B compound or the isobutenyl quaternary ammonium salt polymerization monomer of formula C compound are used.
2. an anionic membrane for dilute hydrochloric acid concentration, it is mainly characterized by film-forming polymer process, mainly comprises the steps:
(2a) polymerization for the first time: by formula A compound, formula B compound or formula C compound, isobutene., initiator and solvent in autoclave
Mixing, under being heated to 60～100 degree, decomposition of initiator is free radical polymerization, generates linear oligomer solution.
(2b) acidifying: linear oligomer solution adds phosphoric acid, methylphosphonic acid or p-methyl benzenesulfonic acid, is heated to 50～90 degree of reactions.
(2c) second time polymerization: the linear oligomer solution after acidifying adds initiator, and homogeneous impregnation is coated on reinforcing fiber gauze and forms thin liquid
Layer, is heated to 60～100 degree and causes cross-linked polymeric, obtains the anionic membrane of fine and close crosslinking.
Polymerization monomer the most according to claim 1 form, its formula be mainly characterized by isobutene., formula A compound and formula B compound mole
Ratio is 10: 0.2～2: 0.5～2.
Polymerization monomer the most according to claim 1 form, its formula be mainly characterized by isobutene., formula A compound and formula C compound mole
Ratio is 10: 0.2～2: 0.5～2.
Polymerization the most according to claim 2, it is mainly characterized by initiator and uses azo-initiator, such as azodiisobutyronitrile, azo
Diisoamyl nitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The most according to claim 2, the anionic membrane being polymerized, it is mainly characterized by ion exchange capacity 0.7～2.4mmol/g.
Anionic membrane the most according to claim 2, it is mainly characterized by ionic membrane thickness 0.2～1.0mm.
Reinforcing fiber gauze the most according to claim 2, it is mainly characterized by selecting glass fibre gauze or politef gauze etc..
Polymerization the most according to claim 2, it is mainly characterized by addition is total formulation weight the 0.2～1.0% of initiator.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110270225A (en) * | 2018-03-13 | 2019-09-24 | Bl 科技公司 | The multistage bipolar electrodialysis system produced for high concentrated acid or alkali |
| CN112079736A (en) * | 2020-08-24 | 2020-12-15 | 上海漫关越水处理有限公司 | Quaternary ammonium salt compound of fuel cell anion membrane capable of completely blocking methanol permeation |
| CN112144075A (en) * | 2020-10-09 | 2020-12-29 | 上海漫关越水处理有限公司 | Method for continuously synthesizing potassium tert-butoxide by membrane electrolysis |
-
2015
- 2015-02-13 CN CN201510078453.0A patent/CN105985475A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110270225A (en) * | 2018-03-13 | 2019-09-24 | Bl 科技公司 | The multistage bipolar electrodialysis system produced for high concentrated acid or alkali |
| CN112079736A (en) * | 2020-08-24 | 2020-12-15 | 上海漫关越水处理有限公司 | Quaternary ammonium salt compound of fuel cell anion membrane capable of completely blocking methanol permeation |
| CN112144075A (en) * | 2020-10-09 | 2020-12-29 | 上海漫关越水处理有限公司 | Method for continuously synthesizing potassium tert-butoxide by membrane electrolysis |
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