CN103237796B - Piperazine-N, N '-bis-dithionic acid salt brine solution and manufacture method thereof - Google Patents
Piperazine-N, N '-bis-dithionic acid salt brine solution and manufacture method thereof Download PDFInfo
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- CN103237796B CN103237796B CN201180057459.XA CN201180057459A CN103237796B CN 103237796 B CN103237796 B CN 103237796B CN 201180057459 A CN201180057459 A CN 201180057459A CN 103237796 B CN103237796 B CN 103237796B
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- C07—ORGANIC CHEMISTRY
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
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Abstract
There is provided a kind of when manufacturing the dithionate as the useful piperazine of heavy metal treatment agent without the need to carrying out utilizing the piperazine-N that the raising heavy metal processing power of the distillation Transformatin of the dithiocarbonic anhydride of non-active gas etc. is high, the industrially preparing process of N '-bis-dithionate's ratio.Piperazine-N, the feature of the manufacture method of N '-bis-dithionic acid salt brine solution is, in the manufacture method of the piperazine dithionate mix in aqueous with dithiocarbonic anhydride and alkali metal hydroxide making piperazine, reacted, make to there is hydrophobic solvent during reaction, described dithiocarbonic anhydride is more than reaction equivalent relative to described piperazine.
Description
Technical field
The present invention relates to as the useful piperazine dithionic acid salt brine solution of heavy metal treatment agent and manufacture method thereof, more specifically, the invention provides the piperazine-N not containing piperazine-N-dithionate, the aqueous solution of N '-bis-dithionate and manufacture method thereof.
Background technology
Environmental problem, the problem especially about the environmental pollution of offal treatment is not only the common problem in the Ye Shi world of China.In China, the flying dust produced because of castoff burning is utilized chelating chemical reagent carry out heavy metal insoluble after, process at the final landfill yard (Controlled Final Landfill Site) of management type, establish prevent because castoff burning ash causes soil, underground water the technology of heavy metal contamination.
As making the thawless sequestrant of the heavy metal in flying dust, the dithionate of various amine can be used, especially the dithionate of piperazine not only has immobilization of heavy metals ability, and can not obnoxious flavour be produced when using, as stability and excellent in safety chemical reagent and be widely used (such as with reference to patent documentation 1).
On the other hand, recently, the countries in Asia of China's periphery also begin one's study and utilize sequestrant to process the flying dust after castoff burning, carry out safe process.Correspondingly, the worldwide demand of the sequestrant of flying dust process is also being increased gradually.
For have as heavy metal treatment agent excellent properties piperazine dithionate for, piperazine-N can be there is, N '-bis-dithionate and these two kinds of chemical structures of piperazine-N-dithionate, wherein piperazine-N, N '-bis-dithionate has higher heavy metal processing power.
For the dithionate of piperazine, in aqueous piperazine, dithiocarbonic anhydride and alkali metal hydroxide are mixed, under the low temperature (about 40 DEG C of front and back) below the boiling point of dithiocarbonic anhydride after reaction, need to carry out maturation process.Slaking is in the past carried out under the condition of base excess to suppress the decomposition of dithionate.
In the past, as manufacturing the high piperazine-N of heavy metal processing power, the method of the dithionate of the piperazine that N '-bis-dithionate's ratio is high, excessive dithiocarbonic anhydride is used, the method (such as with reference to patent documentation 1) finally using non-active gas unreacted dithiocarbonic anhydride distillation removal (removal) to be processed when there will be a known reaction.Also there will be a known the method for raw material batch mixing, the method (such as with reference to patent documentation 2,3) of carrying out reacting under the existence of piperazine dithionic acid when reacting.
But, use excessive dithiocarbonic anhydride to improve piperazine-N according to method in the past, in the method for N '-bis-dithionate's ratio, need to use a large amount of nitrogen to carry out distillation Transformatin after the reaction, not industrial preferred method.In addition, utilize the method for batch mixing dithiocarbonic anhydride and alkali metal hydroxide in the aqueous solution of piperazine, although can improve piperazine-N, the ratio of N '-bis-dithionate, needs to increase many number of times in batches, there is the problem that operation becomes numerous and diverse.
The method of carrying out reacting under the existence of piperazine dithionic acid is also same, although piperazine-N can be improved, the ratio of N '-bis-dithionate, but piperazine dithionic acid is insoluble solid, sometimes be difficult to react uniformly, sometimes piperazine dithionic acid precipitate in reactive tank (especially agitating wing), and reaction controlling becomes difficulty, needs to improve.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 3391173 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-221389 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2008-143810 publication
Summary of the invention
the problem that invention will solve
In order to manufacture not containing piperazine-N-dithionate comprise piperazine-N, the heavy metal treatment agent of N '-bis-dithionate, utilize the distillation Transformatin of non-active gas, solid piperazine dithionic acid separate out in reaction controlling be necessary.
The object of the present invention is to provide a kind of not containing piperazine-N-dithionate, the industrial useful piperazine-N carrying out the distillation Transformatin of dithiocarbonic anhydride without using non-active gas, the manufacture method of N '-bis-dithionic acid salt brine solution.
for the scheme of dealing with problems
The discoveries such as the present inventor, for making piperazine and being the method that the dithiocarbonic anhydride of more than reaction equivalent and alkali metal hydroxide react in aqueous relative to this piperazine, by there is hydrophobic solvent when reacting, utilize the reaction controlling in the precipitation of the distillation Transformatin of non-active gas, piperazine dithionic acid just can manufacture the piperazine-N not containing piperazine-N-dithionate without the need to carrying out after reaction, N '-bis-dithionic acid salt brine solution, thus complete the present invention.
That is, the present invention is the invention with following main idea.
(1) a kind of piperazine-N, the manufacture method of N '-bis-dithionic acid salt brine solution, it is characterized in that, in the manufacture method of the piperazine dithionate mix in aqueous with dithiocarbonic anhydride and alkali metal hydroxide making piperazine, reacted, make to there is hydrophobic solvent during reaction, described dithiocarbonic anhydride is more than reaction equivalent relative to described piperazine.
(2) manufacture method according to above-mentioned (1), wherein, is more than 2.00 times of equivalents relative to the mol ratio of the dithiocarbonic anhydride of piperazine and below 3.00 times of equivalents.
(3) manufacture method according to above-mentioned (1) or (2), wherein, is more than 1.95 times of equivalents relative to the mol ratio of the alkali metal hydroxide of piperazine and below 2.05 times of equivalents.
(4) manufacture method according to any one of above-mentioned (1) ~ (3), wherein, hydrophobic solvent is less than 1 % by weight to the solubleness of water.
(5) manufacture method according to any one of above-mentioned (1) ~ (4), wherein, relative to excessive dithiocarbonic anhydride, the amount of hydrophobic solvent is 100 % by weight ~ 10,000 % by weight.
(6) manufacture method according to any one of above-mentioned (1) ~ (5), wherein, hydrophobic solvent is at least one solvent selected in the group of normal hexane, normal heptane, toluene, chlorobenzene and dichlorobenzene formation.
(7) manufacture method according to any one of above-mentioned (1) ~ (6), wherein, alkali metal hydroxide is potassium hydroxide and/or sodium hydroxide.
(8) manufacture method according to any one of above-mentioned (1) ~ (7), wherein, after reaction terminates, comprise piperazine-N, further mixed alkali metal oxyhydroxide in the piperazine dithionic acid salt brine solution of N '-bis-dithionate what be separated hydrophobic solvent.
(9) a kind of piperazine-N, N '-bis-dithionic acid salt brine solution, is characterized in that, not containing piperazine-N-dithionate.
(10) piperazine-N according to above-mentioned (9), N '-bis-dithionic acid salt brine solution, wherein, piperazine-N, N '-bis-dithionate is sylvite.
the effect of invention
Manufacturing method according to the invention, just can manufacture without the need to carrying out utilizing the reaction controlling in the precipitation of the distillation Transformatin of the excessive dithiocarbonic anhydride of non-active gas, solid-state piperazine dithionic acid and comprise piperazine-N not containing piperazine-N-dithionate, the heavy metal treatment agent of N '-bis-dithionate, can obtain at the stable heavy metal treatment effect of aspect of performance.
Accompanying drawing explanation
Fig. 1 is the aqueous solution obtained in embodiment 6
13c-NMR spectrogram.
Fig. 2 is the aqueous solution obtained in embodiment 6
1h-NMR spectrogram.
Fig. 3 is the aqueous solution obtained in comparative example 1
13c-NMR spectrogram.
Fig. 4 is the aqueous solution obtained in comparative example 1
1h-NMR spectrogram.
Embodiment
The present invention will be described in detail below, but the present invention is not limited thereto.
The present invention relates to the piperazine-N not containing piperazine-N-dithionate, N '-bis-dithionic acid salt brine solution.Time containing piperazine-N-dithionate, can obtain heavy metal processing power high, at the stable heavy metal treatment effect of aspect of performance, and then, the reduction of processing power when preserving for a long time can be suppressed.In addition, in the present invention, do not refer to containing piperazine-N-dithionate and pass through
1h-NMR and
13c-NMR does not detect piperazine-N-dithionate.
As the piperazine-N in piperazine-N, N ' of the present invention-bis-dithionic acid salt brine solution, N '-bis-dithionate, such as, can enumerate an alkali metal salt such as sylvite, sodium salt.Wherein especially preferred sylvite.
Piperazine-N of the present invention, the feature of the manufacture method of N '-bis-dithionic acid salt brine solution is, in the manufacture method of the piperazine dithionate mix in aqueous with dithiocarbonic anhydride and alkali metal hydroxide making piperazine, reacted, make to there is hydrophobic solvent during reaction, described dithiocarbonic anhydride is more than reaction equivalent relative to described piperazine.
By making to there is hydrophobic solvent during reaction in the present invention, the excessive dithiocarbonic anhydride in the past needing to distill after the reaction removal can be caught in hydrophobic solvent, make its with piperazine-N, N '-bis-dithionate is the piperazine dithionic acid salt brine solution two-phase laminated flow of main component, thus, easily only the water-soluble liquid phase of necessity is taken out.In addition, the unwanted side reaction because excessive dithiocarbonic anhydride causes can be suppressed.And then, the hydrophobic solvent capturing excessive dithiocarbonic anhydride can be recycled.During recycling hydrophobic solvent, owing to having captured excessive dithiocarbonic anhydride in solvent, therefore can reduce the use of excessive dithiocarbonic anhydride in ensuing reaction.
It should be noted that, here, the dithiocarbonic anhydride that excessive dithiocarbonic anhydride represents more than by reaction equivalent deducts the dithiocarbonic anhydride of reaction equivalent and the dithiocarbonic anhydride obtained.
Utilize manufacture method of the present invention and obtain with piperazine-N, N '-bis-dithionate is not containing piperazine-N-dithionate in the piperazine dithionic acid salt brine solution of main component.Therefore, measure
13during C-NMR, do not observe the peak in the piperazine-N-dithionate source near 47ppm; In addition, measure
1during H-NMR, do not observe the peak in the piperazine-N-dithionate source near 2.8ppm.
In manufacture method of the present invention, as the usage quantity of dithiocarbonic anhydride during reaction, preferably relative to the scope of mol ratio more than 2.00 times of equivalents and below 3.00 times of equivalents of the dithiocarbonic anhydride of piperazine, and then to be preferably more than 2.01 times of equivalents and below 2.5 times of equivalents, be especially preferably more than 2.05 times of equivalents and below 2.5 times of equivalents.Above-mentioned scope is in by making the usage quantity of dithiocarbonic anhydride, piperazine-N-dithionate can not be generated, piperazine-N can not be reduced, the production rate of N '-bis-dithionate, there will not be a large amount of excessive dithiocarbonic anhydride in addition, also piperazine-N can not be reduced, the production efficiency of N '-bis-dithionate.
In manufacture method of the present invention, as the usage quantity of alkali metal hydroxide during reaction, preferably be more than 1.95 times of equivalents relative to the mol ratio of the alkali metal hydroxide of piperazine and below 2.05 times of equivalents, be especially preferably more than 1.97 times of equivalents and below 2.02 times of equivalents.
In manufacture method of the present invention, further preferably after the completion of reaction, piperazine-the N obtained relative to being separated hydrophobic solvent, N '-bis-dithionic acid salt brine solution 100 weight part, adds alkali metal hydroxide 0.1 weight part ~ 3.0 weight part, especially preferably adds 0.3 weight part ~ 1.5 weight part.By excessive interpolation alkali metal hydroxide, piperazine-N can be stablized further, N '-bis-dithionic acid salt brine solution.Alkali metal hydroxide directly can add and also can add with the form of the aqueous solution of alkali metal hydroxide, especially preferably adds in form of an aqueous solutions.
As the hydrophobic solvent used in manufacture method of the present invention, have no particular limits, such as, can illustrate: the hydrocarbon such as Skellysolve A, normal hexane, normal heptane, benzene, toluene, chlorobenzene, dichlorobenzene, chloroform, diethyl ether, vinyl acetic monomer, methylene dichloride etc.In these solvents, during solubleness height especially to water, be mixed into piperazine-N, N '-bis-dithionate is the amount increase of the hydrophobic solvent in the piperazine dithionic acid salt brine solution of main component, thus the preferred solubleness to water is the hydrocarbon such as Skellysolve A, normal hexane, normal heptane, benzene, toluene, chlorobenzene, dichlorobenzene, chloroform etc. of less than 1 % by weight, especially preferably the hydrocarbon such as Skellysolve A, normal hexane, normal heptane, toluene, chlorobenzene, dichlorobenzene etc. of less than 0.1 % by weight.The hydrocarbon such as normal hexane, normal heptane that wherein especially preferred specific gravity is light, large with the difference in specific gravity of piperazine-N, N '-bis-dithionic acid salt brine solution.In addition, also can two or more used in combination by these compounds.
In the present invention, the amount of the hydrophobic solvent existed during reaction is preferably 100 % by weight ~ 10,000 % by weight relative to excessive dithiocarbonic anhydride, is especially preferably 200 % by weight ~ 2,000 % by weight.By making the usage quantity of hydrophobic solvent be in this scope, the seizure effect of dithiocarbonic anhydride can not reduce, and thus without the need to dithiocarbonic anhydride distillation being removed, does not also produce the possibility of unwanted side reaction.And then owing to also excessively can not catch dithiocarbonic anhydride, thus the possibility of not residual piperazine-N-dithionate, also can not reduce with piperazine-N, N '-bis-dithionate the production efficiency of the piperazine dithionic acid salt brine solution being main component.
For the hydrophobic solvent existed when reacting in the present invention, various method can being utilized to make it exist when reacting, having no particular limits.Such as can illustrate: from start most to add together with raw material hydrophobic solvent method, add in the reaction hydrophobic solvent method, in advance hydrophobic solvent mixed with dithiocarbonic anhydride and be added into the method etc. of reaction system.
As the alkali metal hydroxide used in manufacture method of the present invention, preferably use potassium hydroxide and/or sodium hydroxide.
Manufacturing method according to the invention, can manufacture the piperazine-N not containing piperazine-N-dithionate in piperazine dithionic acid salt brine solution, N '-bis-dithionic acid salt brine solution.By not containing piperazine-N-dithionate, especially can expect that the ability that heavy metal is fixed becomes higher and more stable performance.
In manufacture method of the present invention, the blending means of raw material during reaction is had no particular limits, the method for interpolation or portion-wise addition continuously when maintaining raw material ratio of components of the present invention can be illustrated in.Especially in the preferred solution comprising piperazine, hydrophobic solvent, dithiocarbonic anhydride and alkali metal hydroxide are divided into more than 2 batches methods of alternately adding; In the solution comprising dithiocarbonic anhydride, hydrophobic solvent, piperazine and alkali metal hydroxide are divided into more than 2 batches methods etc. of alternately adding.And then, be divided into more than 2 batches methods of alternately adding according to the order of dithiocarbonic anhydride, alkali metal hydroxide in the preferred solution comprising piperazine, hydrophobic solvent further; More than 2 batches methods etc. of alternately adding are divided into according to the order of piperazine, alkali metal hydroxide in the solution comprising dithiocarbonic anhydride, hydrophobic solvent.
In manufacture method of the present invention, to during reaction and slaking time temperature have no particular limits, be preferably room temperature (20 DEG C) ~ 45 DEG C, be especially preferably 30 DEG C ~ 45 DEG C.
In the present invention, after terminating the reaction of piperazine-N, N '-bis-dithionate, concentration in aqueous has no particular limits, can for being suitable for the concentration being used as heavy metal treatment agent, be preferably 20 % by weight ~ 50 % by weight, be especially preferably 30 % by weight ~ 45 % by weight.
In the present invention, by adding piperazine further, the reduction of the processing power that longer-term is preserved can be prevented.As the addition of piperazine, have no particular limits, from the aspect that the dithionate of piperazine is stable, preferably relative to piperazine-N, N '-bis-dithionic acid salt brine solution 100 weight part is 0.1 weight part ~ 2 weight part, is especially preferably 0.2 weight part ~ 1 weight part.Piperazine adds with the state of solid or with the form of the aqueous solution of piperazine, especially preferably adds in form of an aqueous solutions.
Embodiment
By the following examples invention is described, but the present invention is not by the restriction of these embodiments.
It should be noted that, the NMR(nucleus magnetic resonance in embodiment) measure (
13c-NMR and
1h-NMR), use the Gemini-200 of VARIAN Inc., use heavy water as solvent, use 3-trimethyl silyl Sodium Propionate-2,2,3,3-d
4carry out as reference material.
Embodiment 1
Possessing the 1L(liter of whipping appts, thermometer, condenser and dropping funnel) 4 mouthfuls of flasks in disposable interpolation water 189.4g, Piperazine anhydrous 56.0g(0.65mol) and normal hexane 75.0g, at 35 DEG C, make piperazine dissolved.By dithiocarbonic anhydride 123.8g(1.63mol) and 48.5 % by weight potassium hydroxide aqueous solution 150.4g(1.30mol) be divided into 4 batches separately, 40 DEG C, under agitation with 6 hours drip, make it react.
In addition, relative to piperazine, the mol ratio of alkali metal hydroxide is 2.00 times of equivalents, the mol ratio of dithiocarbonic anhydride is 2.50 times of equivalents, hydrophobic solvent (normal hexane) is 302 % by weight relative to excessive dithiocarbonic anhydride, the concentration of the piperazine-N in the aqueous solution, N '-bis-dithionate is 40.9 % by weight.
Then, slaking, after 15 minutes, obtains the yellow transparent liquid (aqueous solution) be separated with normal hexane.Utilize separating funnel to be separated, extract gained yellow liquid, stir after 15 minutes, add 48.5 % by weight potassium hydroxide aqueous solution 5.2g, filter.
The aqueous solution that mensuration obtains
13c-NMR, result, only observes the piperazine-N as main component near 53ppm and near 210ppm, the peak in N '-bis-dithionate source, does not observe the peak in the piperazine-N-dithionate source near 47ppm and near 55ppm.
Embodiment 2
Except making normal hexane 75.0g be except santochlor 75.0g, carry out same operation with embodiment 1.The liquid obtained is yellow transparent, measures
13the result of C-NMR, only observes the piperazine-N as main component near 53ppm and near 210ppm, the peak in N '-bis-dithionate source, does not observe the peak in the piperazine-N-dithionate source near 47ppm and near 55ppm.
Embodiment 3
Except making, normal hexane 75.0g is normal heptane 75.0g, dithiocarbonic anhydride is 106.6g(1.40mol) except, same operation is carried out (relative to piperazine with embodiment 1, the mol ratio of alkali metal hydroxide is 2.00 times of equivalents, and the mol ratio of dithiocarbonic anhydride is 2.15 times of equivalents.Hydrophobic solvent (normal heptane): be 987 % by weight relative to excessive dithiocarbonic anhydride.Piperazine-N in the aqueous solution, N '-bis-dithionic acid salt concn is 40.9 % by weight.）。The liquid obtained is yellow transparent, measures
13the result of C-NMR, only observes the piperazine-N as main component near 53ppm and near 210ppm, the peak in N '-bis-dithionate source, does not observe the peak in the piperazine-N-dithionate source near 47ppm and near 55ppm.And then, measure
1the result of H-NMR, does not observe the peak in the two dithionate source of piperazine-N-near 2.8ppm.
Embodiment 4
Except use be separated in embodiment 1 normal hexane, make the addition of dithiocarbonic anhydride for 104.0g(1.37mol) except, carry out same operation with embodiment 1.The liquid obtained is yellow transparent, measures
13the result of C-NMR, only observes the piperazine-N as main component near 53ppm and near 210ppm, the peak in N '-bis-dithionate source, does not observe the peak in the piperazine-N-dithionate source near 47ppm and near 55ppm.
Embodiment 5
Possessing the 500mL(milliliter of whipping appts, condenser and two dropping funnels) 4 mouthfuls of flasks in disposable interpolation water 58.8g, dithiocarbonic anhydride 101.5g(1.33mol) and normal heptane 25.0g, by 30 % by weight piperazine aqueous solution 186.6g(0.65mol) and 48.5 % by weight potassium hydroxide aqueous solution 150.4g(1.30mol) be divided into 3 batches separately, drip according to the sequence alternate of the 30 % by weight piperazine aqueous solution, 48.5 % by weight potassium hydroxide aqueous solutions, in addition, same operation is carried out with embodiment 1.Wherein, relative to piperazine, the mol ratio of alkali metal hydroxide is 2.00 times of equivalents, the mol ratio of dithiocarbonic anhydride is 2.05 times of equivalents, hydrophobic solvent (normal heptane) is 1,000 % by weight relative to excessive dithiocarbonic anhydride, piperazine-N in the aqueous solution, N '-bis-dithionic acid salt concn is 40.9 % by weight.
The liquid (aqueous solution) obtained is yellow transparent, measures
13the result of C-NMR, only observes the piperazine-N as main component near 53ppm and near 210ppm, the peak in N '-bis-dithionate source, does not observe the peak in the piperazine-N-dithionate source near 47ppm and near 55ppm.And then, measure
1the result of H-NMR, does not observe the peak in the two dithionate source of piperazine-N-near 2.8ppm.
Embodiment 6
Possessing the 500mL(milliliter of whipping appts, thermometer, condenser and dropping funnel) 4 mouthfuls of flasks in disposable interpolation water 189.4g, Piperazine anhydrous 56.0g(0.65mol) and normal heptane 5.0g, at 35 DEG C, make piperazine dissolved.By dithiocarbonic anhydride 99.5g(1.31mol) and 48.5 % by weight potassium hydroxide aqueous solution 148.9g(1.29mol) be divided into 4 batches separately, 40 DEG C, under agitation, alternately dripped whole amounts with 6 hours, make it react.
Wherein, relative to piperazine, the mol ratio of alkali metal hydroxide is 1.98 times of equivalents, the mol ratio of dithiocarbonic anhydride is 2.01 times of equivalents, hydrophobic solvent (normal heptane) is 1,010 % by weight relative to excessive dithiocarbonic anhydride, piperazine-N in the aqueous solution, N '-bis-dithionic acid salt concn is 40.9 % by weight.Slaking, after 15 minutes, obtains the yellow transparent liquid (aqueous solution) be separated with normal heptane.Utilize separating funnel to be separated, extract gained yellow liquid, stir after 15 minutes, add 48.5 % by weight potassium hydroxide aqueous solution 6.7g, filter.
The aqueous solution obtained
13the measurement result of C-NMR as shown in Figure 1.Only observe the piperazine-N as main component near 53ppm and near 210ppm, the peak in N '-bis-dithionate source, does not observe the peak in the piperazine-N-dithionate source near 47ppm and near 55ppm.And then,
1the measurement result of H-NMR as shown in Figure 2.Do not observe the peak in the two dithionate source of piperazine-N-near 2.8ppm.
Comparative example 1
Be 98.0g(1.29mol except making the amount of dithiocarbonic anhydride) (relative to piperazine, the mol ratio of dithiocarbonic anhydride is 1.98 times of equivalents.) beyond, carry out same operation with embodiment 1.The liquid (aqueous solution) obtained is yellow transparent, measures
13c-NMR, result (Fig. 3), except near 53ppm and near 210ppm, beyond peak as the piperazine-N of main component, N '-bis-dithionate source, also near 47ppm and near 55ppm, observe the peak that piperazine-N-dithionate originates.And then, measure
1h-NMR, result (Fig. 4), observes the peak in the two dithionate source of piperazine-N-near 2.8ppm.
Owing to not using more than reaction equivalent, (relative to piperazine, the mol ratio of dithiocarbonic anhydride is 2.00 times of equivalents.) dithiocarbonic anhydride, the piperazine-N obtained, N '-bis-dithionic acid salt brine solution comprises piperazine-N-dithionate.
Comparative example 2
Except not using except normal hexane, carry out same operation with embodiment 1.Owing to not using hydrophobic solvent, after slaking terminates, visually confirm unreacted dithiocarbonic anhydride, need to utilize non-active gas to carry out distillation and remove.
utilizability in industry
Utilize manufacture method of the present invention and the aqueous solution of the dithionate of piperazine that obtains can carry out to high-performance soil, waste water, burning ash, flying dust etc. containing the heavy metal process in the material of heavy metal, industrially useful.
In addition, the full content of No. 2011-074065, the Japanese patent application of No. 2010-266294, the Japanese patent application applied on November 30th, 2010, application on March 30th, 2011 and the specification sheets of No. 2011-180509, Japanese patent application of application on August 22nd, 2011, claims, accompanying drawing and specification digest is incorporated in this, introduces as content disclosed in specification sheets of the present invention.
Claims (9)
1. a piperazine-N, the manufacture method of N '-bis-dithionic acid salt brine solution, it is characterized in that, in the manufacture method of the piperazine dithionate mix in aqueous with dithiocarbonic anhydride and alkali metal hydroxide making piperazine, reacted, make to there is hydrophobic solvent during reaction, and hydrophobic solvent is less than 1 % by weight to the solubleness of water, described dithiocarbonic anhydride is more than reaction equivalent relative to described piperazine
Be more than 2.00 times of equivalents relative to the mol ratio of the dithiocarbonic anhydride of piperazine and below 3.00 times of equivalents, relative to excessive dithiocarbonic anhydride, the amount of hydrophobic solvent is 100 % by weight ~ 10,000 % by weight.
2. manufacture method according to claim 1, is characterized in that, is more than 1.95 times of equivalents and below 2.05 times of equivalents relative to the mol ratio of the alkali metal hydroxide of piperazine.
3. manufacture method according to claim 1, is characterized in that, hydrophobic solvent is be selected from least one solvent selected in the group of normal hexane, normal heptane, toluene, chlorobenzene and dichlorobenzene formation.
4. manufacture method according to claim 1, is characterized in that, alkali metal hydroxide is potassium hydroxide and/or sodium hydroxide.
5. manufacture method according to claim 1, is characterized in that, after reaction terminates, comprises piperazine-N, further mixed alkali metal oxyhydroxide in the piperazine dithionic acid salt brine solution of N '-bis-dithionate what be separated hydrophobic solvent.
6. a piperazine-N, the manufacture method of N '-bis-dithionic acid salt brine solution, it is characterized in that, in the manufacture method of the piperazine dithionate mix in aqueous with dithiocarbonic anhydride and alkali metal hydroxide making piperazine, reacted, make to there is hydrophobic solvent during reaction, and hydrophobic solvent is be selected from least one solvent selected in the group of normal hexane, normal heptane, toluene, chlorobenzene and dichlorobenzene formation, described dithiocarbonic anhydride is more than reaction equivalent relative to described piperazine
Be more than 2.00 times of equivalents relative to the mol ratio of the dithiocarbonic anhydride of piperazine and below 3.00 times of equivalents, relative to excessive dithiocarbonic anhydride, the amount of hydrophobic solvent is 100 % by weight ~ 10,000 % by weight.
7. manufacture method according to claim 6, is characterized in that, is more than 1.95 times of equivalents and below 2.05 times of equivalents relative to the mol ratio of the alkali metal hydroxide of piperazine.
8. manufacture method according to claim 6, is characterized in that, alkali metal hydroxide is potassium hydroxide and/or sodium hydroxide.
9. manufacture method according to claim 6, is characterized in that, after reaction terminates, comprises piperazine-N, further mixed alkali metal oxyhydroxide in the piperazine dithionic acid salt brine solution of N '-bis-dithionate what be separated hydrophobic solvent.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-266294 | 2010-11-30 | ||
| JP2010266294 | 2010-11-30 | ||
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| JP2011180509A JP5831036B2 (en) | 2010-11-30 | 2011-08-22 | Piperazine-N, N'-biscarbodithioate aqueous solution and method for producing the same |
| JP2011-180509 | 2011-08-22 | ||
| PCT/JP2011/077578 WO2012073976A1 (en) | 2010-11-30 | 2011-11-29 | Aqueous solution of piperazine-n, n'-bis-carbodithioate, and production method for same |
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| CN112480039B (en) * | 2020-12-18 | 2023-04-07 | 成都恒鑫和环保科技有限公司 | Method for preparing piperazine-N, N' -potassium bisdithio carboxylate by adding different alcohols into reaction liquid |
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| US6545172B1 (en) * | 2002-04-18 | 2003-04-08 | Bayer Corporation | Processes for the production of methyl dithiocarbazinate |
| CN1603249A (en) * | 2004-09-08 | 2005-04-06 | 中山大学 | Heavy metal precipitating agent |
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| JP3391173B2 (en) * | 1994-12-02 | 2003-03-31 | 東ソー株式会社 | Method for immobilizing heavy metals in fly ash and agent for immobilizing heavy metals |
| JP4573343B2 (en) * | 2001-11-21 | 2010-11-04 | 日本曹達株式会社 | Method for producing aqueous solution containing piperazine biscarbodithioate |
| JP4696475B2 (en) * | 2004-05-28 | 2011-06-08 | 東ソー株式会社 | Dithiocarbamate aqueous solution, production method thereof, heavy metal immobilization agent and heavy metal immobilization treatment method |
| JP4792810B2 (en) * | 2005-05-13 | 2011-10-12 | 東ソー株式会社 | Heavy metal treatment agent and heavy metal treatment method using the same |
| JP4796824B2 (en) * | 2005-11-30 | 2011-10-19 | 栗田工業株式会社 | Low temperature storage stabilizer for heavy metal fixing agent |
| JP5493244B2 (en) * | 2006-12-07 | 2014-05-14 | 東ソー株式会社 | Method for producing piperazine heavy metal treating agent |
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| US6545172B1 (en) * | 2002-04-18 | 2003-04-08 | Bayer Corporation | Processes for the production of methyl dithiocarbazinate |
| CN1603249A (en) * | 2004-09-08 | 2005-04-06 | 中山大学 | Heavy metal precipitating agent |
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| Heterocyclo-substituted sulfa drugs: Part XI. Novel biologically active N-(piperidino-, morpholino-, piperazino-) dithiocarbamyl-azo dyes and their chelates;IBRAHIM M.A. AWAD;《Phosphorus, Sulfur and Silicon》;20001231;第163卷;219-251 * |
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| 张志刚 等.1,4-双(二硫代甲酸乙酸酯基)哌嗪衍生物的合成与摩擦学性能研究.《润滑与密封》.2008,第33卷(第1期),81-84. * |
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| CN103237796A (en) | 2013-08-07 |
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