CN102216410A - 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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- CN102216410A CN102216410A CN2009801460724A CN200980146072A CN102216410A CN 102216410 A CN102216410 A CN 102216410A CN 2009801460724 A CN2009801460724 A CN 2009801460724A CN 200980146072 A CN200980146072 A CN 200980146072A CN 102216410 A CN102216410 A CN 102216410A
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- piperazine
- dithionic acid
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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 during use (not producing obnoxious flavour) and the solid-state heavy metal treatment agent of the reaction preference excellence of deleterious lead.
Background technology
The dithionate of amine is used as the immobilization treatment agent of the heavy metal of flying dust, soil, waste water etc.Usually use the aqueous solution about 30～60 weight % as the dithionate of the amine of heavy metal treatment agent, yet the demand to the heavy metal treatment agent of solid (Powdered) increases recently.
At present, proposed in solid excipients, to comprise the dithionate's of amine solid-state heavy metal treatment agent.For example have:, use the method (with reference to patent documentation 1) of 100 weight part alkali metal hydroxides, alkaline earth metal hydroxides with respect to 3～30 weight part dithionates; With the method (with reference to patent documentation 2) of Calucium Silicate powder as carrier; Use the dithionate's of insoluble transition metal method (with reference to patent documentation 3); Use the method (with reference to patent documentation 4) of at high temperature the dithionic acid salts solution being carried out spraying drying and obtaining material; Make and comprise sequestrant in the starch and make pulverous material (with reference to patent documentation 5) etc.
But,, only have the low solid-state heavy metal treatment agent of effective constituent concentration in the solid for existing solid-state heavy metal treatment agent.And then, when using the heavy metal treatment agent of the existing aqueous solution, insoluble dithionate is scattered under the situation about using as slurry in the water, can cause line clogging etc., have awkward problem.By concentrate, spraying drying obtaining in the method for solid-state heavy metal treatment agent, the evaporation of the aqueous solution needs lot of energy and uneconomical.In addition, vehicle being comprised in dithionate's the method,, have the low problem of performance of the chemical reagent of per unit weight because the ratio of the figuration composition in the heavy metal treatment agent is bigger for fear of removing the energy expenditure when desolvating.
On the other hand, piperazine-N, N '-two dithionates are known (with reference to patent documentations 6) as heavy metal processing power height, the excellent heavy metal treatment agent that do not produce obnoxious flavour.Existing with piperazine-N, N '-two dithionates are that only with piperazine-N, N '-two dithionates' the aqueous solution used during the flying dust of effective constituent was handled.
Only known to solid-state piperazine-N, N '-two dithionates, piperazine-the N that obtains by recrystallization in organic solvent, the anhydride of N '-two dithionic acid sodium salts (solid), tetrahydrate (or 4.5 hydrates) or hexahydrate are the colorimetric analysis reagent of trace metal, do not use (with reference to non-patent literature 1～4) as heavy metal treatment agent.
The prior art document
Patent documentation
Patent documentation 1: No. the 3895018th, Japanese Patent
Patent documentation 2: TOHKEMY 2004-97927 number
Patent documentation 3: TOHKEMY 2003-301165 number
Patent documentation 4: TOHKEMY 2003-336035 number
Patent documentation 5: TOHKEMY 2003-113362 number
Patent documentation 6: No. the 3391173rd, Japanese Patent
Non-patent literature
Non-patent literature 1: Mingzhi's university research is reported 23～30 pages (1985) No. 67
Non-patent literature 2: Mingzhi's university research is reported 31～36 pages (1985) No. 67
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 the economy excellence, do not produce when effective constituent concentration can not change, not have excellent storage stability, preservation such as caking in preservation and during use obnoxious flavour and the heavy metal treatment agent high to the selectivity of deleterious lead.
The scheme that is used to deal with problems
The inventor waits counterweight metal treatment ability and usability (economy, storage stability, security) You Yi solid-state heavy metal treatment agent has carried out deep research, found that, at solid-state piperazine-N, in N '-two dithionic acid an alkali metal salts, especially piperazine-N, N '-two dithionic acid sodium hexahydrate (piperazine-N, N '-biscarbodithioic acid sodium hexahydrate), piperazine-N, N '-two dithionic acid potassium dihydrate (piperazine-N, N '-biscarbodithioic acid potassium dihydrate) has the other forms of hydrate of described salt or do not have the high crystalline that hydrate does not have, and the problem that in preservation, does not have changes in weight and caking, contain under the situation about using in the thing and the generation of obnoxious flavoures such as dithiocarbonic anhydride can be reduced to the limit directly being mixed in heavy metal, and, thereby finished the present invention especially to the reaction preference height of deleterious lead.
That is, main idea of the present invention is as follows.
(1) a kind of heavy metal treatment agent is characterized in that, it comprises piperazine-N, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, N '-two dithionic acid potassium dihydrates.
(2) according to above-mentioned (1) described heavy metal treatment agent, it comprises the crystalline piperazine-N of the X-ray diffraction pattern with table 1, N '-two dithionic acid sodium hexahydrates,
[table 1]
(3) according to above-mentioned (1) or (2) described heavy metal treatment agent, it contains the above piperazine-N of 70 weight %, N '-two dithionic acid sodium.
(4) according to above-mentioned (1) described heavy metal treatment agent, it comprises the crystalline piperazine-N of the X-ray diffraction pattern with table 2, N '-two dithionic acid potassium dihydrates,
[table 2]
(5) according to above-mentioned (1) or (4) described heavy metal treatment agent, it contains the above piperazine-N of 85 weight %, N '-two dithionic acid potassium.
(6) according to each the described heavy metal treatment agent 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 '-two dithionic acid an alkali metal salts, it is characterized in that, make piperazine, dithiocarbonic anhydride and alkali metal hydroxide at piperazine-N, react in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts, separate out piperazine-N, N '-two dithionic acid an alkali metal salts, and with this salt separation.
(8) according to above-mentioned (7) described manufacture method, wherein, solid-state piperazine-N, N '-two dithionic acid an alkali metal salts are piperazine-N, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, N '-two dithionic acid potassium dihydrates.
(9) according to above-mentioned (7) or (8) described manufacture method, wherein, be dissolved with the piperazine-N of piperazine, add dithiocarbonic anhydride in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts earlier, alkali metal hydroxide is added in the back.
(10) according to each the described manufacture method in above-mentioned (7)～(9), it adds dithiocarbonic anhydride and alkali metal hydroxide repeatedly alternately to the piperazine-N that is dissolved with piperazine in saturated aqueous solution of N '-two dithionic acid an alkali metal salts.
(11) according to each the described manufacture method 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, each the described heavy metal treatment agent in above-mentioned (1)～(6) is contained thing with heavy metal directly mix.
(13) according to the treatment process of above-mentioned (12) described heavy metal, wherein, contain the total solids composition of each the described heavy metal treatment agent in thing and above-mentioned (1)～(6) with respect to heavy metal, the moisture addition is that 10 weight % are above and below the 50 weight %.
The treatment process of (14) one heavy metal species, wherein, the aqueous solution that will be dissolved with each the described heavy metal treatment agent in above-mentioned (1)～(6) in water contains thing with heavy metal and mixes.
The effect of invention
Piperazine-the N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates is because the containing ratio height with effective constituent of heavy metal processing power, and the changes in weight when not preserving, the problem of caking, therefore conveying property, excellent storage stability, can directly mix and carry out heavy metal and handle by containing thing, not produce obnoxious flavour during preservation and when using and the reaction preference height of deleterious lead with heavy metal.
Description of drawings
Fig. 1 is piperazine-N, the hexahydrate (A) of N '-two dithionic acid sodium, piperazine-N, the dihydrate (B) and the piperazine-N of N '-two dithionic acid sodium, the X-ray diffractogram of the no hydrate (C) of N '-two dithionic acid sodium.
Fig. 2 is piperazine-N, the dihydrate (D) of N '-two dithionic acid potassium, piperazine-N, the X-ray diffractogram of the no hydrate (E) of N '-two dithionic acid potassium.
Fig. 3 is mixing piperazine-N by the X-ray diffraction evaluation, the no hydrate of N '-two dithionic acid sodium with lead chloride (F), mix piperazine-N, the dihydrate of N '-two dithionic acid sodium is with lead chloride (G) and mix piperazine-N, the hexahydrate of N '-two dithionic acid sodium and lead chloride (H) figure that lead complex generates when (all with respect to lead chloride and piperazine-N, the total solids composition of the hydrate of N '-two dithionic acid sodium comprises 20 weight % pure water).Wherein (I) represents independent piperazine-N, and X-ray diffraction, (J) of N '-two dithionic acid lead complexs represent independent piperazine-N, the N '-hexahydrated X-ray diffraction of two dithionic acid sodium.
Fig. 4 is mixing piperazine-N by the X-ray diffraction evaluation, the no hydrate of N '-two dithionic acid sodium with cupric chloride (K), mix piperazine-N, the dihydrate of N '-two dithionic acid sodium is with cupric chloride (L) and mix piperazine-N, the hexahydrate of N '-two dithionic acid sodium and cupric chloride (M) figure that copper complex generates when (all with respect to cupric chloride and piperazine-N, the total solids composition of the hydrate of N '-two dithionic acid sodium comprises 20 weight % pure water).Wherein (N) represents independent piperazine-N, and the N '-copper complex formazan X-ray diffraction of two dithionic acids, (O) represent independent piperazine-N, the N '-hexahydrated X-ray diffraction of two dithionic acid sodium.
Fig. 5 is mixing piperazine-N by the X-ray diffraction evaluation, the no hydrate of N '-two dithionic acid potassium with lead chloride (P), mix piperazine-N, the dihydrate of N '-two dithionic acid potassium and lead chloride (Q) figure that lead complex generates when (all with respect to lead chloride and piperazine-N, the total solids composition of the hydrate of N '-two dithionic acid potassium comprises 20 weight % pure water).Wherein (R) represents independent piperazine-N, and X-ray diffraction, (S) of N '-two dithionic acid lead complexs represent independent piperazine-N, the X-ray diffraction of N '-two dithionic acid potassium dihydrates.
Fig. 6 is mixing piperazine-N by the X-ray diffraction evaluation, the no hydrate of N '-two dithionic acid potassium with cupric chloride (T), mix piperazine-N, the dihydrate of N '-two dithionic acid potassium and cupric chloride (U) figure that copper complex generates when (all with respect to cupric chloride and piperazine-N, the total solids composition of the hydrate of N '-two dithionic acid potassium comprises 20 weight % pure water).Wherein (V) represents independent piperazine-N, and the N '-copper complex formazan X-ray diffraction of two dithionic acids, (W) represent independent piperazine-N, the X-ray diffraction of N '-two dithionic acid potassium dihydrates.In addition, in each figure, (unit is degree to 2 θ values during transverse axis (X-axis) expression X-ray diffraction, and deg), the peak intensity the when longitudinal axis (Y-axis) is represented X-ray diffraction, scale (scale) is arbitrarily.
Embodiment
Below to the piperazine-N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two 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 '-two 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 '-two dithionic acid potassium dihydrates.
[table 4]
Piperazine-N with high crystalline, N '-two dithionic acid sodium hexahydrates and piperazine-N, N '-two dithionic acid potassium dihydrates have following feature: the variation of the moisture content that can not caused by moisture absorption etc. when preserving in atmosphere and cause effective constituent (piperazine-N in the solids component, N '-two dithionic acid sodium and piperazine-N, N '-two dithionic acid potassium) containing ratio change, in addition, be difficult to caking in the preservation.
Because piperazine-N, no hydrate, dihydrate or the piperazine-N of N '-two dithionic acid sodium, the no hydrate of N '-two dithionic acid potassium can absorb the moisture in the atmosphere, therefore thereby the weight ratio of the effective constituent of heavy metal treatment agent can change, need be at the constituent concentration that is used for that efficiency confirmed before heavy metal was handled.On the other hand, because piperazine-N of the present invention, N '-two dithionic acid sodium hexahydrates and piperazine-N, N '-two dithionic acid potassium dihydrates do not have the changes in weight that causes owing to the moisture that absorbs in the atmosphere, therefore need efficiency confirmed when each the use constituent concentration.
Of the present invention with piperazine-N, N '-two dithionic acid sodium hexahydrates are in the heavy metal treatment agent of effective constituent, piperazine-N, the content of N '-two dithionic acid sodium are preferably more than the 60 weight % (is 83 weight % for the hexahydrate crystal), more preferably more than the 70 weight % (is 96.8 weight % for the hexahydrate crystal).Crystal powder at heavy metal treatment agent all is under the hexahydrated situation, and piperazine-N, the content of N '-two dithionic acid sodium are 72.3 weight %.
In addition, of the present invention with piperazine-N, N '-two dithionic acid potassium dihydrates are in the heavy metal treatment agent of effective constituent, piperazine-N, the content of N '-two dithionic acid potassium are preferably more than the 70 weight % (is 78 weight % for dihydrochloride dihydrate crystal), more preferably more than the 85 weight % (is 94.7 weight % for dihydrochloride dihydrate crystal).Crystal powder at heavy metal treatment agent all is under the situation of dihydrate, and piperazine-N, the content of N '-two dithionic acid potassium are 89.7 weight %.
Piperazine-the N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates is not a heavy metal treatment agent as existing solid-state heavy metal treatment agent, that dithionate and other solid salts (carrier) of amine mixed, therefore but purified crystal has high this advantage of containing ratio of the effective constituent in the heavy metal treatment agent.
In addition, even in heavy metal treatment agent of the present invention, include under the situation of hydrate of a part no hydrate or other its forms, because the surface portion of heavy metal treatment agent powder particle is made 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 '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates further has following feature: mix and do not produce obnoxious flavour when using when the preservation of chemical reagent and containing thing with heavy metal.
Use solid-state piperazine-N, no hydrate, dihydrate or the piperazine-N of N '-two dithionic acid sodium, the solid of the no hydrate of N '-two dithionic acid potassium is compared with the situation of the aqueous solution that uses them, and the generation of dithiocarbonic anhydride has the trend of increase.On the other hand, piperazine-N of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, N '-two dithionic acid potassium dihydrates do not have the problem that the generation of deleterious dithiocarbonic anhydride increases.
And then, piperazine-the N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates has following feature: to the reaction preference height of deleterious lead, can carry out immobilization to deleterious lead efficiently and handle.
For example, piperazine-N during the heavy metal that contains thing for heavy metal is handled, N '-two dithionic acid sodium hexahydrates, with respect to total solids composition (flying dust+heavy metal treatment agent) moisture addition is under the situation of 20 weight %, comparing its reaction preference to lead (with to copper relatively) height with dihydrate, no hydrate, is more than 5 times.In addition, even under the situation that the moisture addition increases, also kept dominance to the reaction preference of lead.
Similarly, piperazine-N during the heavy metal that contains thing for heavy metal is handled, N '-two dithionic acid potassium dihydrates, with respect to total solids composition (flying dust+heavy metal treatment agent) moisture addition is under the situation of 20 weight %, compare its reaction preference (with relatively) height to copper to lead with no hydrate, be more than 5 times, even under the situation that the moisture addition increases, also kept dominance to the reaction preference of lead.
In the heavy metal that uses heavy metal treatment agent of the present invention is handled, contain with respect to heavy metal thing and heavy metal treatment agent the total solids composition, moisture addition (weight %) has no particular limits, it is above and 50 weight % are following, it is above and below the 40 weight % to be preferably 20 weight % especially to be preferably 10 weight %.
For example, in the processing of the flying dust that contains thing as heavy metal, if crossing at most, the moisture addition can form huge bulk or pulp-like, the operation (handling) of handling ash becomes difficulty, is to handle under the state of scope of 20～40 weight % with respect to solids component making the moisture addition usually therefore.Therefore, piperazine-the N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates can be brought into play the high reaction preference to lead in the flying dust of common moisture addition is handled.
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 the vehicle (or carrier) as heavy metal treatment agent and use, therefore with respect to piperazine-N, N '-two dithionic acid sodium or piperazine-N, N '-two dithionic acid potassium compositions, its content is enough in 0.01～5 weight %, the particularly scope at 0.1～2 weight %.
As the alkali metal hydroxide that uses, preferred sodium hydroxide, potassium hydroxide, as the alkaline earth metal hydroxides that uses, preferred magnesium hydroxide, calcium hydroxide.
Piperazine-the N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the manufacture method of the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates has no particular limits, and can make by following manufacture method.
Piperazine-N, N '-two dithionic acid sodium hexahydrates or piperazine-N, N '-two dithionic acid potassium dihydrates can followingly be made: make piperazine, dithiocarbonic anhydride and basic metal (sodium or potassium) oxyhydroxide at piperazine-N, react in the saturated aqueous solution of N '-two dithionic acid basic metal (sodium or potassium), 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 '-two dithionic acid sodium, higher (piperazine is about 1.8 moles/L, piperazine-N to piperazine to the solubleness of water, the solubleness of N '-two dithionic acid sodium is 0.9 mole/L (about 25 weight %)), even therefore at piperazine-N, piperazine also can further dissolve in the saturated solution of N '-two dithionic acid sodium salts.
Similarly, for piperazine and piperazine-N, N '-two dithionic acid potassium, higher (piperazine is about 1.8 moles/L, piperazine-N to piperazine to the solubleness of water, N '-two dithionic acid sylvite are 1.3 moles/L (about 40 weight %)), even therefore at piperazine-N, piperazine also can further dissolve in the saturated solution of N '-two dithionic acid sylvite.
Piperazine-the N that generates, N '-two dithionic acid sodium or piperazine-N, the viscosity of the saturated aqueous solution of N '-two dithionic acid potassium is low, and therefore reactive (usability when reacting continuously) also excellent.
On the other hand, because at piperazine-N, the dithionate of the amine beyond N '-two dithionates, for example do not separate out solid in the dithionate's of tetren, diethylenetriamine, polymine etc. the supersaturated solution, become the high aqueous solution of viscosity, the dithionate who therefore obtains solid-state amine is difficult.
In manufacture method of the present invention, preferably, with piperazine dissolved in piperazine-N, in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts (sodium salt or sylvite), and add dithiocarbonic anhydride earlier, alkali metal hydroxide (sodium hydroxide or potassium hydroxide) is added in the back.At piperazine-N, in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts, when under the state of alkali metal hydroxide surplus, making the reaction of piperazine and dithiocarbonic anhydride, generate gelatinous by product sometimes, be difficult to carry out successive reaction.
And then, in the method for the invention, can add piperazine, dithiocarbonic anhydride and alkali metal hydroxide in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts by repeatedly alternately to piperazine-N, make solid-state piperazine-N continuously, N '-two dithionic acid an alkali metal salts.
As particularly preferred embodiment, can the following method of illustration: at piperazine-N, in the reaction in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts, piperazine, dithiocarbonic anhydride and alkali metal hydroxide, make piperazine dissolved in piperazine-N earlier, the saturated aqueous solution of N '-two dithionic acid an alkali metal salts carries out reaction while keep dithiocarbonic anhydride then with respect to the state of alkali metal hydroxide surplus.Under the situation of reacting than the state of alkali metal hydroxide surplus with dithiocarbonic anhydride, though temporarily separate out solid-state piperazine-N, N '-two dithionic acids, but compare with the situation of adding alkali metal hydroxide earlier, the viscosity of the aqueous solution is low, reactivity and operability are good, finally can obtain purified piperazine-N, the crystal of N '-two dithionic acid an alkali metal salts.Particularly preferably be, be divided into the interpolation of dithiocarbonic anhydride and alkali metal hydroxide more than 2 times respectively or the time difference is set and method such as add simultaneously.
For the reaction of the piperazine in the aqueous solution, dithiocarbonic anhydride and alkali metal hydroxide, the piperazine-N-dithionic acid an alkali metal salt beyond the by-product piperazine-N sometimes, N '-two dithionic acid an alkali metal salts, thiocarbonate, the piperazine of remained unreacted sometimes.Because the low piperazine of a functional group thereby heavy metal processing power-N-dithionic acid an alkali metal salt and piperazine-N only arranged, N '-two dithionic acid an alkali metal salts are compared the solvability height, therefore in the method for the invention, can optionally make the high only piperazine-N of heavy metal processing power, the crystal of N '-two dithionic acid an alkali metal salts.
Because piperazine and thiocarbonate be the solubleness height too, therefore residual in the aqueous solution, with piperazine-N, N '-two dithionic acid an alkali metal salts can separate.Utilize to concentrate, in the method for organic solvent extraction, have piperazine-N-dithionic acid an alkali metal salt, piperazine and thiocarbonate and piperazine-N, the problem that N '-two dithionic acid an alkali metal salts are separated out simultaneously, but in the method for the invention, can be used as crystal and optionally make the high piperazine-N of heavy metal processing power, N '-two dithionic acid an alkali metal salt compositions.
In the present invention, the crystalline drying means of separating out has no particular limits, get final product so long as can obtain the method for hydrate of the present invention (for piperazine-N, N '-two dithionic acid sodium salts are hexahydrate, for piperazine-N, N '-two dithionic acid potassium are dihydrate).Even cause under the situation that crystallinity descends by over-drying at the crystal of separating out, also can be by further in containing the atmosphere of moisture, carrying out the crystal that hydration-treated obtains hydrate of the present invention.The crystallization that is caused by dried hydration preferably carries out in pulverizing or forced-flow.
By with the piperazine-N that comprises of the present invention, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two 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 during the immobilization of heavy metals of heavy metal treatment agent of the present invention is handled can be suitable for the common method same with other heavy metal treatment agents, as required, can in heavy metal treatment agent, pH regulator agent such as suitable mixing water, mixed alkali metal oxyhydroxide, iron(ic) chloride use.
Comprise piperazine-N, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, the heavy metal treatment agent of N '-two dithionic acid potassium dihydrates can contain thing with heavy metal in the back that is dissolved in the water and mix use, preferably, directly mix simultaneously with water and to use, particularly preferably be, after directly mixing, add water and use.
Embodiment
Below with embodiment invention is described, but the present invention is not limited to these embodiment.
Embodiment 1
The 61.01g piperazine is dissolved under 40 ℃ in the 212.4g pure water, in stream of nitrogen gas, while stirring the aqueous sodium hydroxide solution of 106.77g dithiocarbonic anhydride and 119.82g 48 weight % is divided into 4 parts then respectively and carries out alternative and drip.Drip the end back and obtain to have separated out piperazine-N, the pulp solution of N '-two dithionic acid sodium.Leach the piperazine-N that separates out, N '-two dithionic acid sodium removes the moisture and the drying of attachment removal in vacuum drier.
Gained piperazine-N, N '-thermoanalytical result of two dithionic acid sodium is a hexahydrate, X-ray diffraction pattern as shown in Figure 1, it has high crystalline.
With gained piperazine-N, N '-two dithionic acid sodium hexahydrates are dissolved in the pure water and carry out
13C-NMR (nuclear magnetic resonance spectroscopy(NMR spectroscopy), Nuclear Magnetic Resonance) measures, and the result does not detect piperazine and the two dithionic acid sodium of piperazine-N-.
In 250g embodiment 1, leached piperazine-N, filtrate (piperazine-the N of N '-two dithionic acid sodium, the saturated aqueous solution of N '-two dithionic acid sodium) further adds 42.57g piperazine and 50.73g pure water in, 40 ℃ of down dissolvings, in stream of nitrogen gas, while stirring 74.50g dithiocarbonic anhydride and 82.19g 48 weight % aqueous sodium hydroxide solutions are divided into 2 parts respectively and replace dropping.Drip the end back and obtain to have separated out piperazine-N, the pulp solution of N '-two dithionic acid sodium.
Reuse saturated solution, confirm to have obtained piperazine-N, N '-two dithionic acid sodium hexahydrates.
Comparative example 1
Further in moisture eliminator under 50 ℃ and 100 ℃ the hexahydrate to embodiment 1 carry out drying, obtain dihydrate and no hydrate respectively.
X-ray diffraction pattern is shown in Fig. 1.The crystallinity of dihydrate and no hydrate is low.
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 weight % aqueous sodium hydroxide solutions are 156.28g, in addition, carry out 1 identical operations, do not obtain solid-state dithionate with embodiment.
Embodiment 3
Use 68.45g piperazine, 123.58g pure water, 121.01g dithiocarbonic anhydride and 186.96g48 weight % potassium hydroxide aqueous solution, make piperazine under 40 ℃, be dissolved in pure water, in stream of nitrogen gas, while stirring dithiocarbonic anhydride and 48 weight % potassium hydroxide are divided into 4 parts respectively then and replace dropping.Drip the end back and obtain to have separated out piperazine-N, the pulp solution of N '-two dithionic acid potassium dihydrates.Leach the piperazine-N that separates out, N '-two dithionic acid potassium removes the moisture of attachment removal and carries out drying in vacuum drier.
Gained piperazine-N, N '-thermoanalytical result of two dithionic acid potassium is a dihydrate, X-ray diffraction pattern as shown in Figure 2, it has high crystalline.
With gained piperazine-N, N '-two dithionic acid potassium dihydrates are dissolved in the pure water and carry out
13C-NMR measures, and the result does not detect piperazine and the two dithionic acid potassium of piperazine-N-.
Embodiment 4
In 300g embodiment 3, leached piperazine-N, filtrate (piperazine-the N of N '-two dithionic acid potassium, the saturated aqueous solution of N '-two dithionic acid potassium) further adds 30.42g piperazine and 31.00g pure water in, 40 ℃ of down dissolvings, in stream of nitrogen gas, while stirring 53.78g dithiocarbonic anhydride and 84.80g 48 weight % potassium hydroxide aqueous solutions are divided into 2 parts respectively and replace dropping.Drip the end back and obtain to have separated out piperazine-N, the pulp solution of N '-two dithionic acid potassium.
Reuse saturated solution, confirm to have obtained piperazine-N, N '-two dithionic acid potassium dihydrates.
Comparative example 3
Further in moisture eliminator under 100 ℃ the dihydrate to embodiment 3 carry out drying, obtain no hydrate.As shown in Figure 2, no hydrate is different with the dihydrate crystallinity, and its crystallinity is low.
(storage stability is estimated 1 (changes in weight))
With the piperazine-N that obtains in embodiment 1 and the comparative example 1, hexahydrate, the dihydrate of N '-two dithionic acid sodium and do not have hydrate and in atmosphere, place, gravimetry change through the time change.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 ( |
5.00 | 5.99 |
| Comparative example 1 (sodium salt does not have hydrate) | 5.00 | 6.71 |
Confirm, piperazine-N, the no hydrate of N '-two dithionic acid sodium, dihydrate through the time changes in weight has taken place, and piperazine-N, changes in weight does not take place in N '-two dithionic acid sodium hexahydrates, preserves stable in atmosphere.
In addition, unconfirmed after in atmosphere, placing to the hexahydrate caking, and confirm the flowability decline of dihydrate and no hydrate, attached on the container.
Similarly, with the piperazine-N that obtains in embodiment 3 and the comparative example 3, N '-two dithionic acid potassium dihydrates and no hydrate are placed in atmosphere, gravimetry change through the time variation.The results are shown in table 6.
[table 6]
| Initial weight g | Weight g after one month | |
| Embodiment 3 ( |
5.00 | ?5.00 |
| Comparative example 3 (sylvite does not have hydrate) | 5.00 | ?5.56 |
Confirm, piperazine-N, N '-two dithionic acid potassium do not have hydrate changes in weight have taken place, and piperazine-N, changes in weight does not take place in N '-two dithionic acid potassium dihydrates, preserves stable in atmosphere.
After in atmosphere, placing, unconfirmed to piperazine-N, N '-two dithionic acid potassium dihydrates cakings, and confirm the flowability decline of no hydrate, attached on the container.
(heavy metal Processing Test)
To be respectively piperazine-N of the embodiment 1 of 0.5 weight part (no hydrate converts) with respect to 50 weight part flying dust A (Pb=2500ppm), piperazine-N of N '-two dithionic acid sodium hexahydrates, embodiment 3, N '-two dithionic acid potassium dihydrates are dissolved in separately in 25 weight parts waters and are mixing with flying dust A.In addition, will be piperazine-N of the embodiment 1 of 0.5 weight part (no hydrate converts) with respect to 50 weight part flying dust A (Pb=2500ppm), N '-two dithionic acid sodium hexahydrates directly make an addition to flying dust A, and the water that adds 25 weight parts then carries out mixing.According to No. 13rd, Environmental Agency bulletin test (clear and 48 year) each mixing thing carried out dissolution test thereafter.
Plumbous stripping is satisfied environmental criteria all less than 0.05ppm.
(eudiometry 1)
At Tedlar sampler bag (Tedlar Bag, volume 1L) puts into 2.74g piperazine-N in, the hexahydrate of N '-two dithionic acid sodium (press piperazine-N, the N '-two dithionic acid sodium meter that converts is equivalent to 2g) also loads the 500mL air, places respectively 1 hour under room temperature and 65 ℃.After the placement, the dithiocarbonic anhydride concentration of the upper space in the Tedlar sampler bag (head space) is measured with detector tube.
In order to compare, load piperazine-N, the dihydrate of N '-two dithionic acid sodium and no hydrate (press piperazine-N, N '-two dithionic acid sodium convert and score not and hexahydrate equivalent) are also measured dithiocarbonic anhydride concentration same as described abovely.The results are shown in table 7.
At piperazine-N, confirm the generation of dithiocarbonic anhydride in the dihydrate of N '-two dithionic acid sodium and the no hydrate, and at piperazine-N, fail to detect dithiocarbonic anhydride (ND) in N '-two dithionic acid sodium hexahydrates or dithiocarbonic anhydride few.
[table 7]
Similarly in Tedlar sampler bag (volume 1L), put into 2.2g piperazine-N, N '-two dithionic acid potassium dihydrates (are pressed piperazine-N, the N '-two dithionic acid potassium meter that converts is equivalent to 2.0g) and load the 500mL air, under room temperature and 65 ℃, placed respectively 1 hour.After the placement, the dithiocarbonic anhydride concentration of the upper space of Tedlar sampler bag is measured with detector tube.
In order to compare, add piperazine-N, the no hydrate of N '-two dithionic acid potassium (press piperazine-N, N '-two dithionic acid potassium convert and score not and dihydrate equivalent) is also measured dithiocarbonic anhydride concentration same as described abovely.The results are shown in table 8.
At piperazine-N, N '-two dithionic acid potassium do not have the generation that confirms dithiocarbonic anhydride in the hydrate, and at piperazine-N, fail to detect dithiocarbonic anhydride (ND) in N '-two dithionic acid potassium dihydrates.
[table 8]
(eudiometry 2)
In Tedlar sampler bag (volume 1L) filling 30g flying dust B (Pb=2700ppm), be the pure water of 35 weight % and piperazine-N of 0.74 weight % with respect to flying dust B, N '-two dithionic acid sodium hexahydrates, mix back filling 500mL air, under room temperature and 65 ℃, placed respectively 1 hour.After the placement, the hydrogen sulfide and the dithiocarbonic anhydride concentration of the upper space in the Tedlar sampler bag are measured with detector tube.
Add 30g flying dust C (Pb=9800ppm), be the pure water of 20 weight % and piperazine-N of 3.0 weight % with respect to flying dust C, N '-two dithionic acid sodium hexahydrates are also similarly handled with above-mentioned, carry out eudiometry then.
In order to compare, similarly add piperazine-N with above-mentioned to flying dust C, the no hydrate of N '-two dithionic acid sodium and dihydrate (press piperazine-N, N '-two dithionic acid sodium convert score not and hexahydrate equivalent), and this situation is carried out 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, the generation of dithiocarbonic anhydride at piperazine-N, confirms the generation (increase) of dithiocarbonic anhydride less than 1ppm in N '-two dithionic acid sodium hexahydrates in N '-two dithionic acid sodium dihydrates and the no 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 weight % and piperazine-N of 0.7 weight % with respect to flying dust B, N '-two dithionic acid potassium dihydrates mixes back filling 500mL air, heats 1 hour down at 65 ℃.After the heating, the hydrogen sulfide and the dithiocarbonic anhydride concentration of the upper space of Tedlar sampler bag are measured with detector tube.
Add 30g flying dust C (Pb=9800ppm), be the pure water of 20 weight % and piperazine-N of 1.1 weight % with respect to flying dust C, N '-two dithionic acid potassium dihydrates are also similarly handled with above-mentioned, carry out eudiometry then.
Each the results are shown in table 11.All fail to detect hydrogen sulfide and dithiocarbonic anhydride in either event.
[table 11]
(to the reaction preference of lead)
Will be by piperazine-N, N '-two dithionic acid sodium compositions convert and count respectively is piperazine-N of 10g, hexahydrate, the dihydrate of N '-two dithionic acid sodium and do not have 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 '-two dithionic acid sodium is 20 weight % and 30 weight %) mix, by X-ray diffraction the generation that mixes each metal complex of back is measured.
For lead complex, copper complex and piperazine-N, 9.4 ° (from peaks (a) of lead complex) of the diffraction angle of N '-two dithionic acid sodium, 12.9 ° (from copper complex formazan peak (b)) and 21.3 ° are (from piperazine-N, the peak (c) of N '-two dithionic acid sodium compositions) each diffracted intensity, establishing a/c is the selectivity (3) of the ratio of copper reactivity (2), (1)/(2) for lead for plumbous reactive (1), b/c.Moisture content is to the results are shown in table 12,13 under the situation of 20 weight % and 30 weight %.
With piperazine-N, the dihydrate of N '-two dithionic acid sodium is compared with no hydrate, piperazine-N, N '-two dithionic acid sodium hexahydrates are to the selectivity height of lead, and its trend is: the moisture content that heavy metal contains in the thing (comprising heavy metal treatment agent) is few more remarkable more.
[table 12]
(moisture 20 weight %)
[table 13]
(moisture 30 weight %)
Similarly, will be by piperazine-N, N '-two dithionic acid potassium compositions convert and count respectively is piperazine-N of 10g, the dihydrate of N '-two dithionic acid potassium and do not have 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 '-two dithionic acid potassium is 20 weight % and 30 weight %) mix, by X-ray diffraction the generation that mixes each metal complex of back is measured.
For lead complex, copper complex and piperazine-N, 9.4 ° (from peaks (a) of lead complex) of the diffraction angle of N '-two dithionic acid potassium, 15.1 ° (from copper complex formazan peak (b)) and 33.1 ° are (from piperazine-N, the peak (c) of N '-two dithionic acid potassium compositions) each diffracted intensity, establishing a/c is the selectivity (3) of the ratio of copper reactivity (2), (1)/(2) for lead for plumbous reactive (1), b/c.Under the situation of moisture content 20 weight % and 30 weight %, the results are shown in table 14,15.
With piperazine-N, the no hydrate of N '-two dithionic acid potassium is compared, piperazine-N, and N '-two dithionic acid potassium dihydrates are to the reaction preference height of lead, and its trend is: the moisture content that heavy metal contains in the thing is few more remarkable more.
[table 14]
(moisture 20 weight %)
[table 15]
(moisture 30 weight %)
Utilizability on the industry
Heavy metal treatment agent of the present invention can be used for the immobilization processing that heavy metal contains heavy metal in the thing, particularly can process for the heavy metal of the flying dust that comprises a large amount of lead aptly.
In addition, quoted and the full content of Japanese patent application 2009-162099 number specification sheets, claim, Figure of description and summary of application on July 8th, 2009 at this Japanese patent application 2009-152158 number of application on June 26th, Japanese patent application 2008-294911 number 1 of application on November 18th, Japanese patent application 2008-294910 number 1 of on November 18th, 2008 application, and incorporated into as the disclosure of specification sheets of the present invention.
Claims (14)
1. a heavy metal treatment agent is characterized in that it comprises piperazine-N, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, N '-two dithionic acid potassium dihydrates.
2. heavy metal treatment agent according to claim 1, it comprises the crystalline piperazine-N of the X-ray diffraction pattern with table 1, N '-two dithionic acid sodium hexahydrates,
[table 1]
3. heavy metal treatment agent according to claim 1 and 2, it contains the above piperazine-N of 70 weight %, N '-two dithionic acid sodium.
4. heavy metal treatment agent according to claim 1, it comprises the crystalline piperazine-N of the X-ray diffraction pattern with table 2, N '-two dithionic acid potassium dihydrates,
[table 2]
5. according to claim 1 or 4 described heavy metal treatment agents, it contains the above piperazine-N of 85 weight %, N '-two dithionic acid potassium.
6. according to each the described heavy metal treatment agent in the claim 1～5, it further comprises alkali metal hydroxide and/or alkaline earth metal hydroxides.
7. solid-state piperazine-N, the manufacture method of N '-two dithionic acid an alkali metal salts, it is characterized in that, make piperazine, dithiocarbonic anhydride and alkali metal hydroxide at piperazine-N, react in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts, separate out piperazine-N, N '-two dithionic acid an alkali metal salts, and with this salt separation.
8. manufacture method according to claim 7, wherein, solid-state piperazine-N, N '-two dithionic acid an alkali metal salts are piperazine-N, N '-two dithionic acid sodium hexahydrates and/or piperazine-N, N '-two dithionic acid potassium dihydrates.
9. according to claim 7 or 8 described manufacture method, wherein, be dissolved with the piperazine-N of piperazine, adding dithiocarbonic anhydride in the saturated aqueous solution of N '-two dithionic acid an alkali metal salts earlier, alkali metal hydroxide is added in the back.
10. according to each the described manufacture method in the claim 7～9, it adds dithiocarbonic anhydride and alkali metal hydroxide repeatedly alternately to the piperazine-N that is dissolved with piperazine in saturated aqueous solution of N '-two dithionic acid an alkali metal salts.
11. according to each the described manufacture method in the claim 7～10, wherein, basic metal is sodium or potassium.
12. the treatment process of a heavy metal species is characterized in that, each the described heavy metal treatment agent in the claim 1～6 is contained thing with heavy metal directly mix.
13. the treatment process of heavy metal according to claim 12 wherein, contains the total solids composition of each the described heavy metal treatment agent in thing and the claim 1～6 with respect to heavy metal, the moisture addition is that 10 weight % are above and below the 50 weight %.
14. the treatment process of a heavy metal species, wherein, the aqueous solution that will be dissolved with each the described heavy metal treatment agent in the claim 1～6 in water contains thing with heavy metal and mixes.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-294910 | 2008-11-18 | ||
| JP2008-294911 | 2008-11-18 | ||
| JP2008294910 | 2008-11-18 | ||
| JP2008294911 | 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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| CN102216410A true CN102216410A (en) | 2011-10-12 |
| CN102216410B CN102216410B (en) | 2014-10-15 |
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