CN102216410B - Solid heavy metal processing agent, method for producing same and use of same - Google Patents
Solid heavy metal processing agent, method for producing same and use of same Download PDFInfo
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- CN102216410B CN102216410B CN200980146072.4A CN200980146072A CN102216410B CN 102216410 B CN102216410 B CN 102216410B CN 200980146072 A CN200980146072 A CN 200980146072A CN 102216410 B CN102216410 B CN 102216410B
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Abstract
Disclosed is a solid heavy metal processing agent having excellent economical efficiency in transportation, excellent storage stability (stability of effective component concentration and caking prevention) and excellent heavy metal processing ability, which also has excellent safety in use (no generation of a harmful gas) and excellent reaction selectivity to harmful lead. The heavy metal processing agent is characterized by containing piperazine-N,N'-biscarbodithioic acid sodium hexahydrate and/or piperazine-N,N'-biscarbodithioic acid potassium dihydrate.
Description
Technical field
The invention provides and carry economy, storage stability (effective constituent concentration stabilize, prevent caking) excellence, the security (not producing obnoxious flavour) when use and the solid heavy metal processing agent to harmful plumbous reaction preference excellence.
Background technology
The dithionate of amine is used as the immobilization treatment agent of the heavy metal of flying dust, soil, waste water etc.Conventionally use the aqueous solution of 30～60 % by weight left and right as the dithionate of the amine of heavy metal treatment agent, but the demand of the heavy metal treatment agent to solid (Powdered) increases recently.
The dithionate's who comprises amine in solid excipients solid heavy metal processing agent has been proposed at present.For example have: with respect to 3～30 weight part dithionates, use the method (with reference to patent documentation 1) of 100 weight part alkali metal hydroxides, alkaline earth metal hydroxides; Method (with reference to patent documentation 2) using Calucium Silicate powder as carrier; Use the dithionate's of insoluble transition metal method (with reference to patent documentation 3); Use at high temperature dithionic acid salts solution is sprayed and is dried and the method (with reference to patent documentation 4) of acquisition material; Make to comprise sequestrant in starch and make pulverous material (with reference to patent documentation 5) etc.
But, for existing solid heavy metal processing agent, only there is the low solid heavy metal processing agent of effective constituent concentration in solid.And then, in the time using the heavy metal treatment agent of the existing aqueous solution using during insoluble dithionate is scattered in water as slurry uses, can cause line clogging etc., there is awkward problem.Being dried to obtain in the method for solid heavy metal processing agent by concentrated, spraying, the evaporation of the aqueous solution needs a large amount of energy and uneconomical.In addition, make in the energy expenditure for fear of when the desolventizing, in method that vehicle comprises dithionate, because the ratio of the figuration composition in heavy metal treatment agent is larger, to have the low problem of performance of the chemical reagent of per unit weight.
On the other hand, piperazine-N, N '-bis-dithionates excellent heavy metal treatment agent high as heavy metal processing power, that do not produce obnoxious flavour is known (with reference to patent documentation 6).Existing with piperazine-N, during the flying dust that N '-bis-dithionates are effective constituent is processed, only with piperazine-N, N '-bis-dithionates' the aqueous solution uses.
Only known to solid-state piperazine-N, N '-bis-dithionates, piperazine-the N obtaining by recrystallization in organic solvent, anhydride, tetrahydrate (or 4.5 hydrates) or the hexahydrate of N '-bis-dithionic acid sodium salts (solid) are the colorimetric analysis reagent of trace metal, do not use (with reference to non-patent literature 1～4) as heavy metal treatment agent.
Prior art document
Patent documentation
Patent documentation 1: No. 3895018th, Japanese Patent
Patent documentation 2: No. 2004-97927, TOHKEMY
Patent documentation 3: No. 2003-301165, TOHKEMY
Patent documentation 4: No. 2003-336035, TOHKEMY
Patent documentation 5: No. 2003-113362, TOHKEMY
Patent documentation 6: No. 3391173rd, Japanese Patent
Non-patent literature
Non-patent literature 1: No. 67 23～30 pages (1985) of Mingzhi's university research report
Non-patent literature 2: No. 67 31～36 pages (1985) of Mingzhi's university research report
Non-patent literature 3:Spectrochemica Acta, Vol.40A, pp343-346, (1984)
Non-patent literature 4:CHEMICA ANALITYCZNA, Vol.10, p837-844, (1965)
Summary of the invention
the problem that invention will solve
The object of the present invention is to provide and carry economy excellence, in preservation effective constituent concentration can not change, without excellent storage stabilities such as cakings, while preserving and the time of use does not produce obnoxious flavour and to the high heavy metal treatment agent of plumbous selectivity being harmful to.
for the scheme of dealing with problems
The counterweight metal treatment abilities such as the inventor and usability (economy, storage stability, security) excellent solid heavy metal processing agent conducts in-depth research, found that, at solid-state piperazine-N, in N '-bis-dithionic acid an alkali metal salts, especially piperazine-N, N '-bis-dithionic acid sodium hexahydrate (piperazine-N, N '-biscarbodithioic acid sodium hexahydrate), piperazine-N, N '-bis-dithionic acid potassium dihydrate (piperazine-N, N '-biscarbodithioic acid potassium dihydrate) there is the other forms of hydrate of described salt or the high crystalline not having without hydrate, and in preservation, there is no the problem of changes in weight and caking, the generation of the obnoxious flavoures such as dithiocarbonic anhydride can be reduced to the limit being directly mixed in the in the situation that heavy metal using in containing thing, and especially high to harmful plumbous reaction preference, thereby complete the present invention.
, main idea of the present invention is as follows.
(1) heavy metal treatment agent, is characterized in that, it comprises piperazine-N, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, N '-bis-dithionic acid potassium dihydrates.
(2) according to the heavy metal treatment agent above-mentioned (1) Suo Shu, crystalline piperazine-N that it comprises the X-ray diffraction pattern with table 1, N '-bis-dithionic acid sodium hexahydrates,
[table 1]
(3) according to the heavy metal treatment agent above-mentioned (1) or (2) Suo Shu, it contains piperazine-N more than 70 % by weight, N '-bis-dithionic acid sodium.
(4) according to the heavy metal treatment agent above-mentioned (1) Suo Shu, crystalline piperazine-N that it comprises the X-ray diffraction pattern with table 2, N '-bis-dithionic acid potassium dihydrates,
[table 2]
(5) according to the heavy metal treatment agent above-mentioned (1) or (4) Suo Shu, it contains piperazine-N more than 85 % by weight, N '-bis-dithionic acid potassium.
(6) according to the heavy metal treatment agent described in any one in above-mentioned (1)～(5), it further comprises alkali metal hydroxide and/or alkaline earth metal hydroxides.
(7) a kind of solid-state piperazine-N, the manufacture method of N '-bis-dithionic acid an alkali metal salts, it is characterized in that, make piperazine, dithiocarbonic anhydride and alkali metal hydroxide at piperazine-N, in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, react, separate out piperazine-N, N '-bis-dithionic acid an alkali metal salts, and this salt is separated.
(8) according to the manufacture method above-mentioned (7) Suo Shu, wherein, solid-state piperazine-N, N '-bis-dithionic acid an alkali metal salts are piperazine-N, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, N '-bis-dithionic acid potassium dihydrates.
(9) according to the manufacture method above-mentioned (7) or (8) Suo Shu, wherein, be dissolved with the piperazine-N of piperazine, in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, first add dithiocarbonic anhydride, rear interpolation alkali metal hydroxide.
(10) according to the manufacture method described in any one in above-mentioned (7)～(9), it,, repeatedly alternately to the piperazine-N that is dissolved with piperazine, adds dithiocarbonic anhydride and alkali metal hydroxide in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts.
(11), according to the manufacture method described in any one in above-mentioned (7)～(10), wherein, basic metal is sodium or potassium.
The treatment process of (12) one heavy metal species, is characterized in that, the heavy metal treatment agent described in any one in above-mentioned (1)～(6) is contained to thing with heavy metal and directly mix.
(13) according to the treatment process of the heavy metal above-mentioned (12) Suo Shu, wherein, the total solids composition that contains the heavy metal treatment agent described in any one in thing and above-mentioned (1)～(6) with respect to heavy metal, moisture addition is that 10 % by weight are above and below 50 % by weight.
The treatment process of (14) one heavy metal species, wherein, contains thing by the aqueous solution of the heavy metal treatment agent described in any one being dissolved with in water in above-mentioned (1)～(6) with heavy metal and mixes.
the effect of invention
Piperazine-the N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates is high owing to having the containing ratio of effective constituent of heavy metal processing power, and the changes in weight while preservation, the problem of caking, therefore transporting, excellent storage stability, can directly mix to carry out heavy metal processing by containing thing with heavy metal, when preservation and while use, not produce obnoxious flavour and high to harmful plumbous reaction preference.
Brief description of the drawings
Fig. 1 is piperazine-N, the hexahydrate (A) of N '-bis-dithionic acid sodium, piperazine-N, dihydrate (B) and the piperazine-N of N '-bis-dithionic acid sodium, the X-ray diffractogram without hydrate (C) of N '-bis-dithionic acid sodium.
Fig. 2 is piperazine-N, the dihydrate (D) of N '-bis-dithionic acid potassium, piperazine-N, the X-ray diffractogram without hydrate (E) of N '-bis-dithionic acid potassium.
Fig. 3 is mixing piperazine-N by X-ray diffraction evaluation, N '-bis-dithionic acid sodium without hydrate with lead chloride (F), mix piperazine-N, the dihydrate of N '-bis-dithionic acid sodium is with lead chloride (G) and mix piperazine-N, the figure that when hexahydrate of N '-bis-dithionic acid sodium and lead chloride (H) (all with respect to lead chloride and piperazine-N, the total solids composition of the hydrate of N '-bis-dithionic acid sodium comprises 20 % by weight pure water), lead complex generates.Wherein (I) represents independent piperazine-N, and X-ray diffraction, (J) of N '-bis-dithionic acid lead complexs represent independent piperazine-N, the hexahydrated X-ray diffraction of N '-bis-dithionic acid sodium.
Fig. 4 is mixing piperazine-N by X-ray diffraction evaluation, N '-bis-dithionic acid sodium without hydrate with cupric chloride (K), mix piperazine-N, the dihydrate of N '-bis-dithionic acid sodium is with cupric chloride (L) and mix piperazine-N, the figure that when hexahydrate of N '-bis-dithionic acid sodium and cupric chloride (M) (all with respect to cupric chloride and piperazine-N, the total solids composition of the hydrate of N '-bis-dithionic acid sodium comprises 20 % by weight pure water), copper complex generates.Wherein (N) represents independent piperazine-N, and the copper complex formazan X-ray diffraction of N '-bis-dithionic acids, (O) represent independent piperazine-N, the hexahydrated X-ray diffraction of N '-bis-dithionic acid sodium.
Fig. 5 is mixing piperazine-N by X-ray diffraction evaluation, N '-bis-dithionic acid potassium without hydrate with lead chloride (P), mix piperazine-N, the figure that when dihydrate of N '-bis-dithionic acid potassium and lead chloride (Q) (all with respect to lead chloride and piperazine-N, the total solids composition of the hydrate of N '-bis-dithionic acid potassium comprises 20 % by weight pure water), lead complex generates.Wherein (R) represents independent piperazine-N, and X-ray diffraction, (S) of N '-bis-dithionic acid lead complexs represent independent piperazine-N, the X-ray diffraction of N '-bis-dithionic acid potassium dihydrates.
Fig. 6 is mixing piperazine-N by X-ray diffraction evaluation, N '-bis-dithionic acid potassium without hydrate with cupric chloride (T), mix piperazine-N, the figure that when dihydrate of N '-bis-dithionic acid potassium and cupric chloride (U) (all with respect to cupric chloride and piperazine-N, the total solids composition of the hydrate of N '-bis-dithionic acid potassium comprises 20 % by weight pure water), copper complex generates.Wherein (V) represents independent piperazine-N, and the copper complex formazan X-ray diffraction of N '-bis-dithionic acids, (W) represent independent piperazine-N, the X-ray diffraction of N '-bis-dithionic acid potassium dihydrates.In addition, in each figure, peak intensity when the 2 θ values (unit is degree, deg) when transverse axis (X-axis) represents X-ray diffraction, the longitudinal axis (Y-axis) represent X-ray diffraction, scale (scale) is arbitrarily.
Embodiment
Below to the piperazine-N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates is elaborated.
Particularly preferably be, heavy metal treatment agent of the present invention comprises the piperazine-N that has following main X-ray diffraction peak and have high crystalline, N '-bis-dithionic acid sodium hexahydrates.
[table 3]
In addition, particularly preferably be, heavy metal treatment agent of the present invention comprises the piperazine-N that has following main X-ray diffraction peak and have high crystalline, N '-bis-dithionic acid potassium dihydrates.
[table 4]
There is the piperazine-N of high crystalline, N '-bis-dithionic acid sodium hexahydrates and piperazine-N, N '-bis-dithionic acid potassium dihydrates have following feature: the variation of the moisture content that can not caused by moisture absorption etc. while preservation in atmosphere and cause the effective constituent (piperazine-N in solids component, N '-bis-dithionic acid sodium and piperazine-N, N '-bis-dithionic acid potassium) containing ratio change, in addition, in preservation, be difficult to caking.
Due to piperazine-N, N '-bis-dithionic acid sodium without hydrate, dihydrate or piperazine-N, N '-bis-dithionic acid potassium can absorb the moisture in atmosphere without hydrate, thereby the weight ratio of the effective constituent of heavy metal treatment agent can change, therefore need to before processing for heavy metal, confirm the validity constituent concentration.On the other hand, due to piperazine-N of the present invention, N '-bis-dithionic acid sodium hexahydrates and piperazine-N, the changes in weight that N '-bis-dithionic acid potassium dihydrates do not cause due to the moisture absorbing in atmosphere therefore need to not confirm the validity constituent concentration in the time of each use.
Of the present invention with piperazine-N, in the heavy metal treatment agent that N '-bis-dithionic acid sodium hexahydrates are effective constituent, piperazine-N, more than the content of N '-bis-dithionic acid sodium is preferably 60 % by weight (being 83 % by weight for hexahydrate crystal), more preferably more than 70 % by weight (being 96.8 % by weight for hexahydrate crystal).All in hexahydrated situation at the crystal powder of heavy metal treatment agent, piperazine-N, the content of N '-bis-dithionic acid sodium is 72.3 % by weight.
In addition, of the present invention with piperazine-N, in the heavy metal treatment agent that N '-bis-dithionic acid potassium dihydrates are effective constituent, piperazine-N, more than the content of N '-bis-dithionic acid potassium is preferably 70 % by weight (being 78 % by weight for dihydrochloride dihydrate crystal), more preferably more than 85 % by weight (being 94.7 % by weight for dihydrochloride dihydrate crystal).All dihydrate at the crystal powder of heavy metal treatment agent, piperazine-N, the content of N '-bis-dithionic acid potassium is 89.7 % by weight.
Piperazine-the N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates is not heavy metal treatment agent as existing solid heavy metal processing agent, that the dithionate of amine and other solid salts (carrier) are mixed, but therefore pure crystal has high this advantage of containing ratio of the effective constituent in heavy metal treatment agent.
In addition, even include in heavy metal treatment agent of the present invention the hydrate of a part without hydrate or other its forms, because the surface part of heavy metal treatment agent powder particle is made up of hydrate crystal of the present invention, therefore also can bring into play above-mentioned effect of the present invention.
Piperazine-the N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates further has following feature: in the time of the preservation of chemical reagent and containing thing with heavy metal, mix while using and do not produce obnoxious flavour.
Use solid-state piperazine-N, N '-bis-dithionic acid sodium without hydrate, dihydrate or piperazine-N, the solid without hydrate of N '-bis-dithionic acid potassium is compared with using their situation of the aqueous solution, the generation of dithiocarbonic anhydride has the trend of increase.On the other hand, piperazine-N of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the problem that the generation of N '-dithiocarbonic anhydride that bis-dithionic acid potassium dihydrates are not harmful to increases.
And then, piperazine-the N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates has following feature: high to harmful plumbous reaction preference, can process harmful being fixed of lead efficiently.
For example, the thing of piperazine-N in the heavy metal processing that contains to(for) heavy metal, N '-bis-dithionic acid sodium hexahydrates, be in the situation of 20 % by weight with respect to total solids composition (flying dust+heavy metal treatment agent) moisture addition, with dihydrate, without it,, to plumbous reaction preference (with to copper comparison) height, is more than 5 times compared with hydrate.In addition, even if also maintained the dominance to plumbous reaction preference in the situation that moisture addition increases.
Similarly, the thing of piperazine-N in the heavy metal processing that contains to(for) heavy metal, N '-bis-dithionic acid potassium dihydrates, be in the situation of 20 % by weight with respect to total solids composition (flying dust+heavy metal treatment agent) moisture addition, with compared with hydrate its to plumbous reaction preference (with to copper comparison) height, be more than 5 times, even if also maintained the dominance to plumbous reaction preference in the situation that moisture addition increases.
In the heavy metal that uses heavy metal treatment agent of the present invention is processed, the total solids composition that contains thing and heavy metal treatment agent with respect to heavy metal, moisture addition (% by weight) has no particular limits, and is preferably that 10 % by weight are above and 50 % by weight are following, to be particularly preferably 20 % by weight above and below 40 % by weight.
For example, in the processing of the flying dust that contains thing as heavy metal, if crossing, moisture addition can form at most huge bulk or pulp-like, processing grey operation (handling) and become difficulty, is therefore to process under the state of scope of 20～40 % by weight with respect to solids component making moisture addition conventionally.Therefore, piperazine-the N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates can be brought into play the high reaction preference to lead in the flying dust of common moisture addition is processed.
In order to improve stability, can make heavy metal treatment agent of the present invention further contain alkali metal hydroxide, alkaline earth metal hydroxides.These alkali compositions are not vehicle (or carrier) as heavy metal treatment agent and using, therefore with respect to piperazine-N, N '-bis-dithionic acid sodium or piperazine-N, N '-bis-dithionic acid potassium compositions, its content in 0.01～5 % by weight, be particularly enough in the scope of 0.1～2 % by weight.
As the alkali metal hydroxide using, preferably sodium hydroxide, potassium hydroxide, as the alkaline earth metal hydroxides using, preferably magnesium hydroxide, calcium hydroxide.
Piperazine-the N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the manufacture method of the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates has no particular limits, and can manufacture by following manufacture method.
Piperazine-N, N '-bis-dithionic acid sodium hexahydrates or piperazine-N, N '-bis-dithionic acid potassium dihydrates can be manufactured as follows: make piperazine, dithiocarbonic anhydride and basic metal (sodium or potassium) oxyhydroxide at piperazine-N, in the saturated aqueous solution of N '-bis-dithionic acid basic metal (sodium or potassium), react, separate out piperazine-N, the two dithionic acid an alkali metal salts of N ' (sodium salt or sylvite) also separate this salt from saturated aqueous solution.
For piperazine and piperazine-N, N '-bis-dithionic acid sodium, piperazine to the solubleness of water higher (piperazine be approximately 1.8 moles/L, piperazine-N, the solubleness of N '-bis-dithionic acid sodium is 0.9 mole/L (approximately 25 % by weight)), even therefore at piperazine-N, in the saturated solution of N '-bis-dithionic acid sodium salts, piperazine also can further dissolve.
Similarly, for piperazine and piperazine-N, N '-bis-dithionic acid potassium, piperazine to the solubleness of water higher (piperazine be approximately 1.8 moles/L, piperazine-N, N '-bis-dithionic acid sylvite is 1.3 moles/L (approximately 40 % by weight)), even therefore at piperazine-N, in the saturated solution of N '-bis-dithionic acid sylvite, piperazine also can further dissolve.
Piperazine-the N generating, N '-bis-dithionic acid sodium or piperazine-N, the viscosity of the saturated aqueous solution of N '-bis-dithionic acid potassium is low, and therefore reactive (usability while reaction continuously) is also excellent.
On the other hand, due at piperazine-N, the dithionate of the amine beyond N '-bis-dithionates, such as in the dithionate's of tetren, diethylenetriamine, polymine etc. supersaturated solution, do not separate out solid, become the aqueous solution that viscosity is high, the dithionate who therefore obtains solid-state amine is difficult.
In manufacture method of the present invention, preferably, by piperazine dissolved in piperazine-N, in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts (sodium salt or sylvite), and first add dithiocarbonic anhydride, rear interpolation alkali metal hydroxide (sodium hydroxide or potassium hydroxide).At piperazine-N, in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, make piperazine and dithiocarbonic anhydride reaction under the state of alkali metal hydroxide surplus time, generate sometimes gelatinous by product, be difficult to carry out successive reaction.
And then, in the method for the invention, can, by repeatedly alternately to piperazine-N, in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, add piperazine, dithiocarbonic anhydride and alkali metal hydroxide, manufacture continuously solid-state piperazine-N, N '-bis-dithionic acid an alkali metal salts.
As particularly preferred embodiment, can illustrate following method: at piperazine-N, in reaction in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, piperazine, dithiocarbonic anhydride and alkali metal hydroxide, first make piperazine dissolved in piperazine-N, the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, then maintains dithiocarbonic anhydride with respect to the state of alkali metal hydroxide surplus while makes to react and carry out.In the case of reacting than the state of alkali metal hydroxide surplus with dithiocarbonic anhydride, although temporarily separate out solid-state piperazine-N, N '-bis-dithionic acids, but compared with first adding the situation of alkali metal hydroxide, the viscosity of the aqueous solution is low, reactivity and operability are good, finally can obtain pure piperazine-N, the crystal of N '-bis-dithionic acid an alkali metal salts.Particularly preferably be, respectively the interpolation of dithiocarbonic anhydride and alkali metal hydroxide be divided into the methods such as 2 above or poor interpolations simultaneously of setup times.
For the reaction of the piperazine in the aqueous solution, dithiocarbonic anhydride and alkali metal hydroxide, by-product piperazine-N sometimes, piperazine-N-dithionic acid an alkali metal salt beyond N '-bis-dithionic acid an alkali metal salts, thiocarbonate, the piperazine of remained unreacted sometimes.Due to Jin Youyige functional group thereby low piperazine-N-dithionic acid an alkali metal salt and the piperazine-N of heavy metal processing power, it is high that N '-bis-dithionic acid an alkali metal salts are compared solvability, therefore in the method for the invention, can optionally manufacture only piperazine-N that heavy metal processing power is high, the crystal of N '-bis-dithionic acid an alkali metal salts.
Due to piperazine and thiocarbonate, solubleness is high too, and therefore residual in the aqueous solution, with piperazine-N, N '-bis-dithionic acid an alkali metal salts can separate.In the method for utilizing concentrated, organic solvent extraction, there is piperazine-N-dithionic acid an alkali metal salt, piperazine and thiocarbonate and piperazine-N, the problem that N '-bis-dithionic acid an alkali metal salts are separated out simultaneously, but in the method for the invention, can be used as crystal and optionally manufacture piperazine-N that heavy metal processing power is high, N '-bis-dithionic acid an alkali metal salt compositions.
In the present invention, the drying means of the crystal of separating out has no particular limits, as long as obtaining the method for hydrate of the present invention (for piperazine-N, N '-bis-dithionic acid sodium salts are hexahydrate, for piperazine-N, N '-bis-dithionic acid potassium is dihydrate).Even if caused crystallinity decline by over-drying at the crystal of separating out, also can obtain by further carrying out hydration-treated in the atmosphere that contains moisture the crystal of hydrate of the present invention.The crystallization being caused by dried hydration preferably carries out in pulverizing or forced-flow.
By by the piperazine-N that comprises of the present invention, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates mixes with the soil that contains heavy metal, waste water, waste, lime-ash etc., can prevent the stripping of heavy metal.Using method in the immobilization of heavy metals processing of heavy metal treatment agent of the present invention can be suitable for the common method same with other heavy metal treatment agents, as required, can be in heavy metal treatment agent suitably the pH adjusting agent such as mixing water, mixed alkali metal oxyhydroxide, iron(ic) chloride use.
Comprise piperazine-N, N '-bis-dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-bis-dithionic acid potassium dihydrates can contain thing with heavy metal and mix use after being dissolved in the water, preferably, directly mix to use with water simultaneously, particularly preferably be, after directly mixing, add water and use.
Embodiment
With embodiment, invention is described below, but the present invention is not limited to these embodiment.
Embodiment 1
61.01g piperazine is dissolved in 212.4g pure water at 40 DEG C, then in stream of nitrogen gas, while stirring the aqueous sodium hydroxide solution of 106.77g dithiocarbonic anhydride and 119.82g 48 % by weight is divided into respectively to 4 parts and carries out dropping alternately.Dropping finishes rear acquisition and has separated out piperazine-N, the pulp solution of N '-bis-dithionic acid sodium.Leach the piperazine-N separating out, N '-bis-dithionic acid sodium, the moisture except attachment removal in vacuum drier is also dry.
Gained piperazine-N, the thermoanalytical result of N '-bis-dithionic acid sodium is hexahydrate, as shown in Figure 1, it has high crystalline to X-ray diffraction pattern.
By gained piperazine-N, N '-bis-dithionic acid sodium hexahydrates are dissolved in pure water and carry out
13c-NMR (nuclear magnetic resonance spectroscopy(NMR spectroscopy), Nuclear Magnetic Resonance) measures, and result does not detect piperazine and the two dithionic acid sodium of piperazine-N-.
Embodiment 2
To the piperazine-N that leached in 250g embodiment 1, filtrate (piperazine-the N of N '-bis-dithionic acid sodium, the saturated aqueous solution of N '-bis-dithionic acid sodium) in further add 42.57g piperazine and 50.73g pure water, at 40 DEG C, dissolve, in stream of nitrogen gas, while stirring 74.50g dithiocarbonic anhydride and 82.19g 48 % by weight aqueous sodium hydroxide solutions are divided into respectively to 2 parts and replace dropping.Dropping finishes rear acquisition and has separated out piperazine-N, the pulp solution of N '-bis-dithionic acid sodium.
Reuse saturated solution, confirm to have obtained piperazine-N, N '-bis-dithionic acid sodium hexahydrates.
Comparative example 1
Further in moisture eliminator, at 50 DEG C and 100 DEG C, the hexahydrate of embodiment 1 is dried, obtains respectively dihydrate and without hydrate.
X-ray diffraction pattern is shown in Fig. 1.Dihydrate and low without the crystallinity of hydrate.
Comparative example 2
Replace piperazine with tetren, and tetren is that 88.11g, pure water are that 128.11g, dithiocarbonic anhydride are that 127.50g, 48 % by weight aqueous sodium hydroxide solutions are 156.28g, in addition, carry out the operation identical with embodiment 1, do not obtain solid-state dithionate.
Embodiment 3
Use 68.45g piperazine, 123.58g pure water, 121.01g dithiocarbonic anhydride and 186.96g48 % by weight potassium hydroxide aqueous solution, make piperazine be dissolved in pure water at 40 DEG C, then in stream of nitrogen gas, while stirring dithiocarbonic anhydride and 48 % by weight potassium hydroxide are divided into respectively to 4 parts and replace dropping.Dropping finishes rear acquisition and has separated out piperazine-N, the pulp solution of N '-bis-dithionic acid potassium dihydrates.Leach the piperazine-N separating out, N '-bis-dithionic acid potassium removes the moisture of attachment removal and is dried in vacuum drier.
Gained piperazine-N, the thermoanalytical result of N '-bis-dithionic acid potassium is dihydrate, as shown in Figure 2, it has high crystalline to X-ray diffraction pattern.
By gained piperazine-N, N '-bis-dithionic acid potassium dihydrates are dissolved in pure water and carry out
13c-NMR measures, and result does not detect piperazine and the two dithionic acid potassium of piperazine-N-.
Embodiment 4
To the piperazine-N that leached in 300g embodiment 3, filtrate (piperazine-the N of N '-bis-dithionic acid potassium, the saturated aqueous solution of N '-bis-dithionic acid potassium) in further add 30.42g piperazine and 31.00g pure water, at 40 DEG C, dissolve, in stream of nitrogen gas, while stirring 53.78g dithiocarbonic anhydride and 84.80g 48 % by weight potassium hydroxide aqueous solutions are divided into respectively to 2 parts and replace dropping.Dropping finishes rear acquisition and has separated out piperazine-N, the pulp solution of N '-bis-dithionic acid potassium.
Reuse saturated solution, confirm to have obtained piperazine-N, N '-bis-dithionic acid potassium dihydrates.
Comparative example 3
Further in moisture eliminator, at 100 DEG C, the dihydrate of embodiment 3 is dried, obtains without hydrate.As shown in Figure 2, different from dihydrate crystallinity without hydrate, and its crystallinity is low.
(storage stability is evaluated 1 (changes in weight))
By the piperazine-N obtaining in embodiment 1 and comparative example 1, hexahydrate, the dihydrate of N '-bis-dithionic acid sodium and placing in atmosphere without hydrate, the rheological parameters' change with time that gravimetry changes.The results are shown in table 5.
[table 5]
| Initial weight g | Weight g after one month | |
| Embodiment 1 (sodium salt 6 hydrates) | 5.00 | 5.00 |
| Comparative example 1 (sodium salt 2 hydrates) | 5.00 | 5.99 |
| Comparative example 1 (sodium salt is without hydrate) | 5.00 | 6.71 |
Confirm, piperazine-N, N '-bis-dithionic acid sodium without hydrate, dihydrate through time there is changes in weight, and piperazine-N, there is not changes in weight in N '-bis-dithionic acid sodium hexahydrates, preserves stable in atmosphere.
In addition, after placing in atmosphere, unconfirmed to hexahydrate caking, and confirm dihydrate and decline, be attached on container without the mobility of hydrate.
Similarly, by the piperazine-N obtaining in embodiment 3 and comparative example 3, N '-bis-dithionic acid potassium dihydrates and placing in atmosphere without hydrate, the rheological parameters' change with time that gravimetry changes.The results are shown in table 6.
[table 6]
| Initial weight g | Weight g after one month | |
| Embodiment 3 (sylvite 2 hydrates) | 5.00 | 5.00 |
| Comparative example 3 (sylvite is without hydrate) | 5.00 | 5.56 |
Confirm, piperazine-N, N '-there is changes in weight without hydrate in bis-dithionic acid potassium, and piperazine-N, there is not changes in weight in N '-bis-dithionic acid potassium dihydrates, preserves stable in atmosphere.
After placing in atmosphere, unconfirmed to piperazine-N, N '-bis-dithionic acid potassium dihydrate cakings, decline, are attached on container and confirm without the mobility of hydrate.
(heavy metal is processed test)
To be respectively with respect to 50 weight part flying dust A (Pb=2500ppm) piperazine-N of the embodiment 1 of 0.5 weight part (converting without hydrate), piperazine-N of N '-bis-dithionic acid sodium hexahydrates, embodiment 3, N '-bis-dithionic acid potassium dihydrates are dissolved in separately in 25 weight parts waters and are mixing with flying dust A.In addition, to be piperazine-N of the embodiment 1 of 0.5 weight part (converting without hydrate) with respect to 50 weight part flying dust A (Pb=2500ppm), N '-bis-dithionic acid sodium hexahydrates directly make an addition to flying dust A, and the water that then adds 25 weight parts carries out mixing.,, according to No. 13rd, Environmental Agency's bulletin test (clear and 48 years), each mixing thing is carried out to dissolution test thereafter.
Plumbous stripping is all less than 0.05ppm, meets environmental criteria.
(eudiometry 1)
At Tedlar sampler bag (Tedlar Bag, volume 1L) in put into 2.74g piperazine-N, the hexahydrate of N '-bis-dithionic acid sodium (is pressed piperazine-N, the N '-bis-dithionic acid sodium meter that converts is equivalent to 2g) and load 500mL air, at room temperature and 65 DEG C, place respectively 1 hour.After placement, the Carbon Disulfide of the upper space in Tedlar sampler bag (head space) is measured with detector tube.
In order to compare, filling piperazine-N, the dihydrate of N '-bis-dithionic acid sodium and without hydrate (press piperazine-N, N '-bis-dithionic acid sodium convert score not with hexahydrate equivalent) also in the same manner as described above Carbon Disulfide is measured.The results are shown in table 7.
At piperazine-N, the dihydrate of N '-bis-dithionic acid sodium and without the generation that confirms dithiocarbonic anhydride in hydrate, and at piperazine-N, in N '-bis-dithionic acid sodium hexahydrates, fail to detect dithiocarbonic anhydride (ND) or dithiocarbonic anhydride few.
[table 7]
Similarly in Tedlar sampler bag (volume 1L), put into 2.2g piperazine-N, N '-bis-dithionic acid potassium dihydrates (are pressed piperazine-N, the N '-bis-dithionic acid potassium meter that converts is equivalent to 2.0g) and load 500mL air, at room temperature and 65 DEG C, place respectively 1 hour.After placement, the Carbon Disulfide of the upper space with detector tube to Tedlar sampler bag is measured.
In order to compare, add piperazine-N, also in the same manner as described above Carbon Disulfide being measured without hydrate (press piperazine-N, N '-bis-dithionic acid potassium converts score not and dihydrate equivalent) of N '-bis-dithionic acid potassium.The results are shown in table 8.
At piperazine-N, N '-bis-dithionic acid potassium is without the generation that confirms dithiocarbonic anhydride in hydrate, and at piperazine-N, in N '-bis-dithionic acid potassium dihydrates, fails to detect dithiocarbonic anhydride (ND).
[table 8]
(eudiometry 2)
In Tedlar sampler bag (volume 1L), load 30g flying dust B (Pb=2700ppm), be the pure water of 35 % by weight and the piperazine-N of 0.74 % by weight with respect to flying dust B, N '-bis-dithionic acid sodium hexahydrates, filling 500mL air after mixing is placed respectively 1 hour at room temperature and 65 DEG C.After placement, hydrogen sulfide and Carbon Disulfide with detector tube to the upper space in Tedlar sampler bag are measured.
Add 30g flying dust C (Pb=9800ppm), be the pure water of 20 % by weight and the piperazine-N of 3.0 % by weight with respect to flying dust C, N '-bis-dithionic acid sodium hexahydrates are also similarly processed with above-mentioned, then carry out eudiometry.
In order to compare, similarly add piperazine-N to flying dust C with above-mentioned, N '-bis-dithionic acid sodium without hydrate and dihydrate (press piperazine-N, N '-bis-dithionic acid sodium converts score not and hexahydrate equivalent), and this situation is carried out to the mensuration of gas concentration.The results are shown in table 9,10.
All fail to detect hydrogen sulfide.On the other hand, at piperazine-N, in N '-bis-dithionic acid sodium hexahydrates, the generation of dithiocarbonic anhydride is less than 1ppm, at piperazine-N, and N '-bis-dithionic acid sodium dihydrates and without the generation (increase) that confirms dithiocarbonic anhydride in hydrate.
[table 9]
[table 10]
Similarly, in Tedlar sampler bag (volume 1L), add 30g flying dust B (Pb=2700ppm), be the pure water of 35 % by weight and the piperazine-N of 0.7 % by weight with respect to flying dust B, N '-bis-dithionic acid potassium dihydrates, after mixing, filling 500mL air heats 1 hour at 65 DEG C.After heating, hydrogen sulfide and the Carbon Disulfide of the upper space with detector tube to Tedlar sampler bag are measured.
Add 30g flying dust C (Pb=9800ppm), be the pure water of 20 % by weight and the piperazine-N of 1.1 % by weight with respect to flying dust C, N '-bis-dithionic acid potassium dihydrates are also similarly processed with above-mentioned, then carry out eudiometry.
Each the results are shown in table 11.All fail in either event to detect hydrogen sulfide and dithiocarbonic anhydride.
[table 11]
(to plumbous reaction preference)
Will be by piperazine-N, N '-bis-dithionic acid sodium compositions convert and count is respectively piperazine-N of 10g, the hexahydrate of N '-bis-dithionic acid sodium, dihydrate and without hydrate respectively with 9.8g lead chloride and 4.8g cupric chloride and pure water (with respect to lead chloride or cupric chloride and piperazine-N, the total solids composition of the hydrate of N '-bis-dithionic acid sodium is 20 % by weight and 30 % by weight) mix, by X-ray diffraction, the generation that mixes rear each metal complex is measured.
For lead complex, copper complex and piperazine-N, 9.4 ° (from peaks (a) of lead complex) of diffraction angle of N '-bis-dithionic acid sodium, 12.9 ° (from copper complex formazan peak (b)) and 21.3 ° are (from piperazine-N, the peak (c) of N '-bis-dithionic acid sodium compositions) each diffracted intensity, the ratio that to establish a/c be copper reactivity (2), (1)/(2) for plumbous reactive (1), b/c is plumbous selectivity (3).Moisture content is to the results are shown in table 12,13 in the situation of 20 % by weight and 30 % by weight.
With piperazine-N, the dihydrate of N '-bis-dithionic acid sodium with compare without hydrate, piperazine-N, N '-bis-dithionic acid sodium hexahydrates are high to plumbous selectivity, and its trend is: it is more few more remarkable that heavy metal contains moisture content in thing (comprising heavy metal treatment agent).
[table 12]
(moisture 20 % by weight)
[table 13]
(moisture 30 % by weight)
Similarly, will be by piperazine-N, N '-bis-dithionic acid potassium compositions convert and count is respectively piperazine-N of 10g, the dihydrate of N '-bis-dithionic acid potassium and without hydrate respectively with 8.8g lead chloride and 4.3g cupric chloride and pure water (wherein, with respect to lead chloride or cupric chloride and piperazine-N, the total solids composition pure water of the hydrate of N '-bis-dithionic acid potassium is 20 % by weight and 30 % by weight) mix, by X-ray diffraction, the generation that mixes rear each metal complex is measured.
For lead complex, copper complex and piperazine-N, 9.4 ° (from peaks (a) of lead complex) of diffraction angle of N '-bis-dithionic acid potassium, 15.1 ° (from copper complex formazan peak (b)) and 33.1 ° are (from piperazine-N, the peak (c) of N '-bis-dithionic acid potassium compositions) each diffracted intensity, the ratio that to establish a/c be copper reactivity (2), (1)/(2) for plumbous reactive (1), b/c is plumbous selectivity (3).The in the situation that of moisture content 20 % by weight and 30 % by weight, the results are shown in table 14,15.
With piperazine-N, the comparing without hydrate of N '-bis-dithionic acid potassium, piperazine-N, N '-bis-dithionic acid potassium dihydrates are high to plumbous reaction preference, and its trend is: it is more few more remarkable that heavy metal contains moisture content in thing.
[table 14]
(moisture 20 % by weight)
[table 15]
(moisture 30 % by weight)
utilizability in industry
Heavy metal treatment agent of the present invention can be used for the immobilization processing that heavy metal contains heavy metal in thing, particularly can be aptly for the heavy metal processing of the flying dust that comprises a large amount of lead.
In addition, quote the full content of specification sheets, claim, Figure of description and the summary of No. 2009-162099, No. 2009-152158, the Japanese patent application of Japanese patent application application on June 26th, No. 2008-294911 1 of Japanese patent application application on November 18th, No. 2008-294910 1 of on November 18th, 2008 application and the Japanese patent application of application on July 8th, 2009 at this, and be incorporated to as the disclosure of specification sheets of the present invention.
Claims (10)
1. a heavy metal treatment agent, is characterized in that, it comprises piperazine-N, N '-bis-dithionic acid potassium dihydrates, or comprise piperazine-N, and N '-bis-dithionic acid sodium hexahydrates and piperazine-N, N '-bis-dithionic acid potassium dihydrates, wherein
Described piperazine-N, N '-bis-dithionic acid sodium hexahydrates have the X-ray diffractogram as shown in (A) in Fig. 1;
Described piperazine-N, N '-bis-dithionic acid potassium dihydrates have the X-ray diffractogram as shown in (D) in Fig. 2.
2. heavy metal treatment agent according to claim 1, it contains piperazine-N more than 70 % by weight, N '-bis-dithionic acid sodium.
3. heavy metal treatment agent according to claim 1, it contains piperazine-N more than 85 % by weight, N '-bis-dithionic acid potassium.
4. heavy metal treatment agent according to claim 1, it further comprises alkali metal hydroxide and/or alkaline earth metal hydroxides.
5. according to the manufacture method of the heavy metal treatment agent described in claim 1-4 any one, it is characterized in that, make piperazine, dithiocarbonic anhydride and alkali metal hydroxide at piperazine-N, in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts, react, separate out piperazine-N, N '-bis-dithionic acid an alkali metal salts, and this salt is separated.
6. manufacture method according to claim 5, wherein, is being dissolved with the piperazine-N of piperazine, first adds dithiocarbonic anhydride, rear interpolation alkali metal hydroxide in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts.
7. according to the manufacture method described in claim 5 or 6, it,, repeatedly alternately to the piperazine-N that is dissolved with piperazine, adds dithiocarbonic anhydride and alkali metal hydroxide in the saturated aqueous solution of N '-bis-dithionic acid an alkali metal salts.
8. the treatment process of a heavy metal species, is characterized in that, the heavy metal treatment agent described in any one in claim 1-4 is contained to thing with heavy metal and directly mix.
9. the treatment process of heavy metal according to claim 8, wherein, the total solids composition that contains the heavy metal treatment agent described in any one in thing and claim 1-4 with respect to heavy metal, moisture addition is that 10 % by weight are above and below 50 % by weight.
10. the treatment process of a heavy metal species, wherein, contains thing by the aqueous solution of the heavy metal treatment agent described in any one being dissolved with in water in claim 1-4 with heavy metal and mixes.
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| JP2008294911 | 2008-11-18 | ||
| JP2008294910 | 2008-11-18 | ||
| JP2008-294911 | 2008-11-18 | ||
| JP2008-294910 | 2008-11-18 | ||
| JP2009-152158 | 2009-06-26 | ||
| JP2009152158A JP5439979B2 (en) | 2008-11-18 | 2009-06-26 | Solid heavy metal treating agent, production method and use thereof |
| JP2009162099A JP5439990B2 (en) | 2008-11-18 | 2009-07-08 | Solid heavy metal treating agent, production method and use thereof |
| JP2009-162099 | 2009-07-08 | ||
| PCT/JP2009/069500 WO2010058774A1 (en) | 2008-11-18 | 2009-11-17 | Solid heavy metal processing agent, method for producing same and use of same |
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| CN103933697B (en) * | 2014-04-08 | 2017-04-12 | 同济大学 | Compound stabilizer for stabilizing heavy metals in fly ash generated by waste incineration and preparation method of compound stabilizer |
| CN111773607A (en) * | 2020-08-05 | 2020-10-16 | 成都赢纳环保科技有限公司 | Heavy metal chelating agent and solid product thereof |
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