CN103237796A - Aqueous solution of piperazine-N, N'-bis-carbodithioate, and production method for same - Google Patents
Aqueous solution of piperazine-N, N'-bis-carbodithioate, and production method for same Download PDFInfo
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- CN103237796A CN103237796A CN201180057459XA CN201180057459A CN103237796A CN 103237796 A CN103237796 A CN 103237796A CN 201180057459X A CN201180057459X A CN 201180057459XA CN 201180057459 A CN201180057459 A CN 201180057459A CN 103237796 A CN103237796 A CN 103237796A
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- piperazine
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- dithiocarbonic anhydride
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- C07D—HETEROCYCLIC COMPOUNDS
- 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
Abstract
Provided is an industrial production method for increasing the ratio of piperazine-N, N'-bis-carbodithioate which has excellent heavy metal treatment ability, when producing a piperazine carbodithioate useful as a heavy metal treatment agent and without requiring distilling off of carbon disulfide by inert gas. Specifically provided is a method for producing an aqueous solution of piperazine-N, N'-bis-carbodithioate characterized by the presence of a hydrophobic solvent during reaction, in a method for producing piperazine carbodithioate by mixing piperazine, at least the reaction equivalent of carbon disulfide relative to piperazine, and an alkali metal hydroxide, and reacting same.
Description
Technical field
The present invention relates to as heavy metal treatment agent useful piperazine dithionic acid salt brine solution and manufacture method thereof, more specifically, the invention provides the piperazine-N that does not contain piperazine-N-dithionate, N '-two dithionates' the aqueous solution and manufacture method thereof.
Background technology
Environmental problem, especially being not only China about the environmental pollution problems of offal treatment also is the common problem in the world.In China, to utilize because of the flying dust that castoff burning produces the chelating chemical reagent carry out heavy metal insoluble after, final landfill yard (Controlled Final Landfill Site) at management type is handled, and has established preventing because of the soil that the castoff burning ash causes, the technology of phreatic heavy metal contamination.
As the thawless sequestrant of heavy metal that can make in the flying dust, can use the dithionate of various amine, especially the dithionate of piperazine not only has the immobilization of heavy metals ability, and can not produce obnoxious flavour when using, be widely used as the chemical reagent of stability and excellent in safety by (for example with reference to patent documentation 1).
On the other hand, recently, the flying dust that the countries in Asia of China's periphery also begin one's study after utilizing sequestrant to castoff burning is handled, and carries out safe processing.Correspondingly, the worldwide demand that flying dust is handled the sequestrant of usefulness is also increasing gradually.
For the dithionate of the piperazine that has excellent properties as heavy metal treatment agent, can there be piperazine-N, these two kinds of chemical structures of N '-two dithionates and piperazine-N-dithionate, piperazine-N wherein, N '-two dithionates have higher heavy metal processing power.
For the dithionate of piperazine, in the aqueous solution, piperazine, dithiocarbonic anhydride and alkali metal hydroxide are mixed, after the low temperature below the boiling point of dithiocarbonic anhydride (about 40 ℃ of front and back) reacts down, need carry out maturation process.Slaking is in the past carried out under the condition of base excess for the decomposition that suppresses the dithionate.
In the past, as making the high piperazine-N of heavy metal processing power, the dithionate's of N '-piperazine that two dithionate's ratios are high method, use excessive dithiocarbonic anhydride during known responding, use non-active gas that the method (for example with reference to patent documentation 1) that (removal) handled is removed in unreacted dithiocarbonic anhydride distillation at last.Also known have when reaction the method for raw material batch mixing, the method for reacting in the presence of the piperazine dithionic acid (for example with reference to patent documentation 2,3).
But, use excessive dithiocarbonic anhydride to improve piperazine-N according to method in the past, in the method for N '-two dithionate's ratios, need after reaction, use a large amount of nitrogen to distill and remove processing, be not industrial preferable methods.In addition, utilize the method for batch mixing dithiocarbonic anhydride and alkali metal hydroxide in the aqueous solution of piperazine, though can improve piperazine-N, N '-two dithionates' ratio needs to increase many number of times in batches, has the numerous and diverse problem of operation change.
The method of reacting in the presence of the piperazine dithionic acid also is same, though can improve piperazine-N, N '-two dithionates' ratio, but the piperazine dithionic acid is insoluble solid, sometimes be difficult to react uniformly, sometimes the piperazine dithionic acid precipitate in the reactive tank (especially agitating wing), and reaction control becomes difficult, need improve.
The prior art document
Patent documentation
Patent documentation 1: No. 3391173 communique of Japanese Patent
Patent documentation 2: TOHKEMY 2003-221389 communique
Patent documentation 3: TOHKEMY 2008-143810 communique
Summary of the invention
The problem that invention will solve
In order to make the piperazine-N that comprises that does not contain piperazine-N-dithionate, N '-two dithionates' heavy metal treatment agent utilizes the distillation of non-active gas to remove to handle, the reaction control in separating out of the piperazine dithionic acid of solid is necessary.
The object of the present invention is to provide a kind of distillation that does not contain piperazine-N-dithionate, need not to utilize non-active gas to carry out dithiocarbonic anhydride to remove the industrial useful piperazine-N that handles, the manufacture method of N '-two dithionic acid salt brine solutions.
For the scheme of dealing with problems
Discoveries such as the inventor, for making piperazine and being dithiocarbonic anhydride and the alkali metal hydroxide method of in the aqueous solution reacting of reaction more than the equivalent with respect to this piperazine, by when reacting, there being hydrophobic solvent, need not to utilize the distillation of non-active gas to remove after the reaction to handle, the reaction control of piperazine dithionic acid in separating out just can make the piperazine-N that does not contain piperazine-N-dithionate, N '-two dithionic acid salt brine solutions, thus the present invention finished.
That is, the present invention is the invention with following main idea.
(1) a kind of piperazine-N, the manufacture method of N '-two dithionic acid salt brine solutions, it is characterized in that, in the piperazine dithionate's who makes piperazine and dithiocarbonic anhydride and alkali metal hydroxide in the aqueous solution, mix, react manufacture method, have hydrophobic solvent when making reaction, described dithiocarbonic anhydride is more than the reaction equivalent with respect to described piperazine.
(2) according to above-mentioned (1) described manufacture method, wherein, it is 2.00 times more than the equivalent and 3.00 times below the equivalent with respect to the mol ratio of the dithiocarbonic anhydride of piperazine.
(3) according to above-mentioned (1) or (2) described manufacture method, wherein, it is 1.95 times more than the equivalent and 2.05 times below the equivalent with respect to the mol ratio of the alkali metal hydroxide of piperazine.
(4) according to each described manufacture method of above-mentioned (1)～(3), wherein, hydrophobic solvent is below the 1 weight % to the solubleness of water.
(5) according to each described manufacture method of above-mentioned (1)～(4), wherein, with respect to excessive dithiocarbonic anhydride, the amount of hydrophobic solvent is 100 weight %～10000 weight %.
(6) according to each described manufacture method of above-mentioned (1)～(5), wherein, at least a solvent of hydrophobic solvent for selecting in the group that constitutes from normal hexane, normal heptane, toluene, chlorobenzene and dichlorobenzene.
(7) according to each described manufacture method of above-mentioned (1)～(6), wherein, alkali metal hydroxide is potassium hydroxide and/or sodium hydroxide.
(8) according to each described manufacture method of above-mentioned (1)～(7), wherein, reaction is separating the piperazine-N that comprises of hydrophobic solvent after finishing, further mixed alkali metal oxyhydroxide in N '-two dithionates' the piperazine dithionic acid salt brine solution.
(9) a kind of piperazine-N, N '-two dithionic acid salt brine solutions is characterized in that, does not contain piperazine-N-dithionate.
(10) according to above-mentioned (9) described piperazine-N, N '-two dithionic acid salt brine solutions, wherein, and piperazine-N, N '-two dithionates are sylvite.
The effect of invention
Manufacturing method according to the invention, need not to utilize the distillation of the excessive dithiocarbonic anhydride of non-active gas to remove to handle, the reaction control in the separating out of solid-state piperazine dithionic acid just can make the piperazine-N that comprises that does not contain piperazine-N-dithionate, N '-two dithionates' heavy metal treatment agent can obtain at the stable heavy metal treatment effect of aspect of performance.
Description of drawings
Fig. 1 is for the aqueous solution that obtains in embodiment 6
13The C-NMR spectrogram.
Fig. 2 is for the aqueous solution that obtains in embodiment 6
1The H-NMR spectrogram.
Fig. 3 is for the aqueous solution that obtains in comparative example 1
13The C-NMR spectrogram.
Fig. 4 is for the aqueous solution that obtains in comparative example 1
1The H-NMR spectrogram.
Embodiment
Below the present invention will be described in detail, but the present invention is not limited thereto.
The present invention relates to not contain piperazine-N of piperazine-N-dithionate, N '-two dithionic acid salt brine solutions.When not containing piperazine-N-dithionate, can obtain heavy metal processing power height, at the stable heavy metal treatment effect of aspect of performance, and then, the reduction of the processing power in the time of can suppressing prolonged preservation.In addition, among the present invention, do not contain piperazine-N-dithionate refer to by
1H-NMR and
13C-NMR does not detect piperazine-N-dithionate.
As piperazine-N of the present invention, the piperazine-N in N '-two dithionic acid salt brine solutions, N '-two dithionates for example can enumerate an alkali metal salts such as sylvite, sodium salt.Especially preferred sylvite wherein.
Piperazine-N of the present invention, the manufacture method of N '-two dithionic acid salt brine solutions is characterised in that, in the piperazine dithionate's who makes piperazine and dithiocarbonic anhydride and alkali metal hydroxide in the aqueous solution, mix, react manufacture method, have hydrophobic solvent when making reaction, described dithiocarbonic anhydride is more than the reaction equivalent with respect to described piperazine.
There is hydrophobic solvent when reacting by making among the present invention, can in hydrophobic solvent, catch and after reaction, to distill the excessive dithiocarbonic anhydride of removing in the past, make its with piperazine-N, N '-two dithionates are that the piperazine dithionic acid salt brine solution two-phase of main component is separated, thus, only the water-soluble liquid phase of necessity is taken out easily.In addition, can suppress the unwanted side reaction that causes because of excessive dithiocarbonic anhydride.And then, can recycling have caught the hydrophobic solvent of excessive dithiocarbonic anhydride.During the recycling hydrophobic solvent, owing to caught excessive dithiocarbonic anhydride in the solvent, therefore can reduce the use of excessive dithiocarbonic anhydride in the ensuing reaction.
Need to prove that, excessive dithiocarbonic anhydride is represented to deduct the dithiocarbonic anhydride that reacts equivalent and the dithiocarbonic anhydride that obtains by the dithiocarbonic anhydride more than the reaction equivalent here.
Utilize manufacture method of the present invention and obtain with piperazine-N, N '-two dithionates are not for containing piperazine-N-dithionate in the piperazine dithionic acid salt brine solution of main component.Therefore, measure
13During C-NMR, do not observe near the peak in the piperazine of 47ppm-N-dithionate source; In addition, measure
1During H-NMR, do not observe near the peak in the piperazine of 2.8ppm-N-dithionate source.
In the manufacture method of the present invention, the usage quantity of dithiocarbonic anhydride during as reaction, preferably with respect to the mol ratio of the dithiocarbonic anhydride of piperazine at 2.00 times more than the equivalent and 3.00 times of scopes below the equivalent, and then it is above and 2.5 times below the equivalent to be preferably 2.01 times of equivalents, and it is above and 2.5 times below the equivalent especially to be preferably 2.05 times of equivalents.Be in above-mentioned scope by the usage quantity that makes dithiocarbonic anhydride, can not generate piperazine-N-dithionate, can not reduce piperazine-N, N '-two dithionates' production rate, a large amount of excessive dithiocarbonic anhydride can not appear in addition, can not reduce piperazine-N, N '-two dithionates' production efficiency yet.
In the manufacture method of the present invention, the usage quantity of alkali metal hydroxide during as reaction, be 1.95 times more than the equivalent and 2.05 times below the equivalent with respect to the mol ratio of the alkali metal hydroxide of piperazine preferably, it is above and 2.02 times below the equivalent especially to be preferably 1.97 times of equivalents.
In the manufacture method of the present invention, further preferably after reaction finishes, piperazine-the N that has obtained with respect to having separated hydrophobic solvent, N '-two dithionic acid salt brine solution 100 weight parts adds alkali metal hydroxide 0.1 weight part～3.0 weight parts, especially preferably adds 0.3 weight part～1.5 weight parts.By excessive interpolation alkali metal hydroxide, can further stablize piperazine-N, N '-two dithionic acid salt brine solutions.Alkali metal hydroxide can directly add also and can add with the form of the aqueous solution of alkali metal hydroxide, especially preferably adds with the form of the aqueous solution.
Hydrophobic solvent as using in the manufacture method of the present invention has no particular limits, for example can illustration: 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, when especially high to the solubleness of water, sneak into piperazine-N, N '-two dithionates are that the amount of the hydrophobic solvent in the piperazine dithionic acid salt brine solution of main component increases, thereby be hydrocarbon, benzene, toluene, chlorobenzene, dichlorobenzene, chloroforms etc. such as Skellysolve A, normal hexane, normal heptane below the 1 weight % to the solubleness of water preferably, hydrocarbon, toluene, chlorobenzene, dichlorobenzene etc. such as the following Skellysolve A of especially preferred 0.1 weight %, normal hexane, normal heptane.Wherein especially preferred specific gravity light, with piperazine-N, hydrocarbon such as the normal hexane that the difference in specific gravity of N '-two dithionic acid salt brine solutions is big, normal heptane.In addition, also the two or more mixing of these compounds can be used.
Among the present invention, the amount of the hydrophobic solvent that exists during reaction is 100 weight %～10000 weight % with respect to excessive dithiocarbonic anhydride preferably, especially is preferably 200 weight %～2000 weight %.Be in this scope by the usage quantity that makes hydrophobic solvent, the seizure effect of dithiocarbonic anhydride can not reduce, thereby need not the dithiocarbonic anhydride distillation is removed, and does not produce the possibility of unwanted side reaction yet.And then, owing to can excessively not catch dithiocarbonic anhydride yet, thereby do not have residual piperazine-N-dithionate's possibility, can not reduce with piperazine-N yet, N '-two dithionates are the production efficiency of the piperazine dithionic acid salt brine solution of main component.
For the hydrophobic solvent that when reacting, exists among the present invention, can utilize the whole bag of tricks that it is existed when reaction, have no particular limits.For example can illustration: from begin most with raw material add the method for hydrophobic solvent, in the reaction add the method for hydrophobic solvent, hydrophobic solvent is mixed and is added into the method etc. of reaction system with dithiocarbonic anhydride in advance.
As the alkali metal hydroxide that uses in the manufacture method of the present invention, preferably use potassium hydroxide and/or sodium hydroxide.
Manufacturing method according to the invention can be made the piperazine-N that does not contain piperazine-N-dithionate in the piperazine dithionic acid salt brine solution, N '-two dithionic acid salt brine solutions.By not containing piperazine-N-dithionate, especially can expect the performance that the fixing ability of heavy metal becomes higher and more stable.
In the manufacture method of the present invention, the blending means of raw material has no particular limits to when reaction, can be illustrated in to add continuously under the situation of keeping raw material ratio of components of the present invention or the method for portion-wise addition.Especially preferably in the solution that comprises piperazine, hydrophobic solvent, dithiocarbonic anhydride and alkali metal hydroxide are divided into the method for alternately adding more than 2 batches; In the solution that comprises dithiocarbonic anhydride, hydrophobic solvent, piperazine and alkali metal hydroxide be divided into the method for alternately adding more than 2 batches etc.And then, further preferred in the solution that comprises piperazine, hydrophobic solvent the order according to dithiocarbonic anhydride, alkali metal hydroxide be divided into the method for alternately adding more than 2 batches; In the solution that comprises dithiocarbonic anhydride, hydrophobic solvent, be divided into the method for alternately adding more than 2 batches etc. according to the order of piperazine, alkali metal hydroxide.
In the manufacture method of the present invention, the temperature during to when reaction and slaking has no particular limits, and is preferably room temperature (20 ℃)～45 ℃, especially is preferably 30 ℃～45 ℃.
Among the present invention, to piperazine-N, N '-two dithionates' reaction finishes the concentration of back in the aqueous solution and has no particular limits, can be for suiting as the concentration of heavy metal treatment agent, be preferably 20 weight %～50 weight %, especially be preferably 30 weight %～45 weight %.
Among the present invention, by further interpolation piperazine, can prevent for the more reduction of the processing power of prolonged preservation.Addition as piperazine, have no particular limits, from the stable aspect of the dithionate of piperazine, preferably with respect to piperazine-N, N '-two dithionic acid salt brine solution 100 weight parts are 0.1 weight part～2 weight parts, especially are 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 with the form of the aqueous solution.
Embodiment
By the following examples invention is described, but the present invention is not subjected to the restriction of these embodiment.
Need to prove, for the NMR(nucleus magnetic resonance among the embodiment) measure (
13C-NMR reaches
1H-NMR), use the Gemini-200 of VARIAN corporate system, use heavy water as solvent, use 3-trimethyl silyl Sodium Propionate-2,2,3,3-d
4Carry out as reference material.
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, under 35 ℃, make piperazine dissolved.With dithiocarbonic anhydride 123.8g(1.63mol) and 48.5 weight % potassium hydroxide aqueous solution 150.4g(1.30mol) be divided into 4 batches separately, 40 ℃, under agitation dripped with 6 hours, make its reaction.
In addition, with respect 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 weight % with respect to excessive dithiocarbonic anhydride, piperazine-N in the aqueous solution, N '-two dithionates' concentration is 40.9 weight %.
Then, slaking is after 15 minutes, obtains the yellow transparent liquid (aqueous solution) that has been separated with normal hexane.Utilize separating funnel to separate, extract the gained yellow liquid, stir after 15 minutes, add 48.5 weight % potassium hydroxide aqueous solution 5.2g, filter.
The aqueous solution that mensuration obtains
13C-NMR, the result is only observing piperazine-N as main component near the 53ppm and near the 210ppm, and the peak in N '-two dithionates source does not observe near the 47ppm and near the peak in the piperazine the 55ppm-N-dithionate source.
Be the santochlor 75.0g except making normal hexane 75.0g, carry out same operation with embodiment 1.The liquid that obtains is yellow transparent, measures
13The result of C-NMR is only observing piperazine-N as main component near the 53ppm and near the 210ppm, the peak in N '-two dithionates source does not observe near the 47ppm and near the peak in the piperazine the 55ppm-N-dithionate source.
Be that normal heptane 75.0g, dithiocarbonic anhydride are 106.6g(1.40mol except making normal hexane 75.0g), carry out same operation (with respect 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 weight % with respect to excessive dithiocarbonic anhydride.Piperazine-N in the aqueous solution, N '-two dithionic acid salt concn are 40.9 weight %.）。The liquid that obtains is yellow transparent, measures
13The result of C-NMR is only observing piperazine-N as main component near the 53ppm and near the 210ppm, the peak in N '-two dithionates source does not observe near the 47ppm and near the peak in the piperazine the 55ppm-N-dithionate source.And then, measure
1The result of H-NMR does not observe the peak that near the two dithionates of the piperazine-N-of 2.8ppm originate.
Except using in embodiment 1 normal hexane that separates, making the addition of dithiocarbonic anhydride be 104.0g(1.37mol), carry out same operation with embodiment 1.The liquid that obtains is yellow transparent, measures
13The result of C-NMR is only observing piperazine-N as main component near the 53ppm and near the 210ppm, the peak in N '-two dithionates source does not observe near the 47ppm and near the peak in the piperazine the 55ppm-N-dithionate source.
At the 500mL(milliliter that possesses 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, with 30 weight % piperazine aqueous solution 186.6g(0.65mol) and 48.5 weight % potassium hydroxide aqueous solution 150.4g(1.30mol) be divided into 3 batches separately, sequence alternate according to the 30 weight % piperazine aqueous solution, 48.5 weight % potassium hydroxide aqueous solutions drips, in addition, carry out same operation with embodiment 1.Wherein, with respect 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 1000 weight % with respect to excessive dithiocarbonic anhydride, piperazine-N in the aqueous solution, N '-two dithionic acid salt concn are 40.9 weight %.
The liquid that obtains (aqueous solution) is yellow transparent, measures
13The result of C-NMR is only observing piperazine-N as main component near the 53ppm and near the 210ppm, the peak in N '-two dithionates source does not observe near the 47ppm and near the peak in the piperazine the 55ppm-N-dithionate source.And then, measure
1The result of H-NMR does not observe the peak that near the two dithionates of the piperazine-N-of 2.8ppm originate.
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, under 35 ℃, make piperazine dissolved.With dithiocarbonic anhydride 99.5g(1.31mol) and 48.5 weight % potassium hydroxide aqueous solution 148.9g(1.29mol) be divided into 4 batches separately, 40 ℃, under agitation, alternately drip whole amounts with 6 hours, make its reaction.
Wherein, with respect 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 1010 weight % with respect to excessive dithiocarbonic anhydride, piperazine-N in the aqueous solution, N '-two dithionic acid salt concn are 40.9 weight %.After the slaking 15 minutes, obtain the yellow transparent liquid (aqueous solution) that has been separated with normal heptane.Utilize separating funnel to separate, extract the gained yellow liquid, stir after 15 minutes, add 48.5 weight % potassium hydroxide aqueous solution 6.7g, filter.
The aqueous solution that obtains
13The measurement result of C-NMR as shown in Figure 1.Only observing piperazine-N as main component near the 53ppm and near the 210ppm, the peak in N '-two dithionates source does not observe near the 47ppm and near the peak in the piperazine the 55ppm-N-dithionate source.And then,
1The measurement result of H-NMR as shown in Figure 2.Do not observe near the peak in the two dithionates of the piperazine-N-of 2.8ppm source.
Comparative example 1
Except the amount that makes dithiocarbonic anhydride is 98.0g(1.29mol) (with respect to piperazine, the mol ratio of dithiocarbonic anhydride is 1.98 times of equivalents.) in addition, carry out same operation with embodiment 1.The liquid that obtains (aqueous solution) is yellow transparent, measures
13C-NMR, result (Fig. 3), except near the 53ppm and near the 210ppm, as the piperazine-N of main component, beyond the peak in N '-two dithionates source, also near near the peak that is observing piperazine-N-dithionate source the 47ppm and the 55ppm.And then, measure
1H-NMR, result (Fig. 4) observes the peak that near the two dithionates of the piperazine-N-of 2.8ppm originate.
(with respect to piperazine, the mol ratio of dithiocarbonic anhydride is 2.00 times of equivalents because more than using the reaction equivalent.) dithiocarbonic anhydride, the piperazine-N that obtains, N '-two dithionic acid salt brine solutions comprise piperazine-N-dithionate.
Comparative example 2
Except not using normal hexane, carry out same operation with embodiment 1.Owing to do not use hydrophobic solvent, after slaking finished, Visual Confirmation need utilize non-active gas to distill removal to unreacted dithiocarbonic anhydride.
Utilizability on the industry
The dithionate's of the piperazine that utilizes manufacture method of the present invention and obtain the aqueous solution can carry out to high-performance the heavy metal that soil, waste water, burning ash, flying dust etc. contain in the material of heavy metal to be handled, industrial useful.
In addition, the full content of Japanese patent application 2011-180509 number specification sheets, claims, accompanying drawing and specification digest of Japanese patent application 2011-074065 number of the application on March 30th, Japanese patent application 2010-266294 number 1 of on November 30th, 2010 application and application on August 22nd, 2011 is incorporated in this, introduces as the disclosed content of specification sheets of the present invention.
Claims (10)
1. piperazine-N, the manufacture method of N '-two dithionic acid salt brine solutions, it is characterized in that, in the piperazine dithionate's who makes piperazine and dithiocarbonic anhydride and alkali metal hydroxide in the aqueous solution, mix, react manufacture method, have hydrophobic solvent when making reaction, described dithiocarbonic anhydride is more than the reaction equivalent with respect to described piperazine.
2. manufacture method according to claim 1 is characterized in that, is 2.00 times more than the equivalent and 3.00 times below the equivalent with respect to the mol ratio of the dithiocarbonic anhydride of piperazine.
3. manufacture method according to claim 1 and 2 is characterized in that, is 1.95 times more than the equivalent and 2.05 times below the equivalent with respect to the mol ratio of the alkali metal hydroxide of piperazine.
4. according to each described manufacture method of claim 1～3, it is characterized in that hydrophobic solvent is below the 1 weight % to the solubleness of water.
5. according to each described manufacture method of claim 1～4, it is characterized in that with respect to excessive dithiocarbonic anhydride, the amount of hydrophobic solvent is 100 weight %～10000 weight %.
6. according to each described manufacture method of claim 1～5, it is characterized in that at least a solvent of hydrophobic solvent for selecting in the group that constitutes from normal hexane, normal heptane, toluene, chlorobenzene and dichlorobenzene.
7. according to each described manufacture method of claim 1～6, it is characterized in that alkali metal hydroxide is potassium hydroxide and/or sodium hydroxide.
8. according to each described manufacture method of claim 1～7, it is characterized in that, reaction is separating the piperazine-N that comprises of hydrophobic solvent after finishing, further mixed alkali metal oxyhydroxide in N '-two dithionates' the piperazine dithionic acid salt brine solution.
9. piperazine-N, N '-two dithionic acid salt brine solutions is characterized in that, does not contain piperazine-N-dithionate.
10. piperazine-N according to claim 9, N '-two dithionic acid salt brine solutions is characterized in that, piperazine-N, N '-two dithionates are sylvite.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010266294 | 2010-11-30 | ||
| JP2010-266294 | 2010-11-30 | ||
| JP2011074065 | 2011-03-30 | ||
| JP2011-074065 | 2011-03-30 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621904A (en) * | 2017-10-06 | 2019-04-16 | 东曹株式会社 | The purification method of nickeliferous aqueous solution cleanser and nickeliferous aqueous solution |
| CN112480039A (en) * | 2020-12-18 | 2021-03-12 | 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 |
| CN112552262A (en) * | 2020-08-13 | 2021-03-26 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6360986A (en) * | 1986-08-29 | 1988-03-17 | Idemitsu Petrochem Co Ltd | Dithiocarbamate and production thereof |
| JPH08224560A (en) * | 1994-12-02 | 1996-09-03 | Tosoh Corp | Fixing of heavy metals in fly ash |
| US6545172B1 (en) * | 2002-04-18 | 2003-04-08 | Bayer Corporation | Processes for the production of methyl dithiocarbazinate |
| JP2003221389A (en) * | 2001-11-21 | 2003-08-05 | Nippon Soda Co Ltd | Method for producing aqueous solution containing piperazine biscarbodithioate |
| CN1603249A (en) * | 2004-09-08 | 2005-04-06 | 中山大学 | Heavy metal precipitating agent |
| JP2005336128A (en) * | 2004-05-28 | 2005-12-08 | Tosoh Corp | Aqueous dithiocarbamic acid salt solution, method for producing the same, heavy metal-fixing agent and method for fixing heavy metal |
| JP2006316183A (en) * | 2005-05-13 | 2006-11-24 | Tosoh Corp | Heavy metal treating agent and treating method of heavy metal using the same |
| JP2007146089A (en) * | 2005-11-30 | 2007-06-14 | Kurita Water Ind Ltd | Low-temperature storage stabilizing agent for heavy metal immobilization agent |
| JP2008143810A (en) * | 2006-12-07 | 2008-06-26 | Tosoh Corp | Method for producing piperazine-based heavy metal treating agent |
-
2011
- 2011-08-22 JP JP2011180509A patent/JP5831036B2/en active Active
- 2011-11-29 WO PCT/JP2011/077578 patent/WO2012073976A1/en active Application Filing
- 2011-11-29 CN CN201180057459.XA patent/CN103237796B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6360986A (en) * | 1986-08-29 | 1988-03-17 | Idemitsu Petrochem Co Ltd | Dithiocarbamate and production thereof |
| JPH08224560A (en) * | 1994-12-02 | 1996-09-03 | Tosoh Corp | Fixing of heavy metals in fly ash |
| JP2003221389A (en) * | 2001-11-21 | 2003-08-05 | Nippon Soda Co Ltd | Method for producing aqueous solution containing piperazine biscarbodithioate |
| US6545172B1 (en) * | 2002-04-18 | 2003-04-08 | Bayer Corporation | Processes for the production of methyl dithiocarbazinate |
| JP2005336128A (en) * | 2004-05-28 | 2005-12-08 | Tosoh Corp | Aqueous dithiocarbamic acid salt solution, method for producing the same, heavy metal-fixing agent and method for fixing heavy metal |
| CN1603249A (en) * | 2004-09-08 | 2005-04-06 | 中山大学 | Heavy metal precipitating agent |
| JP2006316183A (en) * | 2005-05-13 | 2006-11-24 | Tosoh Corp | Heavy metal treating agent and treating method of heavy metal using the same |
| JP2007146089A (en) * | 2005-11-30 | 2007-06-14 | Kurita Water Ind Ltd | Low-temperature storage stabilizing agent for heavy metal immobilization agent |
| JP2008143810A (en) * | 2006-12-07 | 2008-06-26 | Tosoh Corp | Method for producing piperazine-based heavy metal treating agent |
Non-Patent Citations (3)
| Title |
|---|
| IBRAHIM M.A. AWAD: "Heterocyclo-substituted sulfa drugs: Part XI. Novel biologically active N-(piperidino-, morpholino-, piperazino-) dithiocarbamyl-azo dyes and their chelates", 《PHOSPHORUS, SULFUR AND SILICON》 * |
| 崔元臣 等: "1,4-双-（二硫代酯基）哌嗪及其聚合物的研究进展", 《河南大学学报》 * |
| 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》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621904A (en) * | 2017-10-06 | 2019-04-16 | 东曹株式会社 | The purification method of nickeliferous aqueous solution cleanser and nickeliferous aqueous solution |
| CN109621904B (en) * | 2017-10-06 | 2023-06-06 | 东曹株式会社 | Purifying agent for nickel-containing aqueous solution and method for purifying nickel-containing aqueous solution |
| CN112552262A (en) * | 2020-08-13 | 2021-03-26 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
| CN112552262B (en) * | 2020-08-13 | 2022-03-08 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
| CN112480039A (en) * | 2020-12-18 | 2021-03-12 | 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 |
| 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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| JP5831036B2 (en) | 2015-12-09 |
| WO2012073976A1 (en) | 2012-06-07 |
| JP2012214429A (en) | 2012-11-08 |
| CN103237796B (en) | 2015-09-09 |
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