CN102942512A - Preparation method of sulfide heavy metal trapping agent C2H4N2S4 - Google Patents
Preparation method of sulfide heavy metal trapping agent C2H4N2S4 Download PDFInfo
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- CN102942512A CN102942512A CN2012104740519A CN201210474051A CN102942512A CN 102942512 A CN102942512 A CN 102942512A CN 2012104740519 A CN2012104740519 A CN 2012104740519A CN 201210474051 A CN201210474051 A CN 201210474051A CN 102942512 A CN102942512 A CN 102942512A
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Abstract
The invention discloses a preparation method of sulfide heavy metal trapping agent C2H4N2S4. Cyclohexanol and acetone are prepared according to a certain volume ratio and used as a mixed solvent, carbon disulfide is dissolved in the mixed solvent to obtain a carbon disulfide mixed solution, the carbon disulfide mixed solution is slowly added in hydrazine hydrate in dropwise mode under stirring state according to a certain molar ratio, reaction is performed at a certain temperature, suction filtration is performed on reaction products, a filter cake is washed through absolute ethyl alcohol, and C2H4N2S4 can be obtained. The method selects cyclohexanol to replace ethylene glycol, can greatly reduce dosage of cyclohexanol in the mixed solvent, simultaneously improves product yield, and reduces production cost of C2H4N2S4.
Description
Technical field
The present invention relates to a kind of preparation method of sulfide heavy metal chelating agent, particularly relate to a kind of preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid.
Background technology
Although China environmental protection obtains positive progress, the environment situation that the situation is tense does not still change.The environment contradiction of long-term accumulation not yet solves, and particularly the heavy metal contaminants quantity discharged surpasses the environment ability to bear, serious harm the people healthy.In recent years, the discharging of various heavy metal wastewater therebies has caused the severe contamination of soil and water, has caused extensive concern both domestic and external.
Traditional pH regulator precipitator method are processed the waste water that contains heavy metal ion, namely by adding the alkaline chemical such as sodium hydroxide, yellow soda ash, lime, with waste water furnishing alkalescence, form corresponding heavy metal hydroxide precipitation with heavy-metal ion removal.The pH regulator precipitator method need careful control pH value, to guarantee best removal effect.If contain the zwitter-ions such as zine ion, aluminum ion in the waste water, the precipitation of hydroxide of formation is dissolved when high alkalinity, needs to change different pH values, carries out multi stage precipitation and processes.Because the pH value of processed waste water is too high, supernatant liquid must pump into neutralization tank, and acid adding readjustment pH to 6～9 could be discharged, and treatment step is comparatively loaded down with trivial details.
The another kind of actual method that adopts is to adopt the Sodium Sulphide precipitator method to process heavy metal wastewater thereby, utilizes the sodium sulphite and the heavy metal ion that add to form the sulfide precipitation of indissoluble with heavy-metal ion removal.The solubleness of the sulfide precipitation of heavy metal ion in water is than low 3-10 the order of magnitude of corresponding precipitate metal hydroxides, and it is less to remain in the aqueous solution concentration of heavy metal ion, and can remove many kinds of metal ions in a step precipitation process.Regulate the precipitator method with pH and compare, precipitation has the advantages such as easily separated, easy filtration, subsequent disposal be simple.But sodium sulphite is lower for the precipitation removal efficient that contains chelating attitude heavy metal in the use procedure, can produce the peculiar smell of hydrogen sulfide, and heavy metal sulfide precipitation floc particle is tiny, the settling time waits so long very much, reduced the removal effect of heavy metal ion, all there is in practice certain limitation, is difficult to guarantee the complete qualified discharge of heavy metal wastewater thereby.
CN 102070235B discloses a kind of water-soluble organic thiamine heavy metal chelating agent, the preparation method is dissolved in 100～500 mL polyamines (hydrazine hydrate) during 100 mL purify waste water, 50～200 mL organosulfurs (dithiocarbonic anhydride) are dissolved in the 100 mL dehydrated alcohols, add again 5～10 mL emulsifying agent ethoxylated dodecyl alcohols, again above-mentioned two kinds of solution are mixed rear in 40～50 ℃, add 5～20 gram sodium hydroxide or potassium hydroxide, react after 6～8 hours, be cooled to below 10 ℃ after the crystallization, separate solid, and use absolute ethanol washing, obtain heavy metal chelating agent C
2H
4N
2S
4When 40～50 ℃ of reactions, there is certain potential safety hazard in used dehydrated alcohol boiling point lower (78.5 ℃); Use emulsifying agent ethoxylated dodecyl alcohol and mineral alkali sodium hydroxide or potassium hydroxide in the reaction, not only increased production cost, and increased post-processing difficulty; 6～8 hours reaction times, need to be cooled to crystallization below 10 ℃, energy consumption is larger.
The Zhen Hao ripple (preparation of heavy metal chelating agent DTC (TBA) and the research of Treatment of Copper waste water, [D]. South China Science ﹠ Engineering University, 2011) take hydrazine hydrate and dithiocarbonic anhydride as raw material, prepared heavy metal chelating agent tetrathio hydrazino formic acid C
2H
4N
2S
4Reaction formula is as follows:
The optimum synthesis condition of report is: the mol ratio of hydrazine hydrate and dithiocarbonic anhydride is 1.13:1, organic mixed solvent (volume ratio is ethylene glycol and the acetone mixture of 2:1) is 1:2 with the volume ratio of dithiocarbonic anhydride, temperature of reaction is 30～40 ℃, reaction 2h, under optimum synthesis condition, the transformation efficiency of dithiocarbonic anhydride is 87%.Compare with CN 102070235B, make spent glycol as one of solvent in this reaction process, by improving the boiling point of solvent, reduced potential safety hazard.Need not emulsifying agent ethoxylated dodecyl alcohol and mineral alkali sodium hydroxide or potassium hydroxide in the reaction, all there are the reduction of certain amplitude in temperature of reaction and reaction times.But in this reaction process, the mol ratio of hydrazine hydrate and dithiocarbonic anhydride is 1.13:1, and the mol ratio of hydrazine hydrate and dithiocarbonic anhydride should be 0.5:1 in theory, and the mol ratio of hydrazine hydrate and dithiocarbonic anhydride is still higher.In addition, the volume ratio of mixed solvent and dithiocarbonic anhydride, the processing parameters such as selection of mixed solvent still have the space of continuing optimization, with the transformation efficiency of further raising dithiocarbonic anhydride.
Summary of the invention
The object of the invention is to, overcome the defective that prior art exists, a kind of preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid is provided, to improve target product yield, reduce production costs; Prepared sulfide heavy metal chelating agent can be at normal temperatures, with the Hg in the waste water
2+, Cd
2+, Pb
2+, Mn
2+, Cu
2+, Ni
2+, Zn
2+React rapidly etc. heavy metal ion, generate water-insoluble sulfide precipitate.
In order to address the above problem, the present invention by configuration certain volume ratio hexalin and acetone as mixed solvent, the volume ratio according to certain dithiocarbonic anhydride and mixed solvent is dissolved in dithiocarbonic anhydride in the mixed solvent, obtains the mixed solvent solution of dithiocarbonic anhydride.Mol ratio according to certain hydrazine hydrate and dithiocarbonic anhydride places reaction vessel with hydrazine hydrate.When being warming up to certain temperature, under whipped state, slowly drip the mixed solvent solution of dithiocarbonic anhydride, stopped reaction after reaction for some time, reaction product is through suction filtration, and the filter cake absolute ethanol washing makes a kind of efficient sulfide heavy metal chelating agent tetrathio hydrazino formic acid, for the treatment of the trade effluent that contains heavy metal ion, at normal temperatures with waste water in Hg
2+, Cd
2+, Pb
2+, Mn
2+, Cu
2+, Ni
2+, Zn
2+, Cr
3+, Cr
6+React rapidly etc. various heavy metal ion, generate water-insoluble sulfide precipitate.
Realize that the technical scheme that purpose of the present invention adopts is:
A kind of sulfide heavy metal chelating agent tetrathio hydrazino formic acid (C
2H
4N
2S
4) the preparation method, it is characterized in that dithiocarbonic anhydride is dissolved in the mixed solvent that hexalin and acetone forms, and the mixing solutions of the dithiocarbonic anhydride of formation is added drop-wise in the hydrazine hydrate, stirring reaction 2～3 h can obtain tetrathio hydrazino formic acid.
Described sulfide heavy metal chelating agent structural formula is
, the S in the molecule can with heavy metal Cheng Jian, thereby generate stable heavy metal chelate.
In the described mixed solvent, the volume ratio of hexalin and acetone is preferably 2:1～0.2:1.
In the mixing solutions of described dithiocarbonic anhydride, the volume ratio of dithiocarbonic anhydride and mixed solvent is preferably 3:1～3:2.
The mol ratio of described dithiocarbonic anhydride and hydrazine hydrate is preferably 1:0.91～1:1.11.
Described temperature of reaction is preferably 30～35 ℃.
Described reaction product is through suction filtration, and the filter cake absolute ethanol washing can obtain white tetrathio hydrazino formic acid.
More specifically and optimally, the preparation method of described tetrathio hydrazino formic acid is, at 30～35 ℃, 30 mL dithiocarbonic anhydride are dissolved in 20 mL hexalin and the acetone mixed solvent, and wherein hexalin is 3.4 mL, and the mixing solutions of the dithiocarbonic anhydride that forms slowly is added drop-wise to 31 mL 80%(wt%) in the hydrazine hydrate, stirring reaction 2h, reaction product is through suction filtration, and the filter cake absolute ethanol washing can obtain tetrathio hydrazino formic acid.
In the synthesis technique of sulfide heavy metal chelating agent tetrathio hydrazino formic acid of the present invention, owing to selected hexalin to replace the ethylene glycol in the prior art, greatly reduce simultaneously the consumption of hexalin in mixed solvent, when improving yield, reduced production cost.Its technical superiority is mainly reflected in three aspects:
(1) take intelligent clever chemical industry net and Alibaba's Business service platform info quote on November 14th, 2012 as example: the ethylene glycol price is as 8000～8200 yuan/tons; 8500～13000 yuan/tons of hexalin prices.In the better embodiment of the present invention (embodiment 2), the volume ratio of hexalin and acetone is 0.2:1, and the density of hexalin is 0.9624 kg/L, and every liter of acetone needs 0.2 liter of hexalin, namely 2.50 yuan (according to 13000 yuan/tons of meters of your price).In the prior art, ethylene glycol and acetone volume ratio are 2:1 in the mixed solvent, and the density of ethylene glycol is 1.1155 kg/L, and every liter of acetone needs 2 liters of ethylene glycol, and namely 17.85 yuan (according to 8000 yuan/tons of meters of minimum rate) have reduced the mixed solvent cost.
(2) mol ratio of dithiocarbonic anhydride and hydrazine hydrate is preferably 1:0.91～1:1.11, under the prerequisite that guarantees product yield, has reduced the consumption of hydrazine hydrate, has reduced the load that follow-up raw material separates and reclaims.
(3) compared with prior art, product yield can reach more than 92% under the optimal conditions, is significantly improved.
The prepared sulfide heavy metal chelating agent tetrathio of the present invention hydrazino formic acid is a kind of efficient heavy ion-trapping agent.According to heavy metal ion kind and the concentration in the waste water, add an amount of sulfide heavy metal chelating agent of the present invention, also can be used with other water conditioners such as PAM, the heavy metal sulfide deposit seeds that generates is large, flco is closely knit, settling time is short, concentration of heavy metal ion in the processed waste water reaches discharging standards, and the recyclable heavy metal of the residue of generation is difficult for producing secondary pollution; This trapping agent also can be used for the noble metal in the recycle-water solution.
Sulfide heavy metal chelating agent of the present invention for the treatment of the trade effluent that contains heavy metal ion, can effectively be avoided the generation of hydrogen sulfide, at normal temperatures with waste water in Hg
2+, Cd
2+, Pb
2+, Mn
2+, Cu
2+, Ni
2+, Zn
2+React rapidly etc. heavy metal ion, generate water-insoluble sulfide precipitate.The preparation technology of sulfide heavy metal chelating agent of the present invention is simple, and is easy to use, and treatment effect is good.Can use separately, also can be used with other water conditioner.The sulfide precipitation particle of producing is large, flco is closely knit, has shortened the settling time, and the concentration of heavy metal ion in the waste water is reached below the emission standard of national regulation, and the recyclable heavy metal of the residue of generation is difficult for producing secondary pollution; This trapping agent also can be used for the noble metal in the recycle-water solution.Required equipment is simple, and is easy to operate, and expense is cheap, goes for circuit card, plating, metal finishing, film manufacturing, coal-fired plant, municipal administration or the industry wastewater treatments such as industrial refuse and incineration, battery production.
Describe the present invention below in conjunction with specific embodiment.Specific embodiment helps the understanding of the present invention and enforcement, and protection scope of the present invention is not limited with embodiment, and is limited by claim.
Description of drawings
The infrared spectrum of the tetrathio hydrazino formic acid of Fig. 1 embodiment of the invention 1 preparation.
Embodiment
A kind of preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid is as follows:
In the time of 32 ℃, 30 mL dithiocarbonic anhydride are dissolved in the mixed solvent of 5 mL hexalin and the formation of 5 mL acetone, slowly be added drop-wise to 34 mL 80%(wt%) in the there-necked flask of hydrazine hydrate (density is 1.019g/mL), stirring reaction 2.5 h, reaction product is through suction filtration, the filter cake absolute ethanol washing obtains heavy metal chelating trapping agent tetrathio hydrazino formic acid, and the transformation efficiency of dithiocarbonic anhydride is 85.48%.
Its infrared IR of prepared product and nuclear-magnetism NMR characterization result are as follows:
IR (KBr disk, cm
-1): 3315 s (ν-N-H), 3377 w (ν-S-H), 1088 m (ν-N-C=S), 1122 and 1347 ss (ν-C=S), 1515 ss (δ – N-N-), 1450 m (ν C-N), 958 m (ν C-S).
1H?NMR?(D
2O,?500?MHz)?δ(ppm)：1.87?(?SH,?2H),?2.15?(?-NH,?2H)。
Embodiment 2
Present embodiment prepares tetrathio hydrazino formic acid according to method substantially the same manner as Example 1, and difference is feed change proportioning and processing parameter, and the concrete technology condition reaches the results detailed in Table 1.
Embodiment 3
Present embodiment prepares tetrathio hydrazino formic acid according to method substantially the same manner as Example 1, and difference is feed change proportioning and processing parameter, and the concrete technology condition reaches the results detailed in Table 1.
Table 1
| | Embodiment | 1 | Embodiment 2 | Embodiment 3 |
| Dithiocarbonic anhydride/ |
30 | 30 | 30 | |
| Hydrazine hydrate/mL | 34 | 31 | 29 | |
| Hexalin/mL | 5 | 3.4 | 10 | |
| Acetone/mL | 5 | 16.6 | 5 | |
| Mixed solvent/mL | 10 | 20 | 15 | |
| Temperature of reaction/℃ | 32 | 30 | 35 | |
| Reaction times/h | 2.5 | 2 | 3 | |
| Dithiocarbonic anhydride transformation efficiency % | 85.48 | 92.96 | 87.51 |
Embodiment 4
Prepare respectively the copper sulfate (CuSO of 0.001mol/L
4) aqueous solution of the synthetic heavy metal chelating agent tetrathio hydrazino formic acid of solution, 0.001mol/L cupric ethylene diamine tetraacetate sodium (EDTA-Cu) solution and 0.001mol/L.And respectively get 10 mL CuSO
4Solution and EDTA-Cu solution are in Erlenmeyer flask.According to certain tetrathio carboxylamine and the mol ratio of cupric ion, quantitatively drip the tetrathio carboxylamine trapping agent of embodiment 1 preparation.Behind constant temperature oscillator vibration 15min, centrifugation 5 min get supernatant liquor and measure Cu at atomic absorption spectrophotometer
2+Concentration, and calculate Cu
2+Clearance.The results are shown in Table 2.
Table 2
| Mol ratio | Cu 2+ (CuSO 4)/ mg·L -1 | Clearance/% | Cu 2+ (EDTA-Cu)/ mg·L -1 | Clearance/% |
| 0.95 | 0.230 | 99.64 | 1.313 | 97.95 |
| 1.0 | 0.045 | 99.93 | 0.891 | 98.61 |
| 1.05 | 0.059 | 99.91 | 0.913 | 98.57 |
| 1.1 | 0.048 | 99.93 | 0.796 | 98.76 |
| 1.2 | 0.066 | 99.90 | 0.403 | 99.37 |
| 1.3 | 0.072 | 99.89 | 0.070 | 99.89 |
Embodiment 5
Select the electroplating wastewater of Zhenjiang company, record Cu
2+Concentration is 83.1 mg/L, Zn
2+Concentration is 11.8 mg/L, Pb
2+Concentration is 1.32 mg/L, Mn
2+Concentration is 0.03 mg/L, Ni
2+Concentration is 49.6 mg/L.
Add 600mg.L
-1The heavy metal chelating agent of embodiment 3 preparation, stir speed (S.S.) is 30 r.min
-1, after 15 min were stirred in reaction, centrifugation 10 min got that supernatant liquor is measured its Cu, Zn, Pb, Mn, Ni concentration is respectively 0.26 mg.L
-1, 0.41 mg.L
-1, 0.09 mg.L
-1, 0.03 mg.L
-1With 0.07 mg.L
-1, all reach discharging standards.
Sulfide heavy metal chelating agent of the present invention has the same performance that similarly captures to other heavy metal ion.
Claims (7)
1. the preparation method of a sulfide heavy metal chelating agent tetrathio hydrazino formic acid, it is characterized in that, dithiocarbonic anhydride is dissolved in the mixed solvent of hexalin and acetone composition, the mixing solutions of the dithiocarbonic anhydride that forms is added drop-wise in the hydrazine hydrate, stirring reaction 2～3 h can obtain tetrathio hydrazino formic acid.
2. the preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid according to claim 1, it is characterized in that: in the described mixed solvent, the volume ratio of hexalin and acetone is 2:1～0.2:1.
3. the preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid according to claim 1, it is characterized in that: in the mixing solutions of described dithiocarbonic anhydride, the volume ratio of dithiocarbonic anhydride and mixed solvent is 3:1～3:2.
4. the preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid according to claim 1, it is characterized in that: the mol ratio of described dithiocarbonic anhydride and hydrazine hydrate is 1:0.91～1:1.11.
5. the preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid according to claim 1, it is characterized in that: described temperature of reaction is 30～35 ℃.
6. the preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid according to claim 1, it is characterized in that: described reaction product is through suction filtration, and the filter cake absolute ethanol washing gets final product to get tetrathio hydrazino formic acid.
7. the preparation method of sulfide heavy metal chelating agent tetrathio hydrazino formic acid according to claim 1, it is characterized in that: the concrete preparation method of described sulfide heavy metal chelating agent tetrathio hydrazino formic acid is, at 30～35 ℃, 30 mL dithiocarbonic anhydride are dissolved in 20 mL hexalin and the acetone mixed solvent, wherein hexalin is 3.4 mL, the mixing solutions of the dithiocarbonic anhydride that forms slowly is added drop-wise to 31 mL 80%(wt%) in the hydrazine hydrate, stirring reaction 2 h, reaction product is through suction filtration, the filter cake absolute ethanol washing can obtain tetrathio hydrazino formic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601660A (en) * | 2013-10-29 | 2014-02-26 | 南京师范大学 | Heavy metal chelating trapping sulfide agent hexasulfoguanidinoformic acid or salt thereof, and preparation method and application thereof |
| CN104923168A (en) * | 2015-03-24 | 2015-09-23 | 信阳师范学院华锐学院 | Pomelo peel adsorbent modified with sulfo carbamates and preparation method of pomelo peel adsorbent |
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| CN105883998A (en) * | 2015-02-16 | 2016-08-24 | 达兴材料股份有限公司 | Heavy metal trapping agent and method for removing heavy metal in aqueous solution |
| CN107875561A (en) * | 2017-10-31 | 2018-04-06 | 武汉强丰新特科技有限公司 | A kind of selective chelating agent DMTD preparation method and applications of heavy metal ion |
| CN110204029A (en) * | 2019-05-25 | 2019-09-06 | 天津金辰博科环保科技发展有限公司 | A kind of heavy metal chelating agent and preparation method thereof |
| WO2020103847A1 (en) * | 2018-11-23 | 2020-05-28 | 北京师范大学 | Heavy metal removing preparation, synthesis method for same, and applications thereof |
| CN115772106A (en) * | 2022-11-04 | 2023-03-10 | 西北矿冶研究院 | Diamine bisdithiocarbamic acid sodium salt and preparation method thereof |
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|---|---|---|---|---|
| CN103601660A (en) * | 2013-10-29 | 2014-02-26 | 南京师范大学 | Heavy metal chelating trapping sulfide agent hexasulfoguanidinoformic acid or salt thereof, and preparation method and application thereof |
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| CN105883998A (en) * | 2015-02-16 | 2016-08-24 | 达兴材料股份有限公司 | Heavy metal trapping agent and method for removing heavy metal in aqueous solution |
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| CN104923168A (en) * | 2015-03-24 | 2015-09-23 | 信阳师范学院华锐学院 | Pomelo peel adsorbent modified with sulfo carbamates and preparation method of pomelo peel adsorbent |
| CN104923168B (en) * | 2015-03-24 | 2018-04-13 | 信阳学院 | A kind of thiocarbamate class is modified shaddock peel adsorbent and preparation method thereof |
| CN105330234A (en) * | 2015-10-29 | 2016-02-17 | 合肥正拓装饰材料有限公司 | Composite sintering-free water-permeable floor tile adding with modified shaddock peels and bagasse |
| CN107875561A (en) * | 2017-10-31 | 2018-04-06 | 武汉强丰新特科技有限公司 | A kind of selective chelating agent DMTD preparation method and applications of heavy metal ion |
| WO2020103847A1 (en) * | 2018-11-23 | 2020-05-28 | 北京师范大学 | Heavy metal removing preparation, synthesis method for same, and applications thereof |
| CN110204029A (en) * | 2019-05-25 | 2019-09-06 | 天津金辰博科环保科技发展有限公司 | A kind of heavy metal chelating agent and preparation method thereof |
| CN115772106A (en) * | 2022-11-04 | 2023-03-10 | 西北矿冶研究院 | Diamine bisdithiocarbamic acid sodium salt and preparation method thereof |
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Application publication date: 20130227 |