CN104292114B - A kind of preparation method of hydroxide - Google Patents
A kind of preparation method of hydroxide Download PDFInfo
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- CN104292114B CN104292114B CN201310307194.5A CN201310307194A CN104292114B CN 104292114 B CN104292114 B CN 104292114B CN 201310307194 A CN201310307194 A CN 201310307194A CN 104292114 B CN104292114 B CN 104292114B
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Abstract
The invention provides the preparation method of the hydroxide shown in a kind of formula I, comprise the saline solution shown in formula II is sent in bipolar membrane electrodialysis device, carry out bipolar membrane electrodialysis, obtain the aqueous solution that contains the hydroxide shown in formula I, wherein, in the sour chamber of bipolar membrane electrodialysis device, send into neutralizer, described neutralizer contains the material that acid-base reaction can occur with HX. Adopt method of the present invention to prepare hydroxide, the continuous operating time of bipolar membrane electrodialysis device is long, in reducing production costs, can also enhance productivity. Meanwhile, adopt the purity of hydroxide prepared by method of the present invention high, quality better.。
Description
Technical field
The present invention relates to a kind of preparation method of hydroxide, particularly, the present invention relates to a kind of employingBipolar membrane electrodialysis process is prepared the method for hydroxide.
Background technology
Quaternary ammonium base is a kind of important organic base, of many uses, can be used as integrated circuit in electronics industryCleaning agent, etching agent and the polishing agent of plate, can also and urge as the auxiliary agent in oil refining and Chemical EngineeringAgent. And quaternary ammonium base (as TPAOH, tetraethyl ammonium hydroxide) is that synthesis of titanium silicon dividesIrreplaceable alkali source and template in son sieve, HTS has good selective paraffin oxidation catalysisPerformance is to produce indispensable catalyst in hydroquinones, cyclohexanone oxime and expoxy propane process.
At present, the method for production quaternary ammonium base mainly contains the precipitation method, ion-exchange and electroosmose process. Wherein,The precipitation method are that quaternary ammonium salt is dissolved in suitable organic solvent, then add alkali, make the moon in quaternary ammonium saltThe cation of ion in alkali is combined, and is settled out compared with little salt to be formed on solubility in organic solventCome, after separating, obtain the method for quaternary ammonium base; Ion-exchange rule is that employing strongly basic anionic resin willBromination (or chlorination) quaternary ammonium salt aqueous solution carries out ion-exchange, thereby obtains quaternary ammonium base; Electroosmose process isIn diaphragm electrolytic cell, make quaternary ammonium salt and alkali carry out ion-exchange and by the moon in quaternary ammonium salt by barrier filmIon exchange is hydroxide ion, and then acquisition quaternary ammonium base. Wherein, the production cost of the precipitation method is higher,The quality of the product obtaining needs further to improve; Although the quality of product prepared by ion-exchangeBetter, production cost is also lower simultaneously, but in the time that ion exchange resin is regenerated, can produce a large amount ofWaste water, is unfavorable for environmental protection.
Electroosmose process is according to the kind difference of film using, can be divided into one pole EDBM method (, fromProton exchange method) and bipolar membrane electrodialysis method. Although one pole EDBM method can obtain coloryProduct, but the electrolysis installation using is comparatively complicated, and have accessory substance to produce. Bipolar membrane electrodialysis methodBe by under DC electric field effect, use Bipolar Membrane by hydrolytic dissociation, obtain respectively in the both sides of Bipolar MembraneH+And OH-Thereby, quaternary ammonium salt is converted into corresponding quaternary ammonium base. The equipment knot of bipolar membrane electrodialysis processStructure is comparatively simple, and does not substantially have accessory substance to produce.
CN1334796A disclose a kind of in electrodialysis plant by electrodialysis prepare element N, S orP the method for hydroxide, this device has anode, negative electrode and one or more each band acid and returnsThe groove unit in He Jian loop, road, by the He Jian loop, salting liquid lead-ingroove unit of following general formula (I) alsoCarry out electrodialysis,
Wherein, M represents N, S or P; R1、R2、R3And R4Be respectively separate, sometimes with officialEnergy group replaces, the aliphatic series straight chain that carbon number is 1-30 or side chain, saturated or unsaturated,Cyclic aliphatic, araliphatic or aromatic group or R1-R4In two groups and M form heterocycle, X-Represent nValency anion, n represents the number of 1-4,
Wherein, each groove unit is made up of Bipolar Membrane and anion selective membrane, and selects at last anionAnode-side between film and anode has Bipolar Membrane or cation selective membrane.
The disclosed method of CN1334796A can extend the life-span of anode material and cathode material, simultaneouslyTo product material in impurity content low.
Summary of the invention
The present inventor finds in research process, adopts bipolar membrane electrodialysis method to prepare hydrogen-oxygenFor example, when compound (quaternary ammonium base), the seriously corroded of bipolar membrane electrodialysis device (particularly electrode), andAmberplex (the particularly Bipolar Membrane adjacent with electrode chamber) surface is easy to bubbling, causes Bipolar Membrane electricityThe continuous operating time of electrodialysis apparatus is shorter, needs frequent shutdowns to change impaired parts.
The present inventor finds through research, occurs the reason of above-mentioned phenomenon mainly: Bipolar Membrane electricityIn unavoidably can existing in electrodialysis apparatus, blend film infiltration, make the feed liquid in sour chamber enter other chamberIn, cause the acidity of the feed liquid in other chamber to strengthen, aggravation corrosion, particularly makes the corrosion of electrodeAggravation; When feed liquid enters other chamber due to film infiltration in acid chamber, also can cause film surface blisters (spyThe Bipolar Membrane adjacent with electrode chamber), make film cannot realize its function.
The present inventor conducts in-depth research for this reason, finds: adopting bipolar membrane electrodialysis sideWhen method is prepared hydroxide, if added in the sour chamber of bipolar membrane electrodialysis device, contain can be withThere is the neutralizer of acid-base reaction in HX, can significantly alleviate corrosion condition and the ion of electrodialysis plantThe phenomenon of exchange membrane surface blisters, the continuous operating time of prolongation bipolar membrane electrodialysis device. Complete thusThe present invention.
The preparation method who the invention provides the hydroxide shown in a kind of formula I, the method comprises: willThe aqueous solution of the salt shown in formula II is sent in bipolar membrane electrodialysis device, carries out bipolar membrane electrodialysis,To the aqueous solution that contains the hydroxide shown in formula I, wherein, the method comprises to bipolar membrane electrodialysisIn the sour chamber of device, send into neutralizer, described neutralizer contains the material that acid-base reaction can occur with HX,
In formula I and formula II, M is nitrogen, sulphur or phosphorus; R1、R2、R3Identical or different with R4, separatelyFor C1-C20Straight or branched alkyl, C3-C20Replacement or unsubstituted cycloalkyl or C6-C20Replacement or unsubstituted aryl; X is halogen atom.
The method according to this invention, the continuous operating time of bipolar membrane electrodialysis device is long, is reducing productionWhen cost, can also shorten owing to changing parts and cause the time of stopping work, enhance productivity.Meanwhile, adopt the purity of hydroxide prepared by method of the present invention high, quality better.
Brief description of the drawings
Fig. 1 is used for a kind of embodiment of the preparation method that hydroxide of the present invention is described; And
Fig. 2 is used for the preparation method's that hydroxide of the present invention is described another kind of embodiment.
Detailed description of the invention
The preparation method who the invention provides the hydroxide shown in a kind of formula I, the method comprises: willThe aqueous solution of the salt shown in formula II is sent in bipolar membrane electrodialysis device, carries out bipolar membrane electrodialysis,To the aqueous solution that contains the hydroxide shown in formula I, wherein, the method comprises to bipolar membrane electrodialysisIn the sour chamber of device, send into neutralizer, described neutralizer contains the material that acid-base reaction can occur with HX,
The method according to this invention, the salt shown in formula II can be according to the structure of the hydroxide of expectionCarrying out suitable selection, can be the conventional various salt in this area. Usually, in formula I and formula II,M can be N, S or P; R1、R2、R3And R4Identical or different, can be C separately1-C20StraightChain or branched alkyl, C3-C20Replacement or unsubstituted cycloalkyl or C6-C20Replacement or do not getThe aryl in generation.
In the present invention, C1-C20The example of straight or branched alkyl can include but not limited to: methyl,Ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isoamylBase, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, dodecyl,N-hexadecyl and n-octadecane base.
In the present invention, C3-C20Replacement or the example of unsubstituted cycloalkyl can include but not limited to:Cyclopropyl, cyclopenta, cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-n-pro-pyl cyclohexylWith 4-normal-butyl cyclohexyl.
In the present invention, C6-C20Replacement or the example of unsubstituted aryl can include but not limited to: benzeneBase, naphthyl, 4-aminomethyl phenyl and 4-ethylphenyl.
In formula I and formula II, M is preferably N.
In formula I and formula II, R1、R2、R3And R4Be preferably C1-C5Straight or branched alkyl, more excellentElect methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group or the tert-butyl group as.
In formula II, X is preferably chlorine atom or bromine atoms.
Particularly, the example of the salt shown in formula II can include but not limited to: tetramethyl ammonium chloride, fourEthyl ammonium chloride, 4-propyl bromide, 4 bromide, tetraethylammonium bromide, 4-propyl ammonium chloride(comprising the various isomers of 4-propyl ammonium chloride), tetrabutylammonium chloride (comprise tetrabutylammonium chlorideVarious isomers), TBAB (comprising the various isomers of TBAB), four pentyl bromineChange ammonium (comprising the various isomers of four pentyl ammonium bromide) and four decyl ammonium bromides and (comprise four decyl brominationsThe various isomers of ammonium). The example of the hydroxide shown in formula I can include but not limited to: tetramethylBase ammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprise the each of TPAOHKind of isomers), four pentyl ammonium hydroxide (comprising the various isomers of four pentyl ammonium hydroxide) and four last of the ten Heavenly stemsBase ammonium hydroxide (comprising the various isomers of four decyl ammonium hydroxide).
Method of the present invention is for the not special limit of set-up mode of the membrane stack in bipolar membrane electrodialysis deviceFixed, can establish for the various membrane stacks that salt is transformed into hydroxide of can realizing that this area is commonly usedPut mode.
In the first embodiment of the present invention, as shown in Figure 1, described electrodialysis plant comprises negative electrode1, anode 4 and at least two Bipolar Membrane 2 between negative electrode 1 and anode 4 and at least one the moonAmberplex 3, Bipolar Membrane 2 and anion-exchange membrane 3 are arranged alternately between negative electrode 1 and anode 4,And Bipolar Membrane 2 separates negative electrode 1 and anion-exchange membrane 3. Preferably, Bipolar Membrane 2 by anode 4 withAnion-exchange membrane 3 separates.
In the first embodiment, the cation exchange layer of described Bipolar Membrane and described anion-exchange membraneBetween be sour chamber, between the anion exchange floor of described Bipolar Membrane and described anion-exchange membrane, be alkali chamber,Between the cation exchange layer of described Bipolar Membrane and described negative electrode, be cathode chamber, the anion of described Bipolar MembraneBetween exchange layer (or described anion-exchange membrane) and described anode, it is anode chamber.
Adopting this embodiment to carry out electrodialysis when preparing hydroxide to salt, as Fig. 1 instituteShow, can will send in alkali chamber as the saline solution shown in the formula II of feed liquid B, to cathode chamber andIn anode chamber, pass into utmost point liquid A, and pass into neutralizer C in sour chamber, then between anode and negative electrode, executeAdd DC current, thereby carry out bipolar membrane electrodialysis.
In the process of bipolar membrane electrodialysis, Bipolar Membrane is hydrogen ion (H by water decomposition+) and hydroxyl fromSon (OH-），OH-Anion exchange floor by Bipolar Membrane enters alkali chamber, with the salt solution shown in formula IISalt contact in solution, with the X in molecules of salt structure-Replace, thereby obtain shown in formula IIHydroxide. The X displacing-Enter in sour chamber by anion-exchange membrane, with electrodialytic processThe H of middle generation+In conjunction with, and then contact instead with the material that can acid-base reaction occur with HX in neutralizerShould.
In the first embodiment, the Bipolar Membrane in bipolar membrane electrodialysis device and anion-exchange membraneQuantity is not particularly limited, and can carry out suitable selection according to production scale. Usually, described bipolarThe quantity of film can be 2-401, and the quantity of described anion-exchange membrane can be 1-400.
In the second embodiment of the present invention, as shown in Figure 2, described electrodialysis plant comprises anode4, negative electrode 1 and at least two Bipolar Membrane 2 between anode 4 and negative electrode 1, at least one sun fromProton exchange 5 and at least one anion-exchange membrane 3, cation-exchange membrane 5 and anion-exchange membrane 3Between Bipolar Membrane 2, Bipolar Membrane 2 is separated between two.
In the second embodiment, between the cation exchange layer of Bipolar Membrane and anion-exchange membrane, be acidChamber, is alkali chamber between the anion exchange floor of Bipolar Membrane and cation-exchange membrane, and cation-exchange membrane is with cloudyBetween amberplex, be feed liquid chamber, between the cation exchange layer of Bipolar Membrane and negative electrode, be cathode chamber, twoBetween the anion exchange layer of utmost point film and anode, it is anode chamber.
In the time adopting the second embodiment cause salt to prepare hydroxide, as shown in Figure 2, canUsing sending in feed liquid chamber as the saline solution shown in the formula II of feed liquid B, to cathode chamber and anode chamberIn send into utmost point liquid A, simultaneously in sour chamber, send into neutralizer C, in alkali chamber, send into water, then at anodeAnd between negative electrode, apply DC current, thereby carry out bipolar membrane electrodialysis.
In bipolar membrane electrodialysis process, under the effect of electric field, the salt shown in formula II polarizes,And form(hereinafter use Q+Represent) and X-. Wherein, Q+Pass through cation exchangeFilm enters in alkali chamber, with the OH producing in bipolar membrane electrodialysis process-In conjunction with, form the season shown in formula IAmmonium alkali; X-Enter in sour chamber by anion-exchange membrane, and produce in bipolar membrane electrodialysis processH+In conjunction with, and further with neutralizer in the material haptoreaction that acid-base reaction can occur with HX.
In the second embodiment, in the salt shown in formula II, R1、R2、R3And R4Preferably separatelyFor C1-C4Straight or branched alkyl, more preferably respectively do for oneself methyl, ethyl, n-pro-pyl or isopropyl.
In the second embodiment, the quantity of Bipolar Membrane, cation-exchange membrane and anion-exchange membraneCan carry out suitable selection according to concrete production scale. Usually, the quantity of described Bipolar Membrane is passableFor 2-401, the quantity of described cation-exchange membrane and anion-exchange membrane can be 1-400 separately.
The method according to this invention, preferably adopts the first embodiment to carry out bipolar membrane electrodialysis.
Although be described with reference to the accompanying drawings according to the preparation method's of hydroxide of the present inventionTwo kinds of detailed description of the invention, but it will be appreciated by persons skilled in the art that to adopt is different fromThe membrane stack setting of bipolar membrane electrodialysis device mentioned above, as long as this membrane stack setting can be by shown in formula IISalt preparation formula I shown in hydroxide.
The method according to this invention, in described neutralizer can there is the material of acid-base reaction with HX canThink the conventional various chemical combination that acid-base reaction can occur with the HX that generates in bipolar membrane electrodialysis processThing. Preferably, the described material that can acid-base reaction occur with HX is selected from water-soluble alkali, for example: NH3And M ' (OH)n, wherein, M ' be alkali metal (as Li, Na and K), alkaline-earth metal (as Mg) andOne in transition metal, is preferably alkali metal, more preferably Na or K; N is integer, with M's 'Chemical valence and determining.
More preferably, using ammoniacal liquor as neutralizer. During using ammoniacal liquor as neutralizer, can effectively alleviateThe extent of corrosion of bipolar membrane electrodialysis device and auxiliary equipment thereof. And, due to can not in bipolar membrane deviceIn avoiding existing, blend film infiltration, if adopt ammoniacal liquor as neutralizer, because interior leakage or film infiltration enterThe ammoniacal liquor as neutralizer of alkali chamber can be by the hydroxide as product that contains to the output of alkali chamberThe material of thing carries out decompression distillation and separates, so can not introduce for example alkali metal ion in productForeign ion, neutralizer can be collected and be reused as to the ammonia distillate distilling out.
The feed liquid passing in the sour chamber of bipolar membrane electrodialysis device is generally and recycles, if in Bipolar MembraneIn the sour chamber of electrodialysis plant, only pass into water, the X in the water that ought recycle-(particularly X is BrTime) content is while being 2-3 % by weight, just must change recirculated water, otherwise bipolar membrane electrodialysis device very easilyProduce fault. Adopt method of the present invention, even X in the neutralizer recycling-(particularly X isWhen Br) content is more than 8 % by weight, even up to 10 % by weight, bipolar membrane electrodialysis device is stillCan normally move. In addition, the NH in neutralizer3Can separate by decompression distillation. Therefore,Be ammoniacal liquor and X while being Br at neutralizer, discarded neutralizer can also be used for refining bromine, has realizedCompletely without the cleaner production of discharge.
When using ammoniacal liquor as neutralizer, the concentration of ammoniacal liquor can be normal concentration. Preferably, described ammoniaThe concentration of water is 0.5-8 % by weight.
The method according to this invention, the material that acid-base reaction can occur with HX in described neutralizerAmount can be carried out suitable selection according to the amount of sending into the salt in bipolar membrane electrodialysis device. Usually,The amount of substance that can acid-base reaction occur with HX in described neutralizer can be guaranteed to export from sour chamberThe pH value of neutralizer be 5.5-8, be preferably 7-8.
The method according to this invention, to the not special limit of kind of the utmost point liquid passing in cathode chamber and anode chamberFixed, can be the conventional various utmost point liquid in this area, for example: sulfuric acid. The present inventor was studyingJourney is further found, as utmost point liquid phase ratio, adopts the aqueous solution or the hydroxide of NaOH with use sulfuric acidThe aqueous solution of potassium, as utmost point liquid, can further be alleviated the extent of corrosion, particularly anode of electrodialysis plantExtent of corrosion with negative electrode. And, adopt the aqueous solution of NaOH or the aqueous solution conduct of potassium hydroxideUtmost point liquid can also obtain has more highly purified hydroxide. Preferably, described utmost point liquid is NaOHThe aqueous solution. More preferably, described utmost point liquid is that concentration is the aqueous solution of the NaOH of 0.1-5 % by weight.The angle of the purity of the hydroxide of preparing from further raising, described utmost point liquid more preferablyConcentration is the aqueous solution of the NaOH of 0.1-0.5 % by weight.
The method according to this invention, the condition of described bipolar membrane electrodialysis is not particularly limited, and can be thisThe routine in field is selected. Usually, the condition of described bipolar membrane electrodialysis comprises: temperature can be 20-40DEG C, the density of the electric current applying between described anode and negative electrode can be 1.5-10A/dm2。
The method according to this invention, the concentration of described saline solution can be that the routine of this area is selected,Be not particularly limited. Usually, the concentration of described saline solution can be 5-50 % by weight.
The method according to this invention, what obtain by bipolar membrane electrodialysis contains the hydroxide shown in formula IThe aqueous solution of thing can directly use, and also can after by method dehydrations such as distillations, obtain solid quaternary ammoniumAlkali.
The method according to this invention, in actual moving process, can arrange utmost point liquid storage tank, feed liquid storage tank(, saline solution storage tank) and neutralizer storage tank, and by above-mentioned storage tank separately with Bipolar Membrane electric osmoseChamber in analysis apparatus is communicated with, thereby forms loop, realizes serialization operation.
Describe the present invention in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, the liquid that adopts aas determination to contain hydroxideThe content of mutually middle metallic atom; Adopt AgNO3Halogen in the liquid phase that titration measuring contains hydroxideThe content of element atom; Adopt acid base titration method to determine the productive rate of hydroxide.
In following examples and comparative example, wppm represent by weight 1,000,000/.
Embodiment 1-5 is for illustrating the preparation method of hydroxide of the present invention.
Embodiment 1
The membrane stack of the bipolar membrane electrodialysis device using in the present embodiment as shown in Figure 1, wherein, Bipolar MembraneQuantity be 51, the quantity of anion-exchange membrane is 50.
4-propyl bromide is dissolved in the water, is mixed with the aqueous solution that concentration is 25 % by weight, juxtapositionIn feed liquid storage tank. NaOH is dissolved in the water, is mixed with the aqueous solution that concentration is 0.18 % by weight,As utmost point liquid, and be placed in utmost point liquid storage tank. Using concentration be the ammoniacal liquor of 2.5 % by weight as neutralizer, willNeutralizer is placed in neutralizer storage tank.
The 4-propyl bromide aqueous solution of preparation is sent in the alkali chamber of bipolar membrane electrodialysis device, by utmost point liquidSend in the anode chamber and cathode chamber of bipolar membrane electrodialysis device, neutralizer is sent into bipolar membrane electrodialysis dressIn the sour chamber of putting. Then, between the anode of bipolar membrane electrodialysis device and negative electrode, apply direct current,At the temperature of 35 DEG C, carry out continuously the bipolar membrane electrodialysis of 70 hours, obtain containing tetrapropyl hydroxideThe aqueous solution of ammonium. Wherein, current density is 4A/dm2。
Produce in a manner described, electrodialysis plant continuous operation 2000 hours is no abnormal, itsIn, in continuous operation process, the pH value of neutralizer is controlled in the scope of 7-8, and in neutralizationBr in liquid-When being 8-10 % by weight, concentration changes neutralizer.
In process of production, the purity of the aqueous solution that contains TPAOH of each batch is examinedSurvey, found that the purity of the each batch of aqueous solution obtaining is stable, wherein, TPAOH denseDegree is 17 % by weight, Na+Content is for being less than 1wppm, Br-Content is 0.32 % by weight.
After end of run, the TPAOH aqueous solution decompression distillation obtaining is concentrated into tetrapropyl hydrogenThe concentration of amine-oxides is 25 % by weight, obtains containing the distillate of ammonia and is circulated as neutralizer, subtractsPress the condition of distillation to comprise: in absolute pressure, pressure is 0.07-0.08MPa, and temperature is 60 DEG C.
Comparative example 1
Adopt the method identical with embodiment 1 to carry out bipolar membrane electrodialysis, to prepare TPAOH,Different, what be placed in neutralizer storage tank is deionized water, instead of neutralizer.
In continuous operation process, in the water in neutralizer storage tank, Br-When concentration is 2-3 % by weight, moreChange the deionized water in neutralizer storage tank. When bipolar membrane electrodialysis equipment accumulative total runs to 120 hours, twoUtmost point EDBM device cannot normally move, and operation stops. The membrane stack of bipolar membrane electrodialysis device is disassembledAfter, find that anode is corroded, and the Bipolar Membrane bubbling adjacent with positive plate perforation.
In production process, the purity of every batch of aqueous solution that contains TPAOH is detected,In the aqueous solution that what first obtained contain n-pro-pyl ammonium hydroxide, the concentration of TPAOH is16.23 % by weight, Na+Content is 10wppm, Br-Content is 0.38 % by weight. Run to 120 hoursIn the aqueous solution that contains TPAOH obtaining, the concentration of TPAOH is 14.16 weightsAmount %, Na+Content is 75wppm, Br-Content is 5.94 % by weight.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare TPAOH, different, neutralizer isConcentration is the sodium hydrate aqueous solution of 0.8 % by weight, in continuous operation process, by the pH value of neutralizerBe controlled in the scope of 7-8.
Produce in a manner described, electrodialysis plant continuous operation 2000 hours is no abnormal.
In process of production, the purity of the aqueous solution that contains TPAOH of each batch is examinedSurvey, found that the purity of the each batch of aqueous solution obtaining is stable, wherein, TPAOH denseDegree is 17.12 % by weight, Na+Content is 350wppm, Br-Content is 0.38 % by weight.
Embodiment 3
Adopt the method identical with embodiment 1 to carry out bipolar membrane electrodialysis, to prepare hydroxide, noWith:
Etamon chloride is mixed with to the aqueous solution that concentration is 30 % by weight; The neutralizer using is denseDegree is the ammoniacal liquor of 2.5% % by weight; Use utmost point liquid for concentration be the NaOH aqueous solution of 0.18 % by weight;
At the temperature of 40 DEG C, carry out continuously the bipolar membrane electrodialysis of 65 hours, obtain containing tetraethylThe aqueous solution of ammonium hydroxide. Wherein, current density is 3.5A/dm2。
Produce in a manner described, electrodialysis plant continuous operation 2000 hours is no abnormal, itsIn, in continuous operation process, Cl in neutralizer-When being 8-10 % by weight, concentration changes neutralizer.
In process of production, the purity of the aqueous solution that contains tetraethyl ammonium hydroxide of each batch is examinedSurvey, found that the purity of the each batch of aqueous solution obtaining is stable, wherein, tetraethyl ammonium hydroxide denseDegree is 20.5 % by weight, Na+Content is 3wppm, Cl-Content is 0.29 % by weight.
Embodiment 4
The membrane stack of the bipolar membrane electrodialysis device using in the present embodiment as shown in Figure 2, wherein, Bipolar MembraneQuantity be 20, the quantity of anion-exchange membrane is 19, the quantity of cation-exchange membrane is 19.
Tetramethyl ammonium chloride is dissolved in the water, is mixed with the aqueous solution that concentration is 20 % by weight, juxtapositionIn feed liquid storage tank. NaOH is dissolved in the water, is mixed with the aqueous solution that concentration is 0.18 % by weight,As utmost point liquid, and be placed in utmost point liquid storage tank. Using concentration be the ammoniacal liquor of 1.2 % by weight as neutralizer, willNeutralizer is placed in neutralizer storage tank.
The tetramethyl ammonium chloride aqueous solution of preparation is sent in the feed liquid chamber of bipolar membrane electrodialysis device, by the utmost pointLiquid is sent in the anode chamber and cathode chamber of bipolar membrane electrodialysis device, and neutralizer is sent into bipolar membrane electrodialysisIn the sour chamber of device, deionized water is sent in alkali chamber. Then, at the anode of bipolar membrane electrodialysis deviceApply direct current with negative electrode, at the temperature of 40 DEG C, carry out continuously the bipolar membrane electrodialysis of 65 hours,Obtain the aqueous solution that contains TMAH. Wherein, current density is 3A/dm2。
Produce in a manner described, electrodialysis plant continuous operation 2000 hours is no abnormal, itsIn, in continuous operation process, in continuous operation process, the pH value of neutralizer is controlled to the model of 7-8In enclosing, Cl in neutralizer-When being 8-10 % by weight, concentration changes neutralizer.
In process of production, the purity of the aqueous solution that contains TMAH of each batch is examinedSurvey, found that the purity of the each batch of aqueous solution obtaining is stable, wherein, TMAH denseDegree is 12 % by weight, Na+Content is for being less than 1wppm, Cl-Content is 0.029 % by weight.
Comparative example 2
Adopt the method bipolar membrane electrodialysis identical with embodiment 4, to prepare TMAH, noWith, what be placed in neutralizer storage tank is deionized water, instead of neutralizer in embodiment 4.
In continuous operation process, in the water in neutralizer storage tank, Cl-When concentration is 2-3 % by weight, moreChange the deionized water in neutralizer storage tank. When bipolar membrane electrodialysis device accumulative total runs to 255 hours, lean onThe Bipolar Membrane foaming leakage of nearly anode, causes bipolar membrane electrodialysis device normally to move, and operation stops.
In production process, the purity of every batch of aqueous solution that contains TMAH is detected,In the aqueous solution that contains TMAH that first three batch obtains, the concentration of TMAH is12.5 % by weight, Na+Content is 5wppm, Cl-Content is 0.045 % by weight; Run to 255 hoursTime the aqueous solution that contains TMAH that obtains in, the concentration of TMAH is 10.4% by weight, Na+Content is 55wppm, Cl-Content is 0.68 % by weight.
Embodiment 5
Adopt the identical bipolar membrane electrodialysis device of embodiment 1 to carry out bipolar membrane electrodialysis, to prepare hydrogenOxide, different:
Four pentyl ammonium bromide is mixed with to the aqueous solution that concentration is 25 % by weight; The neutralizer using is denseDegree is the ammoniacal liquor of 2.5 % by weight; Use utmost point liquid for concentration be the NaOH aqueous solution of 0.18 % by weight;
At the temperature of 40 DEG C, carry out continuously the bipolar membrane electrodialysis of 65 hours, obtain containing four pentylThe aqueous solution of ammonium hydroxide. Wherein, current density is 3A/dm2。
Produce in a manner described, electrodialysis plant continuous operation 2000 hours is no abnormal.
In process of production, the purity of the aqueous solution that contains four pentyl ammonium hydroxide of each batch is examinedSurvey, found that the purity of the each batch of aqueous solution obtaining is stable, wherein, four pentyl ammonium hydroxide denseDegree is 18.3 % by weight, Na+Content is 2wppm, Br-Content is 0.47 % by weight.
Claims (12)
1. a preparation method for the hydroxide shown in formula I, the method comprises: shown in formula IIThe aqueous solution of salt send in bipolar membrane electrodialysis device, carry out bipolar membrane electrodialysis, obtain containing formulaThe aqueous solution of the hydroxide shown in I, is characterized in that, the method comprises to bipolar membrane electrodialysis and fillingIn the sour chamber of putting, send into neutralizer, described neutralizer contains the material that acid-base reaction can occur with HX,The amount of substance that can acid-base reaction occur with HX in described neutralizer make to export from sour chamber inWith the pH value of liquid be 5.5-8,
In formula I and formula II, M is nitrogen or phosphorus; R1、R2、R3And R4Identical or different, C respectively does for oneself1-C20Straight or branched alkyl, C3-C20Replacement or unsubstituted cycloalkyl or C6-C20Replacement orUnsubstituted aryl; X is halogen atom.
2. method according to claim 1, wherein, described bipolar membrane electrodialysis device comprises sunThe utmost point, negative electrode and at least two Bipolar Membrane and at least one anion between described anode and negative electrodeExchange membrane, described Bipolar Membrane and anion-exchange membrane are arranged alternately between described anode and negative electrode, and instituteState Bipolar Membrane described negative electrode and described anion-exchange membrane are separated, the method comprises shown in formula IIThe aqueous solution of salt is sent in the alkali chamber of bipolar membrane electrodialysis device.
3. method according to claim 1, wherein, described bipolar membrane electrodialysis device comprises sunThe utmost point, negative electrode and at least two Bipolar Membrane between described anode and negative electrode, at least one cationExchange membrane and at least one anion-exchange membrane, described cation-exchange membrane and anion-exchange membrane are positioned at instituteState between Bipolar Membrane, described Bipolar Membrane is separated between two, described cation-exchange membrane and described anion are handed overChanging between film is feed liquid chamber, and the method comprises sends the aqueous solution of the salt shown in formula II into described feed liquid chamberIn.
4. according to the method described in any one in claim 1-3, wherein, to described Bipolar Membrane electricityThe aqueous solution that the utmost point liquid of sending in the anode chamber of electrodialysis apparatus and cathode chamber is NaOH.
5. according to the method described in any one in claim 1-3, wherein, M is nitrogen.
6. according to the method described in any one in claim 1-3, wherein, R1、R2、R3And R4Be C independently of one another1-C5Straight or branched alkyl.
7. method according to claim 6, wherein, R1、R2、R3And R4Be independently of one anotherMethyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group or the tert-butyl group.
8. according to the method described in any one in claim 1-3, wherein, X is chlorine atom or bromineAtom.
9. according to the method described in any one in claim 1-3, wherein, described can with HXThe material that acid-base reaction occurs is water-soluble alkali.
10. method according to claim 9, wherein, described neutralizer is ammoniacal liquor.
11. methods according to claim 10, wherein, the concentration of described ammoniacal liquor is 0.5-8 % by weight.
12. according to the method described in any one in claim 1-3, wherein, and described Bipolar Membrane electric osmoseThe condition of analysing comprises: temperature is 20-40 DEG C, the galvanic electricity applying between described anode and negative electrodeCurrent density is 1.5-10A/dm2。
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| CN111777134A (en) * | 2015-10-30 | 2020-10-16 | 中国石油化工股份有限公司 | Wastewater treatment method, molecular sieve preparation method and molecular sieve preparation system |
| CN105862070B (en) * | 2016-04-11 | 2018-02-23 | 广州大有精细化工厂 | The method that the hydroxymandelic acid of 3 methoxyl group 4 or the hydroxymandelic acid of 3 ethyoxyl 4 are prepared using bipolar membrane electrodialysis |
| CN105833729A (en) * | 2016-05-12 | 2016-08-10 | 浙江赛特膜技术有限公司 | Bipolar membrane electrodialysis system and method for preparing high-purity tetramethylammonium hydroxide through system |
| CN107200690A (en) * | 2017-05-05 | 2017-09-26 | 刘铁群 | A kind of application membrane technology produces the environmental protection method of TPAOH |
| CN107652185A (en) * | 2017-07-03 | 2018-02-02 | 杭州龙智科技有限公司 | The preparation facilities and preparation method of benzyltrimethylammonium hydroxide |
| CN107365258B (en) * | 2017-07-03 | 2020-07-24 | 杭州龙智科技有限公司 | Preparation device and preparation method of tetraethyl ammonium hydroxide solution |
| CN108299209A (en) * | 2018-01-20 | 2018-07-20 | 盐城泛安化学有限公司 | A method of it is prepared using membrane integrating technique and concentrates tetraethyl ammonium hydroxide |
| CN109232264B (en) * | 2018-10-31 | 2021-03-16 | 江西肯特化学有限公司 | Environment-friendly method for producing tetrapropylammonium hydroxide by using membrane technology |
| CN113981476A (en) * | 2021-09-17 | 2022-01-28 | 镇江润晶高纯化工科技股份有限公司 | Preparation method of energy-saving tetraethylammonium hydroxide with high production efficiency |
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