CN1683289A

CN1683289A - Process for ionic compound water soluble liquid

Info

Publication number: CN1683289A
Application number: CNA2005100563394A
Authority: CN
Inventors: 内山实; 山本盛夫; 车谷昌彦
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2004-03-15
Filing date: 2005-03-13
Publication date: 2005-10-19
Also published as: KR20060044330A; TW200602433A

Abstract

The invention provides a method for producing ionic compound aqueous solution concluding the following steps of (a), (b) and (c). The (a) step is to mix a hydrophobic amine and a hydrophobic organic solvent to an aqueous solution containing the ionic compound and the PH value of the aqueous phase part is adjusted to 0.01 to 2, then the organic phase is obtained containing a salt of an anion and hydrophobic amine generated from the ionic compound. Wherein, the ionic compound is provided with at least one aqueous solution radical chosen from the -SO3Na radical, -SO3K radical, -SO3NH4 radical, -COONa radical, -COOK radical, -PO3NA radical, -PO3K radical, -PO3NH4 radical and -COONH4 radical. The (b) step is to mix the organic phase obtained in the step (a) with the compound containing cation as the aqueous solution, and separate the liquid to obtain an aqueous phase containing a salt of the anion and the cation generated from the ionic compound. The (c) step is to remove inorganic salt with a membrane separating device to obtain an aqueous solution of an anion generated from the ionic compound from the counterion to the cation.

Description

The manufacture method of ionic compound water soluble liquid

Technical field

The present invention relates to the manufacture method of ionic compound.

Background technology

Intramolecularly has-SO ₃The Na base ,-SO ₃The K base ,-the COONa base or-ionic compound of water soluble groups such as COOK base, be widely used in dyestuff, agricultural chemicals, medicine, washing composition, foodstuff additive etc.Recently, in the printing press in the information record field that is used for electronic photo, digital photograph etc., extensively adopt following method, that is: make as the ionic compound of dye compound printing ink, be splashed on the recording materials such as common paper, glazed paper, cloth from small drop outlet orifice and carry out record as principal constituent.For ionic compound, require in above-mentioned outlet orifice, not solidify and long-time stable discharge of warp.As suppress the method that ionic compound solidifies in outlet orifice, generally can adopt the counterion of the water soluble group that ionic compound is comprised to be replaced as the method for lithium ion.

Be replaced as the method for required counterion as the counterion with the water soluble group that ionic compound contained, known have the method implemented in two steps based on the desalination of membrane sepn (spy open flat 11-130699 communique (embodiment 1 and 2[0029]～[0038]).

Yet, in aforesaid method, have following problem, that is: should carry out twice desalination based on membrane sepn, and when required positively charged ion must use in a large number during for lithium ion high price lithium salts.

Present inventors etc. study the manufacture method that can address the above problem, and found that, by carrying out desalination someway, not only can reduce the usage quantity of cationic salts, and can easily make ionic compound water soluble liquid by a step desalination.

Summary of the invention

The objective of the invention is to, provide a kind of usage quantity that can reduce cationic salts can carry out the manufacture method of the ionic compound water soluble liquid of a step desalination.

That is, the invention provides following [1]～[11].

[1] a kind of manufacture method of ionic compound water soluble liquid comprises following (a) and (b), (c) three operations:

(a) operation:

In the aqueous solution that contains ionic compound, mix hydrophobic amine and hydrophobic organic solvent, and the pH of water portion is adjusted into 0.01～2 and separatory, obtain to contain the organic phase of the salt of the negatively charged ion that generates from ionic compound and hydrophobic amine then, wherein, described ionic compound has from by-SO ₃The Na base ,-SO ₃The K base ,-SO ₃NH ₄Base ,-the COONa base ,-the COOK base ,-PO ₃The Na base ,-PO ₃The K base ,-PO ₃NH ₄The base and-COONH ₄At least a water soluble group of selecting in the group that base constitutes.

(b) operation:

In the organic phase that obtains in (a) operation, will contain after cationic compound mixes as the aqueous solution, separatory obtains to contain the negatively charged ion that generates from ionic compound and the water of described cationic salt.

(c) operation:

Remove inorganic salt with the water that membrane separation unit obtains from (b) operation, obtaining to contain from counterion is the anionic aqueous solution that described cationic ionic compound generates.

[2] as [1] described manufacture method, add mineral acid, the pH of water portion is adjusted into 0.01～2.

[3] as [1] or [2] described manufacture method, ionic compound is from adding at least a water colo(u)r of selecting the material group that constitutes with dyestuff, substantive dyestuff and reactive dye by matching stain, food.

[4] as any one described manufacture method in [1]～[3], hydrophobic amine is that carbonatoms is the amine more than 12.

[5] as any one described manufacture method in [1]～[4], hydrophobic organic solvent is at least a hydrophobic solvent of selecting from the material group that is made of toluene, dimethylbenzene and monochloro-benzene.

[6] as any one described manufacture method in [1]～[5], containing cationic compound is at least a compound of selecting from the material group that is made of Quilonum Retard, lithium bicarbonate, lithium hydroxide, potassium hydroxide, salt of wormwood, saleratus, ammonium hydroxide and ammonia.

[7] as any one described manufacture method in [1]～[6], membrane separation unit is filtering membrane tripping device or electrodialysis unit.

[8] as any one described manufacture method in [1]～[7], membrane separation unit is the filtering membrane tripping device, and when the aqueous sodium persulfate solution that uses 3.64 weight % carried out membrane sepn, the filtering membrane of this device was by following formula (1)

R＝[1-(Cp/3.64)]×100 (1)

The rejection R that (in the formula, R represents the rejection [%] of filtering membrane, and Cp represents to carry out membrane sepn and the concentration [weight %] that sees through the sodium sulfate in the liquid that obtains by filtering membrane) calculates is below 90%,

[9], be that rejection R is 40～60% filtering membrane as [8] described manufacture method.

[10] as any one described manufacture method in [1]～[9], the filtering membrane of filtering membrane tripping device is ultra-filtration membrane or reverse osmosis membrane.

[11] as any one described manufacture method in [1]～[10], the filtering membrane tripping device is the membrane separation unit that full filters shape or cross-stream ejector half filtration shape.

[12] as any one described manufacture method in [1]～[11], electrodialysis unit uses the penetration speed of 10% tosic acid sodium water solution to be 0.05kgm ^-2H ^-1V ^-1Above anion-exchange membrane.

[13] as any one described manufacture method in [1]～[12], the penetration speed of the tosic acid sodium water solution of electrodialysis unit use 10% is 0.15～0.5kgm ^-2H ^-1V ^-1Anion-exchange membrane.

[14] as any one described manufacture method in [1]～[13], be recovered in the organic phase that contains hydrophobic amine and hydrophobic organic solvent in (b) operation, and the organic layer that reclaims is used as the hydrophobic amine of (a) operation and the part of hydrophobic organic solvent.

The invention provides the manufacture method of the ionic compound water soluble liquid that comprises following (a) and (b), (c) operation.

In the present invention, generally carry out following (a) and (b), (c) operation, can append suitable, necessary operation in the front and back of these operations by (a) and (b), (c) order.

(a) operation is, in containing the aqueous solution of ionic compound, mix hydrophobic amine and hydrophobic organic solvent, and add mineral acid as required, the pH of water portion is adjusted into 0.01～2 and separatory, obtain to contain the operation of organic phase of the salt of the negatively charged ion that generates from ionic compound and hydrophobic amine then, wherein, described ionic compound has from by-SO ₃The Na base ,-SO ₃The K base ,-SO ₃NH ₄Base ,-the COONa base ,-the COOK base ,-PO ₃The Na base ,-PO ₃The K base ,-PO ₃NH ₄The base and-COONH ₄At least a water soluble group of selecting in the group that base constitutes.

(b) operation is, in the organic phase that obtains in (a) operation, will contain after cationic compound mixes as the aqueous solution, and separatory obtains to contain the operation of the water of the negatively charged ion that generates from ionic compound and described cationic salt.

(c) operation is, removes inorganic salt with membrane separation unit, and obtaining to contain from counterion is the operation of the anionic aqueous solution that described cationic ionic compound generated.

At first, (a) operation is described.

(a) operation is, in the aqueous solution that contains ionic compound, mix hydrophobic amine and hydrophobic organic solvent, and add at least a mineral acid of from the material group that constitutes by nitric acid, sulfuric acid and phosphoric acid, selecting as required, with the pH of water portion be adjusted into 0.01～2 and separatory after, acquisition contains the operation of the organic phase of the salt that is formed by negatively charged ion that generates from ionic compound and hydrophobic amine, wherein, described ionic compound has from by-SO ₃The Na base ,-SO ₃The K base ,-SO ₃NH ₄Base ,-the COONa base ,-the COOK base ,-PO ₃The Na base ,-PO ₃The K base ,-PO ₃NH ₄The base and-COONH ₄At least a water-soluble base of selecting in the group that base constitutes.

As ionic compound, specifically can enumerate matching stain, substantive dyestuff, food interpolation water colo(u)rs such as dyestuff and reactive dye.

As matching stain, for example can enumerate following material.

C.I.Acid?Yellow 1

C.I.Acid?Yellow 7

C.I.Acid?Yellow 11

C.I.Acid?Yellow 17

C.I.Acid?Yellow 23

C.I.Acid?Yellow 25

C.I.Acid?Yellow 29

C.I.Acid?Yellow 36

C.I.Acid?Yellow 38

C.I.Acid?Yellow 40

C.I.Acid?Yellow 42

C.I.Acid?Yellow 44

C.I.Acid?Yellow 76

C.I.Acid?Yellow 164

C.I.Acid?Orange 7

C.I.Acid?Orange 8

C.I.Acid?Orange 10

C.I.Acid?Orange 19

C.I.Acid?Orange 20

C.I.Acid?Orange 24

C.I.Acid?Orange 28

C.I.Acid?Orange 33

C.I.Acid?Orange 41

C.I.Acid?Orange 45

C.I.Acid?Orange 51

C.I.Acid?Orange 56

C.I.Acid?Red 1

C.I.Acid?Red 6

C.I.Acid?Red 8

C.I.Acid?Red 13

C.I.Acid?Red 14

C.I.Acid?Red 18

C.I.Acid?Red 26

C.I.Acid?Red 27

C.I.Acid?Red 32

C.I.Acid?Red 35

C.I.Acid?Red 52

C.I.Acid?Red 80

C.I.Acid?Red 82

C.I.Acid?Red 85

C.I.Acid?Red 88

C.I.Acid?Red 97

C.I.Acid?Red 106

C.I.Acid?Red 111

C.I.Acid?Red 114

C.I.Acid?Red 115

C.I.Acid?Red 133

C.I.Acid?Red 134

C.I.Acid?Red 145

C.I.Acid?Red 154

C.I.Acid?Red 155

C.I.Acid?Red 249

C.I.Acid?Red 265

C.I.Acid?Violet 7

C.I.Acid?Violet 41

C.I.Acid?Violet 43

C.I.Acid?Violet 51

C.I.Acid?Blue 9

C.I.Acid?Blue 23

C.I.Acid?Blue 25

C.I.Acid?Blue 27

C.I.Acid?Blue 29

C.I.Acid?Blue 40

C.I.Acid?Blue 41

C.I.Acid?Blue 43

C.I.Acid?Blue 45

C.I.Acid?Blue 62

C.I.Acid?Blue 74

C.I.Acid?Blue 78

C.I.Acid?Blue 80

C.I.Acid?Blue 92

C.I.Acid?Blue 113

C.I.Acid?Blue 117

C.I.Acid?Blue 120

C.I.Acid?Blue 127

C.I.Acid?Blue 138

C.I.Acid?Green 19

C.I.Acid?Green 20

C.I.Acid?Green 25

C.I.Acid?Green 27

C.I.Acid?Green 36

C.I.Acid?Green 41

C.I.Acid?Green 44

C.I.Acid?Brown 2

C.I.Acid?Brown 13

C.I.Acid?Brown 14

C.I.Acid?Brown 20

C.I.Acid?Brown 27

C.I.Acid?Black 1

C.I.Acid?Black 7

C.I.Acid?Black 12

C.I.Acid?Black 24

C.I.Acid?Black 26

C.I.Acid?Black 31

C.I.Acid?Black 94

In these matching stains, preferably use C.I.Acid Red 52, C.I.Acid Blue 9, C.I.Acid Black 12, C.I.Acid Yellow 11.

As substantive dyestuff, for example can enumerate following material.

C.I.Direct?Violet 63

C.I.Direct?Yellow 86

C.I.Direct?Yellow 132

C.I.Direct?Yellow 142

C.I.Direct?Yellow 173

C.I.Direct?Black 17

C.I.Direct?Black 19

C.I.Direct?Black 22

C.I.Direct?Black 154

C.I.Direct?Red 80

C.I.Direct?Red 81

C.I.Direct?Blue 86

C.I.Direct?Blue 185

C.I.Direct?Blue 199

In these substantive dyestuff, the following material of preferred use.

C.I.Direct?Yellow 86

C.I.Direct?Red 80

C.I.Direct?Red 81

C.I.Direct?Black 17

C.I.Direct?Black 19

C.I.Direct?Black 22

C.I.Direct?Black 154

C.I.Direct?Blue 86

C.I.Direct?Blue 185

C.I.Direct?Blue 199

Add as food and to use dyestuff, for example can enumerate C.I.Food Black 2 etc.

As reactive dye, can enumerate and for example have the material as reactive group such as a chlorotriazine base, dichlorotriazine base, trichloropyrimidine base, dichloro-quinoxaline base, Methanesulfonyl chloride picolyl, a chlorine difluoro pyridine base or methyl fluoride triazinyl.

As having, can enumerate for example following material etc. with the material as reactive group such as a chlorotriazine base, dichlorotriazine base, trichloropyrimidine base, dichloro-quinoxaline base, Methanesulfonyl chloride picolyl, a chlorine difluoro pyridine base or methyl fluoride triazinyl.

C.I.Reactive?Orange 1

C.I.Reactive?Orange 2

C.I.Reactive?Red 17

C.I.Reactive?Red 180

C.I.Reactive?Violet 9

C.I.Reactive?Blue 4

C.I.Reactive?Blue 5

C.I.Reactive?Brown 1

C.I.Reactive?Black 10

Wherein, preferably use C.I.Reactive Red 180.

As ionic compound, preferably use water colo(u)r, especially preferably use matching stain, substantive dyestuff.

In addition, as the pigment matrix of above-mentioned ionic compound, can enumerate azo based dyes such as monoazo-dyes, disazo dyes, trisazo dye or Tetrakisazo dyes, anthraquinone based dye, anthrapyridone based dye, Kui phthalein ketone based dye, tritane based dye, phthalocyanine based dye, dioxazine based dye etc.

As the water soluble group that ionic compound contained, can enumerate-SO ₃The Na base ,-SO ₃The K base ,-SO ₃NH ₄Base ,-the COONa base ,-the COOK base ,-PO ₃The Na base ,-PO ₃The K base ,-PO ₃NH ₄The base and-COONH ₄Base etc.For water soluble group, can in same ionic compound, there be different types of water soluble group.In addition, water-soluble base can exist multiple in same ionic compound.

As the counterion of ionic compound, use monovalent cations such as lithium ion, sodium ion, potassium ion, ammonium ion usually.

In addition, the viewpoint of the branch fluidity from (a) operation, the amount of moisture that is contained in the ionic compound water soluble liquid as the raw material use, these aqueous solution 100 weight parts are about 70～98 weight parts relatively usually.

Hydrophobic amine is the amine compound with alkyl, and the carbonatoms of preferred alkyl is about 12～30 tertiary amine.

Specifically; can enumerate lauryl methyl amine, benzyl lauryl amine, myristyl methylamine, palmityl methylamine, stearyl-methylamine, oleyl methylamine, inferior oil base methylamine, dilauryl methylamine, myristyl amine, two palmityl amines, distearyl acyl group amine, two oleyl amine, two inferior oil base amine, dilauryl methylamine, distearyl ylmethyl amine, dioctylamine, didecyl acyl amine, diisooctyl amine, tri-n-butyl amine, three n-octylamine, three-(3; 5,5-trimethylammonium hexyl) amine, three iso-octyl amine, by following formula (I)

The tertiary amine of [in the formula, R represents that carbonatoms is that 8～18 alkyl or carbonatoms are 8～18 thiazolinyl] expression etc.

As hydrophobic amine, especially preferably by the tertiary amine of formula (I) expression.

As the usage quantity of hydrophobic amine, with respect to the water soluble group that ionic compound contained, be generally that 1 equivalent is above, about preferred 1.5～5 equivalents.

As hydrophobic organic solvent, can enumerate for example aliphatic hydrocarbon, ester ring type hydrocarbon, aromatic hydrocarbons etc., wherein, optimization aromatic hydrocarbon especially.Can also be on the aromatic hydrocarbons in conjunction with halogen atom.As the concrete example of hydrophobic organic solvent, can enumerate toluene, dimethylbenzene, monochloro-benzene etc.

About the usage quantity of hydrophobic organic solvent, so long as can dissolve the amount of the ionic compound that uses, just be not particularly limited, but specifically when ionic compound is water colo(u)r, relative water colo(u)r 1 weight part is about 1～20 weight part.

In (a) operation, at first in containing the aqueous solution of ionic compound, mix hydrophobic amine and hydrophobic organic solvent, and add mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid as required, preferred sulfuric acid or the phosphoric acid of adding, preferably sulfuric acid especially, the pH of water portion is adjusted into 0.01～2, preferably is adjusted into 0.5～1.If the pH of the water portion behind the separatory is the pH beyond the above-mentioned scope, then add mineral acid and mix, make its separatory, the pH of water portion is adjusted into the above-mentioned scope that is in.

If the pH of water portion is more than 0.01, the inorganic acid ion in the ionic compound that then obtains in this manufacture method has the tendency of reduction, so preferred; And if pH is below 2, the positively charged ion removed ratios from water portion such as sodium ion as the ionic compound of raw material, cupric ion that then come from have the tendency that increases, so preferred.

For in (a) operation by the organic phase of separatory, before implementing (b) operation, preferably wash with ion exchanged water etc.By washing, can further remove positively charged ion, thereby reduce required positively charged ion positively charged ion in addition described later.

The water yield as this washing is used with respect to organic phase 1 weight part, is generally about 0.1～10 weight part, about preferred 0.2～2 weight part.

Carry out after pH adjusts, make the salt that contains ionic compound and hydrophobic amine in the organic phase, hydrophobic organic solvent etc., this can be used for (b) operation.

In (b) operation, for the organic phase that obtains in (a) operation, after the compound that will contain required cationic mixed as the aqueous solution, separatory can obtain to contain the water of the salt of the negatively charged ion that generates from ionic compound and required cationic.

,, can enumerate lithium ion, potassium ion, ammonium ion etc. here as required positively charged ion, from be suppressed in the outlet orifice the viewpoint of solidifying and as the viewpoint of the printing characteristic of printing ink, preferably use lithium ion, ammonium ion.

Contain normally basic cpd of cationic compound, specifically can enumerate Quilonum Retard, lithium bicarbonate, lithium hydroxide, salt of wormwood, saleratus, potassium hydroxide, ammonium hydroxide and ammonia etc.Wherein, when required positively charged ion is lithium ion, preferably uses lithium hydroxide, and when required positively charged ion is ammonium ion, preferably use ammonium hydroxide, ammonia.

If identical positively charged ion then can use different compounds.For example, when required positively charged ion is lithium ion, can share lithium bicarbonate and lithium hydroxide.

As the amount of moisture that is contained in the aqueous solution that contains cationic compound, be generally about 70～98 weight parts with respect to these aqueous solution 100 weight parts.

As the usage quantity that contains cationic compound, be generally about roughly theoretical equivalent with respect to the hydrophobic amine that in (a) operation, uses.

By (b) operation, can obtain to contain the water of the salt of ionic compound and required cationic and the salt of positively charged ion and mineral acid etc.

Wherein, for the organic phase that in (b) operation, obtains by separatory, owing to contain hydrophobic amine and hydrophobic organic solvent, therefore in industrial this organic phase that can use recovery repeatedly.

In addition, for above-mentioned water,, preferably use hydrophobic organic solvent to clean for reducing the amount of the hydrophobic amine that this aqueous phase contains.Amount as the hydrophobic organic solvent that uses in cleaning with respect to the above-mentioned ionic aqueous solution 1 weight part, is generally about 0.1～10 weight part, about preferred 0.2～2 weight part.

Water for obtaining in (b) operation adds mineral acid as required, and pH is adjusted into 4～10 usually, preferably pH is adjusted into 6～9.When the ionic compound water soluble liquid that uses this water to obtain is when small outlet orifice is splashed to printing ink on the recording materials, if pH is more than 4, then has the corrosive tendency that reduces above-mentioned outlet orifice, so it is preferred, and when pH be 9 when following, then has the tendency that to operate the ionic aqueous solution easily, so preferred.

Therefore in addition, the aqueous phase that obtains in (b) operation contains hydrophobic organic solvent, preferably at normal pressure or add to depress and carry out azeotropic dehydration and distill and remove hydrophobic organic solvent.The amount of the hydrophobic organic solvent by reducing aqueous phase is to the filtering membrane of the membrane separation unit that uses in aftermentioned (c) operation or the tendency of peeling off reduction that ion-exchange membrane carries out bonding tackiness agent, so preferred.

(c) operation is to utilize membrane separation unit to remove inorganic salt also to obtain to contain from the operation of counterion for the anionic solution of the ionic compound generation of required cationic.As desalination, can adopt method based on osmotic pressure (below be sometimes referred to as osmose process) and based on electrodialytic method (below be sometimes referred to as electroosmose process) based on membrane separation unit.

Osmose process at first is described.

This method is used the filtering membrane tripping device, and pressurizes to a side of this film by the filtering membrane of this device, removes the ionic salt of no use of the aqueous phase that obtains in (b) operation thus, and acquisition contains the aqueous solution of the salt of ionic compound and required cationic.

As osmose process, can under normal pressure, implement under the degree of pressurization a little, but, pressurize usually about 0.1～10Mpa in order to shorten the time that desalination needs, preferably pressurize about 1～5Mpa.

For osmose process, the method for waterside desalination is added on the limit when preferably adopting pressurization, and the especially preferred continuous water that adds the amount identical with the capacity that reduces by desalination is so that make the concentration of ionic compound keep certain method.By adopting present method, there is inhibition to increase the tendency of the increase of caused membrane sepn required time, so preferred by the concentration of ionic compound.Here the total weight of the ionic compound water soluble liquid that normally in (b) operation, obtains of the water yield of Tian Jiaing about below 2～30 times about, preferred below 5～20 times about.If the water yield of adding is below 30 times, then has the tendency that shortens the membrane sepn required time, so preferred.In addition, in the present invention, will be used in the water yield of adding in (c) operation value, be called through multiplying power divided by the amount of (c) ionic compound water soluble liquid when operation begins.

In addition, the method for carrying out desalination for continuous interpolation water, preferably adjust the interpolation speed of water so that the moisture content of the ionic compound water soluble liquid that is desalted is generally about 70～98 weight %, especially for about 80～95 weight %.In the time of within this moisture content is in above-mentioned scope, has the tendency that viscosity reduces and velocity of separation improves that makes the ionic compound water soluble liquid that is desalted, so preferred.

As the material of the filtering membrane that in osmose process, uses, can enumerate macromolecular material such as for example natural, synthetic, semi-synthetic etc.Specifically can list Mierocrystalline cellulose, acetylation of cellulose, polypropylene, polystyrene, polyacrylonitrile, fluorinated ethylene propylene, poly-ethylene fluoride, polyvinyl alcohol, polyester, polycarbonate, polysulfones, polyethersulfone, polymeric amide, polyimide etc.Wherein, preferably use polyacrylonitrile, fluorinated ethylene propylene, polysulfones, polyethersulfone, polymeric amide, polyimide.

As the form of filtering membrane, can enumerate for example asymmetric shape/porous phase transformation film, asymmetric phase transformation film, composite membrane, stretched film, fire film, track degraded films etc.

Wherein, preferably use asymmetric shape/porous phase transformation film, asymmetric phase transformation film and composite membrane.

If mesh classification and expression with the kind of the filtering membrane that uses in the osmose process is pressed film then can be illustrated as nanofiltration separatory membrane, reverse osmosis membrane or ultra-filtration membrane etc.

Wherein, carry out membrane sepn when reaching steady state, preferably use by following formula (1) when using 3.64 weight % aqueous sodium persulfate solutions and depressing in adding of normal temperature, 3Mpa

R＝[1-(Cp/3.64)]×100 (1)

(in the formula, R represents the rejection [%] of filtering membrane, and Cp represents to carry out membrane sepn and the concentration [weight %] that sees through the sodium sulfate in the liquid that obtains by filtering membrane) rejection R of calculating is the filtering membrane below 90%.Wherein, more preferably rejection R is 40～60%, further preferred 48～57%.

If rejection is below 90%, then has selectivity and make required positively charged ion become salt and the tendency that keeps, so preferred.That is,, if rejection is below 90%, then has the tendency that sodium ion is carried out membrane sepn, so preferred when the lithium salts of ionic compound is a required compound and when having lithium ion and sodium ion to exist as positively charged ion.

Especially when rejection be 60% when following, the negatively charged ion except that the negatively charged ion that comes from ionic compound such as sulfate ion, chlorion etc. have the tendency of minimizing, so preferred.

In addition, if rejection is more than 40%, then ionic compound is difficult to see through, and yield rate has the tendency of raising, so preferred.

As filtering membrane, for example can use polyethersulfone is filtering membrane SNKCEA, SNKCEB, SNKCEC, G-10, G-20, ASP-50, NF-45 (above can obtaining from (strain) サ Application コ one), and polysulfones is filtering membrane NTR-7450 commercially available filtering membranes such as (day eastern electrician (strain) systems).

The desalination of carrying out based on the membrane sepn that uses filtering membrane is usually about 10～70 ℃, preferably implement under 20～60 ℃ temperature.If desalination temperature is more than 10 ℃, then velocity of separation has the tendency of raising, thus preferred, if this temperature below 70 ℃, then the weather resistance of filtering membrane has the tendency of improvement, so preferred.

As the filtering membrane tripping device that uses in osmose process, specifically can be illustrated as the filtering membrane tripping device of the shape that possesses full filtration shape, cross-stream ejector half filtration shape etc. etc.

Then, electroosmose process is described.

In the method, use electrodialysis unit, the ionic of no use of the aqueous phase that obtains in (b) operation is carried out desalination, obtain to contain the aqueous solution of required cationic as the ionic compound of counterion as membrane separation unit.

One example of the electrodialysis unit that uses as electrodialysis, shown in the synoptic diagram of Fig. 1, can enumerate and be provided with anode 1, negative electrode 2, anion-exchange membrane 3, cationic exchange membrane 4, the A of desalting chamber, concentrate salt chamber B, the C of anolyte compartment and cathode compartment D, and between anode 1 and negative electrode 2, apply the device etc. of volts DS.

In order more effectively to implement electrodialysis, preferably use the electrodialysis unit (Fig. 1) of a plurality of unit of formation (chamber) that between chamber, negative and positive the two poles of the earth, alternately are set up in parallel anion-exchange membrane 3, the A of desalting chamber, cationic exchange membrane 4, the A of desalting chamber, anion-exchange membrane 3.

To describe electrodialysis in detail as (c) operation of the electrodialysis unit of use Fig. 1 of an embodiment of the invention as concrete example.

Ionic compound 10 by the water soluble group of ionic compound (in Fig. 1, be illustration-SO ₃ ^-With-CO ₂ ^-) negatively charged ion and required positively charged ion (in Fig. 1, be illustration lithium cation) form counterion.Then, when external dc electric current between negative electrode 1 and anode 2, then do not become the otiose positively charged ion (in Fig. 1, be illustration sodium cation) and the superfluous required cationic of counterion,, move to cathode side through cationic exchange membrane 4.Thereby in the A of desalting chamber, otiose positively charged ion together reduces from the ionic aqueous solution with the required cationic of surplus.

Simultaneously, superfluous negatively charged ion (be illustration in Fig. 1 sulfate ion) sees through anion-exchange membrane 3, move to concentrated salt chamber B, as previously mentioned, and otiose cation permeation cationic exchange membrane 4, thus in concentrated salt chamber B that salt is concentrated.

In addition, because the ionic compound with counterion does not see through in anion-exchange membrane 3 and the cationic exchange membrane 4 any one, therefore in the A of desalting chamber, the ionic compound with counterion is concentrated.

The aqueous solution in concentration compartments, desalting chamber, anolyte compartment, the cathode compartment circulates between each chamber by pump etc. usually.Cathode compartment and anolyte compartment can mutual circulation.

As the anode of the electrodialysis unit that uses in the present invention, can enumerate for example platinum, the titanium that covers platinum, carbon, nickel, covering ruthenium titanium, cover the titanium of iridium etc.In addition, as negative electrode, can enumerate titanium, carbon, stainless steel of iron, nickel, platinum, covering platinum etc.

As the electrode structure of the anode of electrodialysis unit and negative electrode etc., for example can enumerate mesh-shape, structure such as grid-like, tabular.

As the anion-exchange membrane 3 that the present invention uses, can enumerate the polymer of monomers that for example contains the anionresin base, the monomer that contains the anionresin base and the monomeric multipolymer of hydrocarbon system etc.

As the monomer that contains the anionresin base, can enumerate monomer that contains primary～tertiary amine groups, quaternary ammonium group etc. etc. here.

Specifically, can enumerate N-vinyl imidazole, N-vinyl-glyoxal ethyline, N-vinyl-2,4-methylimidazole, N-vinyl-2-ethyl imidazol(e), N-vinyl-2-ethyl-4-methylimidazole, 2-vinyl imidazole, 1-methyl-vinyl imidazole classes such as 2-vinyl imidazole; Heterocycles such as vinyl pyridine class such as 4-vinylpridine are monomer etc.

In addition, can pass through methyl chloride, methyl iodide, dibromo-hexane, dimethyl sulfate etc., the polymkeric substance that will contain tertiary amine groups is transformed into quaternary ammonium salt.

As the cationic exchange membrane 4 that uses among the present invention, for example can enumerate the polymer of monomers that contains the cationic exchange base, the monomer that contains the anionresin base and the monomeric multipolymer of hydrocarbon system, the hydrocarbon system polymer of monomers be carried out sulfonation and polymkeric substance of obtaining etc. with the vitriol oil, oleum etc.

Here, as the monomer that contains the cationic exchange base, can enumerate and for example contain sulfonic group (SO ₃ ^-), carboxyl (CO ₂ ^-), the monomer of phenol hydroxyl etc. etc.Specifically can enumerate vinyl sulfonic acid, styrene sulfonic acid, vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, vinylphenol etc.

In addition, as the hydrocarbon system monomer, can enumerate for example ethene, propylene, butylene, vinyl cyanide, propenal, methyl vinyl ketone, vinylchlorid, vinylidene chloride, vinylbenzene, acrylate, methacrylic ester, maleic acid ester, maleic anhydride, itaconic ester, itaconic anhydride, Vinylstyrene, divinyl toluene, trivinyl hexanaphthene, divinyl naphthalene, 1-chloro-4-methyl-benzene etc.

About anion-exchange membrane 3 and cationic exchange membrane 4, consider from its manufacture method, for example can enumerate aggretion type, condensation polymer type, even type, non-homogeneous type etc.In addition, in these ion-exchange membranees, can also possess the reinforcing core.In addition, also can be the composite membrane of hydrocarbon system and fluorine system.

Anion-exchange membrane 3 that uses among the present invention and cationic exchange membrane 4 common thickness are about 0.1～0.6mm, resistance is 0.2～10 Ω cm ²About.

As the ion-exchange membrane that uses among the present invention, can use for example ネオセプ (trade(brand)name, (strain) アスト system system), セレミオ Application (trade(brand)name, Asahi Glass (strain) system), Off レミオ Application (trade(brand)name, Asahi Glass (strain) system), Na Off イオ Application commercially available ion-exchange membranees such as (trade(brand)name, Du Pont's systems).

As anion-exchange membrane, the penetration speed of the tosic acid sodium water solution of preferred 10 weight % is 0.05kgm ^-2H ^-1V ^-1Above anion-exchange membrane, more preferably 0.15～0.5kgm ^-2H ^-1V ^-1Anion-exchange membrane.

Here, the penetration speed of anion-exchange membrane (P kgm ^-2H ^-1V ^-1) method of calculation as follows: possessing anion-exchange membrane that need to measure penetration speed and cationic exchange membrane (registered trademark ア Star プレ Star Network ス K-192, Asahi Chemical Industry's system) and the effective film area of this anion-exchange membrane is Sm ²Electrodialysis unit in, the aqueous sodium persulfate solution of 5 weight % is put into anolyte compartment and cathode compartment, and the tosic acid sodium water solution of 10 weight % is put into concentration compartments and desalting chamber, with load voltage AV to desalting chamber's (cationic exchange membrane+anion-exchange membrane, a pair of) energising θ h, then, if will in the concentration compartments, the weight of the paratoluenesulfonic acid sodium salt of dialysis be made as Wkg, then with

P=WS ^-1θ ^-1A ^-1Calculate.

If penetration speed is 0.05kgm ^-2H ^-1V ^-1More than, then have the tendency that optionally makes required positively charged ion become salt, so preferred.That is, when the lithium salts of ionic compound be required compound and when having lithium ion and sodium ion to exist, if penetration speed is 0.05kgm as positively charged ion ^-2H ^-1V ^-1More than, then have the tendency that sodium ion is carried out membrane sepn, so preferred.

Especially at 0.15kgm ^-2H ^-1V ^-1When above, the negatively charged ion except that the negatively charged ion that comes from ionic compound such as sulfate ion, chlorion etc. have significantly reduced tendency, so preferred.

In addition, if penetration speed is 0.05kgm ^-2H ^-1V ^-1Below, then ionic compound is difficult to see through, and yield rate has the tendency of raising, so preferred.

As cationic exchange membrane, for example can use CIMS, CMX-SB commercially available cationic exchange membranes such as (above can the acquisitions) from (strain) アスト system.

As anion-exchange membrane, for example can use commercially available anion-exchange membranes such as AMX-SB, A-201, A-231, A-201F, A-501SB (more than, can obtain, all be ネオセプ series) from (strain) アスト system.

In the present invention, the various solution temperatures during as electrodialysis are normally about 5～70 ℃, more preferably about 20～50 ℃.In addition, current density is about 0.01～20A/dm usually ², preferred about 0.05～10A/dm ²

About the voltage that applies,, be applied to each unitary voltage and be about 0.02～5V, preferred about 0.1～2V degree usually when with the C of anolyte compartment, anion-exchange membrane 3, the A of desalting chamber, cationic exchange membrane 4, when concentrating salt chamber B, cathode compartment D as a unit.Usually be about 5～2000 minutes conduction time, preferred about 20～300 minutes.

In the present invention, be generally more than the 0.1N for the cation concn that in electrodialytic ionic compound water soluble liquid, contained, preferably about 0.1～10N, more preferably about 0.1～3N, further preferred 0.2～2N degree.

In addition, as in the ionic compound concentration of electrodialytic ionic compound water soluble liquid, be 0.01～370g/L, preferred about 1～30g/L.

Electrodialysis can the specific conductivity in dialysis reach termination when stablizing usually.Specifically, when under certain voltage, implementing electrodialysis,, electrodialysis can be stopped, perhaps when under certain electric current, carrying out electrodialysis,, electrodialysis can be stopped if magnitude of voltage does not rise if current value does not reduce.

In addition,, the tendency of the insulation breakdown that suppresses ion-exchange membrane is arranged, so preferred when under certain voltage, carrying out electrodialysis.

By the ionic compound water soluble liquid that method of the present invention obtains, can be used as the printing ink that is splashed on the recording materials from small outlet orifice and use.At this moment, the composition that preferably contains ionic compound 0.01～30 weight % and liquid medium 70～99.99 weight %, the composition that more preferably contains ionic compound 0.1～20 weight % and liquid medium 80～99.9 weight % especially preferably contains the composition of ionic compound 1～5 weight % and liquid medium 95～99 weight %.

The printing ink that splashes to recording materials from small outlet orifice can be the mixture that contains two or more ionic compounds.

Liquid medium in this printing ink is the mixture of water, organic solvent or water and organic solvent preferably.

When liquid medium was the mixture of water and organic solvent, preferred organic solvent was a water miscibility organic solvent.

In addition, preferably 99: 1～1: 99 the scope of weight ratio of water and water miscibility organic solvent, more preferably 99: 1～50: 50 scope, preferred especially 95: 5～80: 20 scope.

As water miscibility organic solvent, for example can enumerate and contain from by mixture of the plural above-mentioned water miscibility organic solvent of selecting the following all kinds of materials etc., that is:

Carbonatomss such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, Pentyl alcohol are 1～6 alkanols;

Ring-type such as hexalin, cyclopentanol alkanols;

1,5-pentanediol, 1, carbonatomss such as 6-hexylene glycol are 2～12 glycols;

Amides such as DIMETHYL FORMAMIDE, N,N-DIMETHYLACETAMIDE;

Amines such as trolamine, thanomin, diethanolamine;

Ketone and ketols such as acetone, ethyl methyl ketone, pimelinketone, diacetone alcohol;

Ethers such as tetrahydrofuran (THF), diox;

Low or polyalkylene glycols such as glycol ether, triglycol, hexylene glycol, polyoxyethylene glycol, polypropylene glycol;

Carbonatomss such as ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, thiodiglycol are 2～6 aklylene glycol or thioglycol class;

Glycerine, 1,2, polyalcohols such as 6-hexanetriol;

Alkyl (carbonatoms is 1～4) ether of the polyvalent alcohol of 2-methyl cellosolve, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy)-ethanol, 2-(2-(2-methoxy ethoxy) oxyethyl group)-ethanol, 2-(2-(2-ethoxy ethoxy) oxyethyl group)-ethanol, 2-(2-butoxy oxyethyl group) ethanol, glycol monomethyl aryl ethers etc.;

2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, hexanolactam, 1, cyclic amides such as 3-methylimidazole alkane ketone;

Cyclic ester such as hexanolactam, gamma-butyrolactone class;

Sulfoxide such as methyl-sulphoxide and tetramethylene sulfone class;

Thioglycol and secondary glycol or glycol ether and 2-Pyrrolidone.

As particularly preferred water miscibility organic solvent, can enumerate 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, ethylene glycol, glycol ether, triglycol, 2-methoxyl group-2-oxyethyl group-cellosolvo and molecular weight at the polyoxyethylene glycol below 500.

The mixture of water and water Combination organic solvent preferably contain the water of 60～99.5 weight % and 0.5～40 weight % from glycol ether, 2-Pyrrolidone, N-Methyl pyrrolidone, hexalin, caprolactone, hexanolactam, 1, the solvent of more than one that select in 5-pentanediol, 2-(2-butoxy oxyethyl group) ethanol and the thioglycol.

Be splashed to printing ink on the recording materials from small outlet orifice, except containing water colo(u)r isoiony compound, water and water miscibility organic solvent, can also contain the supplementary component that in printing ink, often uses, as viscosity and surface tension modifying agent, sanitas, biocide, Kogation suppressant additive and ionic or non-ionic tenside etc.

Use is splashed to the printing press of the printing ink on the recording materials from small outlet orifice, from small outlet orifice the form of this printing ink with drop is splashed on the recording materials usually, applies on recording materials with this.Preferred printing press is piezoelectric type and hot type.This printing press for hot type, by the resistor approaching with outlet orifice, printing ink in ink reservoir adds the pulse of the heat of sequencing, and thus in the process that relatively moves of recording materials and outlet orifice, printing ink is splashed to recording materials with droplet profile.For the piezoelectric type printing press, be to make in the printing ink outlet orifice by small crystal vibration to splash out.

As recording materials, can use paper, plastics, fabric, metal, glass etc., the wherein more preferably lantern slide of paper, overhead projector or fabric quality, preferred especially paper.

As paper, can enumerate common paper and treatment paper (acid, neutral or alkalescence).

Preferred fabric quality can be natural, synthetic and semisynthetic quality, but as preferred natural fabric quality, can enumerate wool, silk, hair, fiber, cotton, jute, fiber crops, flax, linen.

As particularly preferred natural fabric quality, can enumerate cotton, jute, fiber crops, flax, linen.

In addition, as preferred synthetic or semisynthetic quality, can enumerate polymeric amide, polyester, polyacrylonitrile, urethane etc.

For method of the present invention, promptly use membrane separation unit to carry out a desalination, also can obtain sufficient desalting effect, operation is also simple in addition, can make membrane separation plant become simple and easy, is industrial good manufacture method therefore.

In addition, even reduce the usage quantity of the compound that balance cation is provided, the ionic compound that is obtained is also basically by required balance cation displacement, and can also be by suitably selecting filtering membrane or ion-exchange membrane, reduce the otiose ion except that chlorion, sulfate ion etc. comes from the negatively charged ion of ionic compound.

In addition, the method according to this invention also can reduce required cationic amount, has reduced and has given birth to salifiable possibility.Its result also can be suppressed at and produce solidifying of salt in the outlet orifice.

Ionic compound water soluble liquid according to the inventive method obtains can be used in for example aspects such as pigment, dyestuff, agricultural chemicals, medicine, washing composition, foodstuff additive.Wherein, when the ionic compound water soluble liquid that the method according to this invention is obtained is used in printing press as being splashed to the printing ink on the recording materials from small outlet orifice, can in outlet orifice, not solidify, make it through long-time stable the discharge, its result can obtain the recording materials of the information-recording material etc. of printing characteristic good electron photo, digital photographs etc. such as printing ink acceptability.

Description of drawings

Fig. 1 is the mode chart that expression is used for the electrodialytic device of (c) of the present invention operation.

Among the figure: 1-anode, 2-negative electrode, 3-anion-exchange membrane, the 4-cationic exchange membrane, 11-contains the water of the ionic compound that obtains and required cationic salt, 12-ion exchanged water, the Lithium Sulphate aqueous solution of 13-5 weight % in (b) operation, 14-contains the ion exchanged water of salt, the 15-ionic compound water soluble liquid, (A)-concentration compartments, (B)-desalting chamber, (C)-anolyte compartment, (D)-cathode compartment.

Embodiment

Below, by embodiment, be described in more detail the present invention, undoubtedly, the present invention is based on these embodiment, but be not limited to them.

(embodiment 1)

＜(a) operation 〉

At C.I.Acid Yellow 23 by following formula (with the form record of free acid) expression

[purity when being converted into free acid form is 70.7%, the amount of water soluble group is 249 equivalence ratios] add entry 495 weight parts in 55 weight parts and be modulated in the liquid of pigment, add dibenzyl lauryl amine 211 weight parts (577 equivalence ratio) and toluene 407 weight parts, then add 20% sulfuric acid again, the pH of water portion is adjusted into 0.8, and under the state of pH0.8, stirred 30 minutes.Stop then stirring, left standstill 30 minutes.After leaving standstill, extract lower floor's (water).In the upper strata (organic phase) that keeps, add ion exchanged water 500 weight parts, stir after 30 minutes, left standstill 30 minutes.Leave standstill the back and extract water.500 weight parts in the organic phase that extracts water stirred after 30 minutes, left standstill 30 minutes.And then add ion exchanged water 495 weight parts, and stir after 30 minutes, left standstill 30 minutes.Then extract the water after leaving standstill.

＜(b) operation 〉

In the organic phase that in (a) operation, obtains, add 2% lithium hydroxide aqueous solution, 690 weight parts (with respect to N,N-dibenzyldodecyl amine 1 equivalence ratio, lithium hydroxide 1 mol ratio) and stirring.Wherein, be 100 weight parts with respect to C.I.Acid Yellow 23 as free acid, the usage quantity of the lithium hydroxide of use is to be 25.1 weight parts as lithium atom.Then, stop to stir and leaving standstill 30 minutes, extract lower floor's (water) then, and add dilute sulphuric acid and after its pH is adjusted into 7 to the aqueous phase that obtains, under the reduced pressure of 16.7kPa, be heated to about 55 ℃, residual toluene and water are together distilled removal, and the concentration when obtaining to be converted into free acid form is the aqueous solution 716 weight parts of lithium salts of the C.I.Acid Yellow 23 of 6.9 weight %.In the aqueous solution that is obtained, do not detect Na ion concentration, and the lithium concentration of this aqueous solution is that 5300ppm, chlorine ion concentration are that 230ppm, sulfate ion concentration are 15300ppm.

＜(c) operation 〉

For the aqueous solution 150 weight parts that in (b) operation, obtain, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 56.1% described filtering membrane (G-10: can obtain from (strain) サ Application コ one), add ion exchanged water to keep the liquid measure of the aqueous solution that needs desalination, depress in adding of room temperature, 3Mpa simultaneously, with the average flow 23.84L/m of seeing through ²/ hr carries out desalination and reaches 10 times until seeing through multiplying power, and the concentration when obtaining to be converted into free acid form is the aqueous solution 210 weight parts of lithium salts of the C.I.Acid Yellow 23 of 5 weight %.For the liquid measure of keeping the ion exchanged water that liquid measure uses is 1500 weight parts.

The lithium concentration of the thus obtained aqueous solution is that 2200ppm, Na ion concentration are 20ppm and chlorion and sulfate ion are not detected.

(embodiment 2)

＜(a) operation 〉

At C.I.Direct Blue 86 by following formula (with the form record of free acid) expression

[purity when being converted into free acid form is 48.5%, the amount of water soluble group is 170 equivalence ratios] add entry 495 weight parts in 55 weight parts and be modulated into after the liquid of pigment, add dibenzyl lauryl amine 144 weight parts (394 equivalence ratio) and toluene 1336 weight parts therein, then add 98% sulfuric acid, the pH of water portion is adjusted into 0.8, and under the state of pH0.8, stirred 30 minutes.Stop then stirring, left standstill 30 minutes.After leaving standstill, extract lower floor's (water).In the upper strata (organic phase) that keeps, add ion exchanged water 400 weight parts, stir after 30 minutes, left standstill 30 minutes.Leave standstill the back and take out water.Then, add ion exchanged water 495 weight parts in the organic phase after extracting water, stir after 30 minutes, left standstill 30 minutes.Then take out the water after leaving standstill.

＜(b) operation 〉

In the organic phase that in (a) operation, obtains, add 2% lithium hydroxide aqueous solution, 473 weight parts (with respect to N,N-dibenzyldodecyl amine 1 equivalence ratio, lithium hydroxide 1 mol ratio) and stirring.In addition, be 100 weight parts with respect to C.I.Direct Blue 86 as free acid, the usage quantity of the lithium hydroxide of use is to be 17.3 weight parts as lithium atom.Then, stop to stir and leaving standstill 30 minutes, extract lower floor's (water) then, and add toluene 40 weight parts and remove N,N-dibenzyldodecyl amine at toluene layer to the aqueous phase that obtains.After the aqueous phase that obtains behind the separatory adds 98% sulfuric acid and its pH is adjusted into 7, under the reduced pressure of 16.7kPa, be heated to about 55 ℃, residual toluene and water are together distilled removal, and the concentration when obtaining to be converted into free acid form is the aqueous solution 548 weight parts of lithium salts of the C.I.DirectBlue 86 of 4.9 weight %.In the aqueous solution that is obtained, Na ion concentration is 710ppm, and the lithium concentration of this aqueous solution is that 5600ppm, chlorion are not detected, sulfate ion concentration is 29100ppm.

＜(c) operation 〉

For the aqueous solution 150 weight parts that in (b) operation, obtain, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 56.1% described filtering membrane, add ion exchanged water to keep the liquid measure of the aqueous solution that needs desalination, depress in adding of room temperature, 3Mpa simultaneously, with the average flow 37.75L/m of seeing through ²/ hr carries out desalination and reaches 10 times until seeing through multiplying power, and the concentration when obtaining to be converted into free acid form is the aqueous solution 160 weight parts of lithium salts of the C.I.Direct Blue86 of 4.5 weight %.For the liquid measure of keeping the ion exchanged water that liquid measure uses is 1500 weight parts.

The Na ion concentration of the thus obtained aqueous solution is that the lithium concentration in 30ppm and this aqueous solution is that 850ppm, chlorine ion concentration are not detected, sulfate ion concentration is 110ppm.

(embodiment 3)

＜(c) operation 〉

For the aqueous solution 150 weight parts that in (b) operation, obtain with the method identical with embodiment 2, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 56.1% described filtering membrane (G-10: can obtain from (strain) サ Application コ one), add ion exchanged water to keep the liquid measure of the aqueous solution that needs desalination, depress in adding of room temperature, 3Mpa simultaneously, with the average flow 27.00L/m of seeing through ²/ hr carries out desalination and reaches 3 times until seeing through multiplying power, and the concentration when obtaining to be converted into free acid form is the aqueous solution 151 weight parts of lithium salts of the C.I.Direct Blue 86 of 3.8 weight %.For the liquid measure of keeping the ion exchanged water that liquid measure uses is 450 weight parts.

The Na ion concentration of the thus obtained aqueous solution is that the lithium concentration in 1ppm and this aqueous solution is that 1700ppm, chlorine ion concentration are not detected, sulfate ion concentration is 5600ppm.

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 0.030 weight part.

(embodiment 4)

＜(c) operation 〉

For the aqueous solution 150 weight parts that in (b) operation, obtain with the method identical with embodiment 2, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 48.4% filtering membrane (NTR-7450: can obtain from day east electrician (strain)), add ion exchanged water to keep the liquid measure of the aqueous solution that needs desalination, depress in adding of room temperature, 3Mpa simultaneously, with the average flow 34.14L/m of seeing through ²/ hr carries out desalination and reaches 3 times until seeing through multiplying power, and the concentration when obtaining to be converted into free acid form is the aqueous solution 150 weight parts of lithium salts of the C.I.Direct Blue 86 of 3.7 weight %.For the liquid measure of keeping the ion exchanged water that liquid measure uses is 450 weight parts.

The Na ion concentration of the thus obtained aqueous solution is that the lithium concentration in 1ppm and this aqueous solution is that 1700ppm, chlorine ion concentration are not detected, sulfate ion concentration is 5500ppm.

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 0.002 weight part.

(embodiment 5)

＜(c) operation 〉

For the aqueous solution 150 weight parts that in (b) operation, obtain with the method identical with embodiment 2, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 87.7% filtering membrane (NF-45: can obtain from (strain) サ Application コ one), add ion exchanged water to keep the liquid measure of the aqueous solution that needs desalination, depress in adding of room temperature, 3Mpa simultaneously, with the average flow 2.88L/m of seeing through ²/ hr carries out desalination and reaches 3 times until seeing through multiplying power, and the concentration when obtaining to be converted into free acid form is the aqueous solution 153 weight parts of lithium salts of the C.I.Direct Blue 86 of 5.2 weight %.For the liquid measure of keeping the ion exchanged water that liquid measure uses is 450 weight parts.

The Na ion concentration of the thus obtained aqueous solution is that the lithium concentration in 12ppm and this aqueous solution is that 5100ppm, chlorine ion concentration are not detected, sulfate ion concentration is 17000ppm.

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 0.077 weight part.

(embodiment 6)

＜(c) operation 〉

In embodiment 6, used cationic exchange membrane (registered trademark has been installed, ネオセプ CIMS, アスト system system), the electrodialysis unit based on Fig. 1 (microanalyser 3S, アスト system system, the effective film area 0.055m of anion-exchange membrane (registered trademark, ネオセプ AMX-SB, アスト system system) ²).In this desalting chamber, put into the method identical at the aqueous solution 501 weight parts that (b) operation obtains with embodiment 2, make its circulation.In the concentration compartments, put into ion exchanged water 502 weight parts and make its circulation, and add 5 weight % aqueous sodium persulfate solution 500 weight parts in anode chamber and the cathode compartment and make its circulation.Then, between anode and cathode, apply the certain voltage of 10V.Be 4 hours conduction time, and average current value is 0.45A (current density 0.8A/dm ³).

Concentration when desalting chamber obtains to be converted into free acid form is the aqueous solution 398 weight parts of lithium salts of the C.I.DirectBlue 86 of 4.1 weight %.The Na ion concentration of the aqueous solution that obtains is that the lithium concentration in 1ppm and this aqueous solution is that 1000ppm, chlorine ion concentration are not detected, sulfate ion concentration is 170ppm.

Here, in order to calculate the penetration speed (kgm of employed anion-exchange membrane (registered trademark, ネオセプ A-201) ^-2H ^-1V ^-1), in the electrodialysis unit of embodiment 1, in anolyte compartment and cathode compartment, put into aqueous sodium persulfate solution 500 weight parts of 5 weight %, make its circulation.Put into tosic acid sodium water solution 1000 weight parts of 10 weight % in concentration compartments and desalting chamber respectively, connection to load voltage 10V is to the energising 0.92h of desalting chamber (cationic exchange membrane+anion-exchange membrane, 10 pairs).Average current value in the energising is that (current density is 0.3A/dm to 0.17A ³).Be 0.01234kg by the weight of the paratoluenesulfonic acid sodium salt of dialysis this moment in the concentration compartments, and the penetration speed that therefore can be regarded as out the anion-exchange membrane of use is 0.244 (kgm ^-2H ^-1V ^-1).

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 2.9 weight parts.

(embodiment 7)

＜(c) operation 〉

In embodiment 7, as anion-exchange membrane, (penetration speed of measuring in the mode identical with embodiment 6 is 0.166 (kgm except registered trademark ネオセプ AMX-SB, アスト system system are installed ^-2H ^-1V ^-1)) outside, use the electrodialysis unit identical with embodiment 1.

In the desalting chamber of this electrodialysis unit, put into the aqueous solution 400 weight parts that obtain in (b) operation with the method identical, and make its circulation with embodiment 2.In the concentration compartments, put into ion exchanged water 400 weight parts and make its circulation, and add 5 weight % aqueous sodium persulfate solution 400 weight parts in anode chamber and the cathode compartment and make its circulation.Then, between anode and cathode, apply the certain voltage of 10V.Be 4 hours conduction time, and average current value is 0.36A (current density 0.6A/dm ³).

Thus, the concentration when desalting chamber obtains to be converted into free acid form is the aqueous solution 303 weight parts of lithium salts of the C.I.Direct Blue 86 of 4.2 weight %.

The Na ion concentration of the aqueous solution that obtains is that the lithium concentration in 13ppm and this aqueous solution is that 1100ppm, chlorine ion concentration are not detected, sulfate ion concentration is 350ppm.

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 5.0 weight parts.

(embodiment 8)

＜(c) operation 〉

In embodiment 8, as anion-exchange membrane, (penetration speed of measuring in the mode identical with embodiment 6 is 0.099 (kgm except registered trademark ネオセプ A-201F, アスト system system are installed ^-2H ^-1V ^-1)) outside, use the electrodialysis unit identical with embodiment 1.In the desalting chamber of this electrodialysis unit, put into the aqueous solution 400 weight parts that obtain in (b) operation with the method identical, and make its circulation with embodiment 2.In the concentration compartments, put into ion exchanged water 401 weight parts and make its circulation, and add 5 weight % aqueous sodium persulfate solution 400 weight parts in anode chamber and the cathode compartment and make its circulation.Then, between anode and cathode, apply the certain voltage of 10V.Be 4 hours conduction time, and average current value is 0.03A (current density 0.05A/dm ³).

Thus, the concentration when desalting chamber obtains to be converted into free acid form is the aqueous solution 410 weight parts of lithium salts of the C.I.Direct Blue 86 of 3.4 weight %.

The Na ion concentration of the aqueous solution that obtains is that the lithium concentration in 48ppm and this aqueous solution is that 4100ppm, chlorine ion concentration are not detected, sulfate ion concentration is 22000ppm.

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 1.1 weight parts.

(embodiment 9)

＜(c) operation 〉

In embodiment 9, as anion-exchange membrane, (penetration speed of measuring in the mode identical with embodiment 6 is 0.457 (kgm except registered trademark ネオセプ A-231, アスト system system are installed ^-2H ^-1V ^-1)) outside, use the electrodialysis unit identical with embodiment 1.In the desalting chamber of this electrodialysis unit, put into the aqueous solution 400 weight parts that obtain in (b) operation with the method identical, and make its circulation with embodiment 2.In the concentration compartments, put into ion exchanged water 400 weight parts and make its circulation, and add 5 weight % aqueous sodium persulfate solution 400 weight parts in anode chamber and the cathode compartment and make its circulation.Then, between anode and cathode, apply the certain voltage of 10V.Be 4 hours conduction time, and average current value is 0.39A (current density 0.7A/dm ³).

Thus, the concentration when desalting chamber obtains to be converted into free acid form is the aqueous solution 321 weight parts of lithium salts of the C.I.Direct Blue 86 of 4.0 weight %.The Na ion concentration of the aqueous solution that obtains is that the lithium concentration in 1ppm and this aqueous solution is that 960ppm, chlorine ion concentration are not detected, sulfate ion concentration is 170ppm.

With respect to C.I.Direct Blue 86 (as free acid) 100 weight parts that use in (c) operation, the C.I.Direct Blue 86 (as free acid) that has seen through filtering membrane is 3.6 weight parts.

(comparative example 1)

Purity when C.I.Acid Yellow 23[is converted into free acid form is 70.7%, the amount of water soluble group is 249 equivalence ratios] add entry 135 weight parts in 15 weight parts and be modulated into after the liquid of pigment, add lithium chloride 15.5 weight parts therein and form homogeneous solution.Then, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 56.1% filtering membrane (G-10: can obtain from (strain) サ Application コ one), the hybrid ionic exchanged water to be keeping the liquid measure of the aqueous solution that needs desalination, depresses in adding of room temperature, 3Mpa simultaneously, with the average flow 37.97L/m of seeing through ²/ hr carries out desalination and reaches 5 times until seeing through multiplying power.For the amount of keeping the ion exchanged water that liquid measure uses is 750 weight parts.

Add lithium chloride 15.5 weight parts once more, and with above-mentioned same condition under carry out desalination, having obtained concentration is Aqueous Lithium Salts 210 weight parts of the C.I.Acid Yellow 23 of 6 weight %.For the amount of keeping the ion exchanged water that liquid measure uses is 750 weight parts.

The lithium concentration of the aqueous solution that obtains is 2600ppm, but does not detect chlorion and sulfate ion.

In addition, be 100 weight parts with respect to C.I.Acid Yellow 23 as free acid, the amount of the whole lithium salts that use in comparative example 1 is to be 206.7 weight parts as lithium atom.

(comparative example 2)

Purity when C.I.Direct Blue 86[is converted into free acid form is 48.5%, the amount of water soluble group is 46.4 equivalence ratios] add entry 135 weight parts in 15 weight parts and be modulated into after the liquid of pigment, add lithium chloride 15.5 weight parts therein and form homogeneous solution.Then, the rejection that use is equipped with the aqueous solution that contains sodium sulfate 3.64 weight % relatively is the full filtration unit of 56.1% filtering membrane (G-10: can obtain from (strain) サ Application コ one), depresses in adding of room temperature, 3Mpa, with the average flow 38.15L/m of seeing through ²/ hr carries out desalination and reaches 5 times until seeing through multiple.For the amount of keeping the ion exchanged water that liquid measure uses is 750 weight parts.

Add lithium chloride 15.5 weight parts once more, and with above-mentioned same condition under carry out desalination, having obtained concentration is Aqueous Lithium Salts 210 weight parts of the C.I.Direct Blue 86 of 3.4 weight %.For the amount of keeping the ion exchanged water that liquid measure uses is 750 weight parts.

The lithium concentration of the aqueous solution that obtains is that 680ppm, Na ion concentration are that 50ppm, chlorine ion concentration are that 170ppm, sulfate ion concentration are 90ppm.

In addition, be 100 weight parts with respect to C.I.Direct Blue 86 as free acid, the amount of the whole lithium salts that use in comparative example 2 is to be 206.7 weight parts as lithium atom.

Claims

1. the manufacture method of the aqueous solution of an ionic compound is characterized in that, comprises following (a) and (b) and (c) operation:

(a) operation:

In the aqueous solution that contains ionic compound, mix hydrophobic amine and hydrophobic organic solvent, and with the pH of water portion be adjusted into 0.01～2 and separatory after, acquisition contains from the organic phase of the salt of the negatively charged ion of ionic compound generation and hydrophobic amine, wherein, described ionic compound has from by-SO ₃The Na base ,-SO ₃The K base ,-SO ₃NH ₄Base ,-the COONa base ,-the COOK base ,-PO ₃The Na base ,-PO ₃The K base ,-PO ₃NH ₄The base and-COONH ₄At least a water soluble group of selecting in the group that base constitutes;

(b) operation:

In the organic phase that obtains in (a) operation, will contain after cationic compound mixes as the aqueous solution, separatory obtains to contain the negatively charged ion that generates from ionic compound and the water of described cationic salt;

(c) operation:

Use membrane separation unit to remove inorganic salt from the aqueous phase that obtains (b) operation, obtaining to contain from counterion is the anionic aqueous solution that described cationic ionic compound generates.

2. manufacture method as claimed in claim 1 is characterized in that: the interpolation mineral acid is adjusted into 0.01～2 with the pH of water portion.

3. as claim 1 or 2 described manufacture method, it is characterized in that: described ionic compound is from adding at least a water colo(u)r of selecting the material group that constitutes with dyestuff, substantive dyestuff and reactive dye by matching stain, food.

4. as any one described manufacture method in the claim 1～3, it is characterized in that: hydrophobic amine is that carbonatoms is the amine more than 12.

5. as any one described manufacture method in the claim 1～4, it is characterized in that: hydrophobic organic solvent is at least a hydrophobic solvent of selecting from the material group that is made of toluene, dimethylbenzene and monochloro-benzene.

6. as any one described manufacture method in the claim 1～5, it is characterized in that: containing cationic compound is at least a compound of selecting from the material group that is made of Quilonum Retard, lithium bicarbonate, lithium hydroxide, potassium hydroxide, salt of wormwood, saleratus, ammonium hydroxide and ammonia.

7. as any one described manufacture method in the claim 1～6, it is characterized in that: membrane separation unit is filtering membrane tripping device or electrodialysis unit.

8. as any one described manufacture method in the claim 1～7, it is characterized in that: membrane separation unit is the filtering membrane tripping device, and when the aqueous sodium persulfate solution that uses 3.64 weight % carried out membrane sepn, the filtering membrane of this device was by following formula (1)

R＝[1-(Cp/3.64)]×100 (1)

The rejection R that (in the formula, R represents the rejection [%] of filtering membrane, and Cp represents to carry out membrane sepn and the concentration [weight %] that sees through the sodium sulfate in the liquid that obtains by filtering membrane) calculates is below 90%.

9. manufacture method as claimed in claim 8 is characterized in that: be that rejection R is 40～60% filtering membrane.

10. as any one described manufacture method in the claim 1～9, it is characterized in that: the filtering membrane of filtering membrane tripping device is ultra-filtration membrane or reverse osmosis membrane.

11. as any one described manufacture method in the claim 1～10, it is characterized in that: the filtering membrane tripping device is the membrane separation unit that full filters shape or cross-stream ejector half filtration shape.

12. as any one described manufacture method in the claim 1～11, it is characterized in that: electrodialysis unit uses the penetration speed of 10% tosic acid sodium water solution to be 0.05kgm ^-2H ^-1V ^-1Above anion-exchange membrane.

13. as any one described manufacture method in the claim 1～12, it is characterized in that: it is 0.15～0.5kgm that electrodialysis unit uses the penetration speed of the tosic acid sodium water solution of 10 weight % ^-2H ^-1V ^-1Anion-exchange membrane.

14. as any one described manufacture method in the claim 1～13, it is characterized in that: reclaim the organic phase that contains hydrophobic amine and hydrophobic organic solvent in (b) operation, and the organic layer that reclaims is used as the part of the hydrophobic amine of (a) operation and hydrophobic organic solvent.