CN104399730B - A kind of Compound Heavy Metals stabilizer, preparation method and using method thereof containing carbodithioic acid functionalization star-like super-branched polymer - Google Patents
A kind of Compound Heavy Metals stabilizer, preparation method and using method thereof containing carbodithioic acid functionalization star-like super-branched polymer Download PDFInfo
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- 0 C**[C@@](C)CCCC(*)O*C(COC(CCNCC(C1)C(C23)C2C3C1N)(C1)C1O)=CC Chemical compound C**[C@@](C)CCCC(*)O*C(COC(CCNCC(C1)C(C23)C2C3C1N)(C1)C1O)=CC 0.000 description 1
- CGCVLTOGUMLHNP-UHFFFAOYSA-N CC(C)(C(C)(C)N)N Chemical compound CC(C)(C(C)(C)N)N CGCVLTOGUMLHNP-UHFFFAOYSA-N 0.000 description 1
- WDEWKYKJXKICEP-UHFFFAOYSA-N CCC(C)(C)CC(C)(C)CNC Chemical compound CCC(C)(C)CC(C)(C)CNC WDEWKYKJXKICEP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of Compound Heavy Metals stabilizer, preparation method and using method thereof containing carbodithioic acid functionalization star-like super-branched polymer, dithionate's functionalization star dissaving polymer and Alkylenediamine four dithionate by trimethylolpropane is core form, trimethylolpropane be dithionate's functionalization star dissaving polymer chemical formula of core be CH3CH2C[CH2OCOCH2CH2N(CSSM)CH2(CH2)nCH2N(CSSM)2]3, Alkylenediamine four dithionate's chemical formula (MSSC)2NCH2(CH2)nCH2N(CSSM)2, n is 0 ~ 10 positive integer, and M is Na+Or K+Deng.The present invention not only has efficient Stabilization and good anti acid alkali performance energy to heavy metal in incineration of refuse flyash, it is possible to decrease flying dust pollutes the risk of environment in long-term natural environment；Apply also for the waste water of heavy metal pollution and the process of soil.
Description
Technical field
The invention belongs to environmental protection technical field; particularly belong to the solid waste containing toxic heavy metal and field of waste water treatment, be specifically related to a kind of Compound Heavy Metals stabilizer, preparation method and using method thereof containing carbodithioic acid functionalization star-like super-branched polymer.
Background technology
Along with the development of urbanization process, Municipal Garbage Yield sustainable growth, meanwhile incineration treatment of garbage scale increases the most year by year.China's waste incineration scale is increased to 35,840,000 tons in 2012 by 369.9 ten thousand tons of 2003, average annual growth by 96.9%, by 2015, China's incineration treatment of garbage scale to reach 112,110,000 tons (" the application of city life garbage harmless treatment Facilities Construction planning of " 12 " whole nation ", 2012).
But after waste incineration, produce in the flying dust of about 2% ~ 5% containing toxic heavy metals such as As, Cd, Cr, Hg, Pb, it is impossible to directly fill, it is necessary to after reaching the Con trolling index that this standard specifies after process, household refuse landfill sites of being allowed for access fills.
The processing method of flying dust has: embathe method, heat treating process, solidification/stabilization method, chemical agent stabilization method.Wherein chemical agent stabilization method is owing to operating cost is low by extensive concern, and the most Japanese in developed country, the main process disposal options of flying ash is " chemical agent stable+landfill ".
The most conventional flying ash chemical stabilizer has: (1) inorganic medicament such as Calx, phosphoric acid salt, iron salt class (ferrous salt, iron oxides), carbonate, sulfide (sodium thiosulfate, sodium sulfide), aluminium oxide, sodium hydroxide etc.；(2) organic medicament such as thiourea, ethylenediaminetetraacetic acid (EDTA), organic disulfide is for carbaminate and thiophosphate, organic phosphonate, chitosan derivatives etc..
As Chinese patent application 200510011651.1 discloses by the method for soluble phosphate stabilizing flying ash from burn, soluble phosphate includes orthophosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, tertiary sodium phosphate, chemical feeding quantity during its stabilisation flying dust is bigger, usually the 3% ~ 10% of flying dust weight, select any phosphate will be according to the pH of leachate, if pH > 12, then select the one in disodium-hydrogen, sodium dihydrogen phosphate, tertiary sodium phosphate.But PO4 3-The product of stabilisation, in the environment of pH5 ~ 9, is easily converted into H2PO4 -、HPO4 2-(Grubb D. G., Guimaraes M.
S. Valencia R., 2000. Phosphate immobilization using all acidic type fly ash.
J. Hazard. Mater., 76 (2): 217-236), so that heavy metal leaches again, and < when 5, phosphate actually heavy metal loses Stabilization, and therefore pH value plays a key effect in the stabilization procedures of soluble phosphoric acid at pH.For flying dust, whether GB HEVP method, or the pH of TPLC the leaching program, generally its leachate of the U.S. is more than 10, makes phosphate that the stabilization effect of flying dust has been had guarantee.But in long-term natural environment, acid rain can gradually neutralize the alkaline matter of flying dust, and during now flying dust is at the external environment condition of pH < 5, the leaching of heavy metal can quickly increase.The capacity antacid of the most phosphate-stabilized stabilizing fly ash product is not enough, adds its long-term security risks.
Inorganic sulphide is based on generating insoluble metal sulfide (MS) to the stabilisation of flying dust, so that heavy metal is stablized, chemical feeding quantity is usually 3% ~ 10%(Quina M. J., Bordado J.C. of flying dust weight
M., Quinta-Ferreira R. M., 2010. Chemical stabilization of air pollution
control residues from municipal solid waste incineration. Hazard. Mater.
179 (1-3): 382-392.), but sulfide is similar with soluble phosphate, only could effectively stablize the heavy metal in flying dust in the range of certain pH.
All there is the problem that chemical feeding quantity is big, capacity antacid is poor in the inorganic salt stabilization agents such as same iron salt class, carbonate, hydroxide.
Organic stabilizer kind mainly has: thiourea, ethylenediaminetetraacetic acid (EDTA), organic phosphonate, organic disulfide are for carbaminate, thiophosphate etc..
Organic stabilizer thiourea is stablized the effect of heavy metal in flying dust and is substantially better than inorganic matter sodium sulfide, when the addition of thiourea is the 0.7% of flying dust weight, the leaching of Pb can be made to be less than GB limit value, and sodium sulfide needs dosage (the Zhao Y. C. of 5%, Song L.J., Li
G. J., 2002. Chemical stabilization of MSW incinerator fly ashes. J. Hazard.
Mater. 95 (1-2): 47 63.).The Stabilization of thiourea also relies on pH, leachate pH is < when 8 (digestion agent of pH=1), the leaching of heavy metal quickly increases (Chen Dan, money light people, Zhang Houhu, Zhu Huajun, 2006. tea saponins are stablized and modification incineration of refuse flyash experimental study [J]. Northcentral University's journal (natural science edition). and 27 (6): 519-523.).
The Stabilization of ethylenediaminetetraacetic acid (EDTA) heavy metal is also relied on pH, must be at pH > 10 time use (Liu Yuanyuan, Austria in king, Lin Xiang, Cui Zhiqiang, Luo Yu, Hu Gang, 2007. city garbage burning flying ash heavy metal medicament compatibility stabilisation experimentation [J]. environmental project journal, 1 (10): 94-99.), therefore EDTA capacity antacid is the best.
China granted patent ZL 200410067071.X discloses use organic phosphonate and stablizes the technology of heavy metal in flying dust, but organic phosphonate capacity antacid poor (Zhang Houhu etc. Phosphonic Acid HEDP stablizes the research [J] of incineration of refuse flyash heavy metal. Techniques and Equipment for Environmental Pollution Control, 2006,7 (11): 45-48.).
In recent years, occur in that a class class novel stabilizing fly ash agent as chelation group with nabam (DTC) and dithio phosphinylidyne salt (DTP), as Chinese patent application 200410090662.9 discloses the nabam class stabilizing fly ash agent with polymine as basic framework；China's granted patent 200710190138.2 discloses the stabilizing fly ash agent using dialkyl dithiophosphate compounds compounding with flocculant；Chinese patent application 200810032233.4 discloses the stabilizing fly ash agent using dialkyl dithiocarbamate.These organic stabilizers all have the effect of good stabilizing heavy metal.
The evaluation of above-mentioned inorganic and organic stabilizer is all the effect evaluating medicament by old GB " hazardous waste judging standard-leaching characteristic identification (GB5086.2-1997) ", enforcement along with new GB " household refuse landfill sites Environmental capacity standard (GB16889-2008) ", stabilizing fly ashization is processed the requirement proposing tightened up harshness, the leaching concentration that the leaching concentration of such as Pb is reduced to 0.25mg/L, Cd by original 3mg/L is reduced to 0.15mg/L by original 0.3mg/L.Above-mentioned inorganic and organic stabilizer such as to meet new standard, generally requires more pharmaceutical quantities, and processing cost will be greatly improved.Such as when processing the flying dust of certain garbage burning factory with sodium phosphate (Zhou Bin etc., 2009), when dosage is 10%, its Pb leaching concentration is 0.46mg/L, meet the concentration limit of old GB (GB5086.2-1997) 3mg/L, but new GB (GB16889-2008) can not be met, when 30% that chemical feeding quantity is flying dust, the leaching concentration of Pb is 0.27mg/L, still can not meet the concentration limit of new national standard 0.25mg/L.The enforcement of new national standard is had higher requirement to chemical stabilizer.
Therefore, need badly in terms of the research of incineration of refuse flyash stabilizer and seek a kind of novel, efficient, stabilizer that capacity antacid is strong, the breakthrough in structure must be sought, and then improve itself and the binding ability of heavy metal in flying dust, to the flying dust chemical stabilizer obtained efficiently, capacity antacid is strong.
Polymer is developed so far, and in traditional one-dimensional linear, two dimension crosslinking or Slight branching polymer base, occurs in that a class has the highly-branched polymers of three-D space structure.Highly branched polymer can be divided into dendritic, dissaving polymer, star dissaving polymer, star miscellaneous arm dissaving polymer etc. from architectural feature.Dendritic has the polymer of regular texture, and dissaving polymer has the polymer of irregular structure.Star polymer refers to that the side chain of three or more than three is connected in the dissaving polymer on same centronucleus by chemical bond.The chemical composition of each side chain is identical, and molecular weight should not have difference.Star polymer has three-dimensional flakes structure, is the special highly-branched polymers of a class.And Miktoarm star polymer at least side chain or molecular size range different from other side chain in chemical composition has significant difference.
Enter 21 century, the highly-branched polymers of non-linearity is due to its special structure, in having won world wide, the common concern of increasing scientist, has important application prospect in the various fields such as industry, agricultural, national defence, biomedicine, slow-release material, catalysis.
The present invention is then as incinerating flyash, heavy metal stabilizer using dithionate's functionalization star dissaving polymer that trimethylolpropane trimethacrylate is core, with Alkylenediamine four dithionate's compound use, between two kinds of compositions of this complex stabilizer, there is good synergism, not only there is the performance of heavy metal in good stable flying dust, and the heavy metal after stable has the resistance soda acid impact capacity of excellence, it is ensured that the flying dust of stabilisation long-time stability in the environment.
Summary of the invention
It is an object of the invention to overcome existing inorganic stabilizers and the major part weakness that organic stabilizer consumption is big, acid-resisting is not enough, there is provided a kind of in flying dust, heavy metal stabilizing energy is good, resist soda acid ability is strong, have new structure a kind of complex stabilizer containing carbodithioic acid functionalization star-like super-branched polymer, preparation method and using method thereof, to reach to control incineration of refuse flyash stabilizing treatment cost, meet the long-term safety requirement that flying dust processes.
For achieving the above object, a kind of complex stabilizer containing carbodithioic acid functionalization star-like super-branched polymer, described complex stabilizer is made up of, wherein dithionate's functionalization star dissaving polymer that trimethylolpropane is core and Alkylenediamine four dithionate: described trimethylolpropane trimethacrylate is dithionate's functionalization star dissaving polymer of core and the mol ratio of Alkylenediamine four dithionate is 1:1.0 ~ 3.0.
In the present invention, described trimethylolpropane is that the chemical formula of dithionate's functionalization star dissaving polymer of core is: CH3CH2C[CH2OCOCH2CH2N(CSSM)
CH2 (CH2)nCH2N(CSSM)2]3, in formula, n is the positive integer between 0 ~ 10, and its structural formula is:
In formula, n is the positive integer between 0 ~ 10, and M is Na+、K+Or NH4 +In any one.
In the present invention, the chemical formula of described Alkylenediamine four dithionate is: (NaSSC)2NCH2(CH2)nCH2N
(CSSNa)2, its structural formula is:
In formula, n is the positive integer between 0 ~ 10, and M is Na+、K+Or NH4 +In any one.
In the stable incineration of refuse flyash that the present invention proposes, the preparation method of the complex stabilizer of heavy metal, specifically comprises the following steps that
(1) by Alkylenediamine (H2NCH2(CH2)nCH2NH2N is the positive integer between 0 ~ 10, Alkylenediamine, is called for short ADA) and methanol add with stirring, reflux condensing tube and thermometer four-hole boiling flask in; then less than 10 DEG C, nitrogen protection and stirring condition under, be slowly added dropwise trimethylolpropane trimethacrylate (C2H5C(CH2OOCHC=CH2)3, Trimethylolpropane
Triacrylate, is called for short TMPTA) alcoholic solution, and control rate of addition, make temperature be less than 10 DEG C；Drip and finish, heat up, at 25 ~ 30 DEG C, react 20 ~ 48 hr, obtain trimethylolpropane core Alkylenediamine end group star dissaving polymer (Trimethylolpropane
Triacrylate/Alkylenediamine star hyperbranched polymer, is called for short TMPTA/ADA) and the mixture of Alkylenediamine (ADA), reaction equation is as follows:
In formula, n is the positive integer between 0 ~ 4；Trimethylolpropane trimethacrylate, the mol ratio of Alkylenediamine are 1:4.0 ~ 6.0；
(2) in trimethylolpropane core Alkylenediamine end group star dissaving polymer (TMPTA/ADA) prepared to step (1) and the mixture of Alkylenediamine (ADA), it is slowly added to alkaline solution, controlling rate of addition, making reaction mixture temperature is 5 ~ 10 DEG C；Then drip the alcoholic solution of Carbon bisulfide, control rate of addition and make reaction mixture temperature be 5 ~ 10 DEG C；After dropping, in the conditioned response 2 ~ 5 hours of 5 ~ 10 DEG C；Then, rise to 25 DEG C, continue reaction 3 ~ 5 hours；Reaction mixture is stood overnight, white precipitate is i.e. had to separate out, after filtration, clean with a small amount of alcohol, refilter, obtaining target product trimethylolpropane trimethacrylate core dithionate's functionalization star dissaving polymer (be called for short TMPTA/ADA-9CSSM) and the complex stabilizer of Alkylenediamine four dithionate (ADA-4CSSM), trimethylolpropane trimethacrylate core Alkylenediamine end group star dissaving polymer and Alkylenediamine mixture (counting with NH), Carbon bisulfide, the mol ratio of alkali are (NH:CS2: MOH) it is 1:1.25 ~ 1.50:1.25 ~ 1.50；Reaction equation is as follows:
。
In the present invention, raw material trimethylolpropane trimethacrylate, Carbon bisulfide used are commercially available product.
In the present invention, Alkylenediamine class used is commercially available product, and its chemical formula is: NH2CH2(CH2)n
CH2NH2, wherein n is the positive integer between 0 ~ 4.
In the present invention, alkali used is any one in sodium hydroxide, potassium hydroxide or ammonia, is commercially available product.
In the present invention, alcohol used is any one in methanol, ethanol, propanol or butanol etc., is commercially available product.
In the stable incineration of refuse flyash that the present invention proposes, the using method of the complex stabilizer of heavy metal, specifically comprises the following steps that
Complex stabilizer water being prepared as solution, is then added in a certain amount of flying ash, addition is the 0.5 ~ 5% of flying dust weight, continuously stirred 15 ~ 30 minutes, is then dried under the conditions of gravity-flow ventilation, is flying ash stabilizing product.
The complex stabilizer that the present invention prepares is being composited by trimethylolpropane core dithionate functionalization star dissaving polymer (TMPTA/ADA-9CSSM) and Alkylenediamine four dithionate (ADA-4CSSM), wherein star dissaving polymer be end group be dithionate, core be the star dissaving polymer of trimethylolpropane, be a kind of novel dissaving polymer.Experiment shows, complex stabilizer provided by the present invention, wherein trimethylolpropane core dithionate functionalization star dissaving polymer, because of the highly branched structure that it is special, can effectively stablize the heavy metal in flying dust, and with Alkylenediamine four dithionate's compound use, have to work in coordination with and just promoting effect, compared with similar medicament widely used with on market, chemical feeding quantity is low, possesses the ability of good antiacid alkali impact while stabilizing heavy metal.
The complex stabilizer that the present invention provides can not only stablize the heavy metal in incineration of refuse flyash effectively, there is the strongest ability resisting soda acid impact, can be widely applied to incineration of refuse flyash process it can also be used to contain sewage treatment area and the reparation of heavy-metal contaminated soil of heavy metal.
Accompanying drawing explanation
In order to make the object, technical solutions and advantages of the present invention clearer, the following examples will the invention will be further described in conjunction with accompanying drawing, Fig. 1 ~ 5 are and use the salpeter solution of different pH value and sodium hydroxide solution as digestion agent, according to the program of " solid waste Leaching leaching method hac buffer method (HJ/T300-2007) " to the result carrying out Leaching test before and after stabilisation, wherein:
Fig. 1 is the leachate pH impact on As Leaching.
Fig. 2 is the leachate pH impact on Cd Leaching.
Fig. 3 is the leachate pH impact on Cr Leaching.
Fig. 4 is the leachate pH impact on Hg Leaching.
Fig. 5 is the leachate pH impact on Pb Leaching.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in further detail.Finally should be noted that, following example are only in order to illustrate technical scheme and unrestricted, although the present invention being described in detail with reference to preferred embodiment, it will be understood by those within the art that, the technical scheme of invention can be modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, it all should be contained in scope of the presently claimed invention.
Comparative examples below 1 ~ 2 is commercially available stabilizer.
Comparative example:Inorganic stabilizers sodium sulfide (Na2S).
Embodiment
1
: trimethylolpropane core dithionate's functionalization star dissaving polymer and the preparation of hexamethylene diamine four carbodithioic acid sodium complex stabilizer
By 29.00 g(0.25 mol) hexamethylene diamine (1; 6-Hexanediamine; hereinafter referred to as HDA) and 29.0 0g methanol add in the four-hole boiling flask of configuration stirring, reflux condensing tube and thermometer; then less than 10 DEG C, nitrogen protection and stirring condition under; it is slowly added dropwise 29.60 g(50.00%; 0.05 mol) methanol solution of trimethylolpropane trimethacrylate (TMPTA), and control rate of addition, make temperature be less than 10 DEG C.Then heat to 25 DEG C, react 24hr, obtain trimethylolpropane core hexamethylene diamine end group star dissaving polymer (Trimethylolpropane
Triacrylate/Hexanediamine star hyperbranched polymer, is called for short TMPTA/HDA) and the mixture of hexamethylene diamine (HDA).
Be subsequently cooled to 10 DEG C, be slowly added to 88.40 g(50.00%, 1.105 mol) sodium hydroxide solution, control rate of addition, making reaction mixture temperature is less than 10 DEG C.Drip and finish, then drip 167.96 g(50.00%, 1.105 mol) methanol solution of Carbon bisulfide, control rate of addition, make reaction mixture temperature be less than 10 DEG C.Drip and finish, react 5 hours in 10 DEG C.Then 25 DEG C are risen to, stand overnight after continuing reaction 5 hours, white precipitate is i.e. had to separate out, after filtration, clean with a small amount of methanol, refilter, obtain 121.26 g white product, being trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer (TMPTA/HDA-9CSSNa) and the complex stabilizer of hexamethylene diamine four carbodithioic acid sodium (HDA-4CSSNa), yield 95.41%, wherein the mol ratio of TMPTA/HDA-9CSSNa Yu HAD-4CSSNa is 1:2.0.
Gained complex stabilizer13C nuclear magnetic resoance spectrum (D2O) be: 7.26,21.18,26.34,26.51,26.77,26.98,27.42,27.89,48.22,49.09,51.29,31.33,36.25,45.23,69.13,177.26,209.27,211.29,219.56ppm.Illustrate that this complex stabilizer is trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer and the mixture (TMPTA/HDA-9CSSNa+2.0 of hexamethylene diamine four carbodithioic acid sodium
HAD-4CSSNa), its structure is as follows:
Embodiment
2
: trimethylolpropane core dithionate's functionalization star dissaving polymer and the preparation of butanediamine four carbodithioic acid sodium complex stabilizer
22.00 g(0.25mol) butanediamine (1; 4-Butanediamine; hereinafter referred to as BDA) and 22.0 0g ethanol add in the four-hole boiling flask of configuration stirring, reflux condensing tube and thermometer; then less than 10 DEG C, nitrogen protection and stirring condition under; it is slowly added dropwise 29.60 g(50.00%; 0.05 mol) methanol solution of trimethylolpropane trimethacrylate (TMPTA), and control rate of addition, make temperature be less than 10 DEG C.Then heat to 25 DEG C, react 22hr, obtain trimethylolpropane core butanediamine end group star dissaving polymer (Trimethylolpropane
Triacrylate/Butanediamine star hyperbranched polymer, is called for short TMPTA/BDA) and the mixture of butanediamine (BDA).
Be subsequently cooled to 10 DEG C, be slowly added to 95.20 g(50.00%, 1.19 mol) sodium hydroxide solution, control rate of addition, making reaction mixture temperature is less than 10 DEG C.Drip and finish, then drip 180.88 g(50.00%, 1.19 mol) ethanol solution of Carbon bisulfide, control rate of addition, make reaction mixture temperature be less than 10 DEG C.Drip and finish, react 5 hours in 10 DEG C.Then 25 DEG C are risen to, stand overnight after continuing reaction 4 hours, white precipitate is i.e. had to separate out, after filtration, clean with a small amount of methanol, refilter, obtain 114.12 g white product, being trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer (TMPTA/BDA-9CSSNa) and the complex stabilizer of butanediamine four carbodithioic acid sodium (BDA-4CSSNa), yield 95.02%, wherein the mol ratio of TMPTA/BDA-9CSSNa Yu BAD-4CSSNa is 1:2.0.
Gained complex stabilizer13C nuclear magnetic resoance spectrum (D2O) it is: 7.81,22.41,24.35,25.68,26.78,31.43,37.23,46.24,47.55,48.95,52.17,68.32,176.89,201.25,205.36,209.12 ppm.Illustrating that this complex stabilizer is trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer and the mixture (TMPTA/BDA-9CSSNa+2.0BAD-4CSSNa) of butanediamine four carbodithioic acid sodium, its structure is as follows:
Embodiment
3
: trimethylolpropane core dithionate's functionalization star dissaving polymer and the preparation of ethylenediamine tetraacetic carbodithioic acid sodium complex stabilizer
18.00 g(0.30 mol) ethylenediamine (Ethylenediamine; hereinafter referred to as EDA) and 18.0 0g methanol add in the four-hole boiling flask of configuration stirring, reflux condensing tube and thermometer; then less than 10 DEG C, nitrogen protection and stirring condition under; it is slowly added dropwise 29.60 g(50.00%; 0.05 mol) methanol solution of trimethylolpropane trimethacrylate (TMPTA); and control rate of addition, make temperature be less than 10 DEG C.Then heat to 25 DEG C, react 24hr, obtain trimethylolpropane core ethylenediamine end group star dissaving polymer (Trimethylolpropane triacrylate/Ethylenediamine
Star hyperbranched polymer, is called for short TMPTA/EDA) and the mixture of ethylenediamine (EDA), wherein the mol ratio of TMPTA/EDA Yu EDA is 1:3.
Be subsequently cooled to 10 DEG C, be slowly added to 126.00 g(50.00%, 1.575 mol) sodium hydroxide solution, control rate of addition, making reaction mixture temperature is less than 10 DEG C.Drip and finish, then drip 207.48 g(50.00%, 1.365 mol) methanol solution of Carbon bisulfide, control rate of addition, make reaction mixture temperature be less than 10 DEG C.Drip and finish, react 5 hours in 10 DEG C.Then 25 DEG C are risen to, stand overnight after continuing reaction 5 hours, white precipitate is i.e. had to separate out, after filtration, clean with a small amount of methanol, refilter, obtain 130.35 g white product, being trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer (TMPTA/EDA-9CSSNa) and the complex stabilizer of ethylenediamine tetraacetic carbodithioic acid sodium (EDA-4CSSNa), yield 96.06%, wherein the mol ratio of TMPTA/EDA-9CSSNa Yu EDA-4CSSNa is 1:3.0.
Gained complex stabilizer13C nuclear magnetic resoance spectrum (D2O) it is: 7.92,22.15,34.27,37.53,48.92,50.67,53.57,55.78,68.92,177.93,207.82,215.23,218.87 ppm.Illustrate that this complex stabilizer is trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer and the mixture (TMPTA/EDA-9CSSNa+3.0 of ethylenediamine tetraacetic carbodithioic acid sodium
EAD-4CSSNa), its structure is as follows:
Embodiment
4
: the stabilizing treatment of flying ash
Flying ash derives from certain garbage burning factory, the acetic acid that the detection of its Leaching uses industry standard " solid waste Leaching leaching method hac buffer method (HJ/T300-2007) " to specify carries out Leaching test, its pollutant catabolic gene standard is " household refuse landfill sites Environmental capacity standard (GB16889-2008) ", and test result is shown in Table 1.In this flying dust visible, the leaching concentration of Pb is higher, exceedes the Extraction Toxicity Identification Standard of Hazardous Waste of national regulations, and other heavy metal element is without exceeding standard.
Table 1 original fly-ash heavy metal Leaching/mg L-1-1
| Content | As | Cd | Cr | Cu | Hg | Ni | Pb | Zn |
| Leaching | 0.037 | 0.086 | 0.009 | 0.037 | 0.047 | 0 | 11.289 | 0.165 |
| GB limit value | 0.3 | 0.15 | 4.5 | 40 | 0.05 | 0.5 | 0.25 | 100 |
The complex stabilizer being made up of trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer and Alkylenediamine four carbodithioic acid sodium that above-described embodiment 1 ~ 3 is prepared, and the sodium sulfide of comparative example is applied to incineration of refuse flyash stabilizing treatment, method is as follows: be dissolved in 40ml deionized water by a certain amount of stabilization agent, after stirring, add 100g flying ash, stir 30 minutes, form thick shape compound.Then this mixture is dried under the conditions of gravity-flow ventilation, is flying ash stabilizing product.
Stabilisation product carries out Leaching test according to " solid waste Leaching leaching method hac buffer method (HJ/T300-2007) ", its pollutant catabolic gene standard is " household refuse landfill sites Environmental capacity standard (GB16889-2008) ", and experimental result is shown in Table 2.
The Leaching Heavy Metals of table 2 stabilizing fly ash product
From the data of table 2 it can be seen that the stablizing effect of complex stabilizer prepared by the present invention is fine, when addition is flying dust weight the 2.0% of stabilization agent, in the flying dust that complex stabilizer is stable, the leaching concentration of Pb significantly reduces；When 2.0% that dosage is flying dust weight, the concentration limit during the leaching concentration of Pb and Hg is below household refuse landfill sites Environmental capacity standard in stable flying dust.
And when in comparative example, the dosage of sodium sulfide is the 10% of flying dust, the pollutant levels limit value in the leaching concentration of Pb still above " household refuse landfill sites Environmental capacity standard (GB16889-2008) " in the flying dust after stabilizing treatment.
Embodiment
4
: the flying dust capacity antacid test of chemical stabilization
The salpeter solution of the different pH value of employing and sodium hydroxide solution are as digestion agent, according to the leaching program of " solid waste Leaching leaching method hac buffer method (HJ/T300-2007) ", the flying dust of the chemical stabilization of the 5% of original flying dust and flying dust quality is carried out Leaching test, result see Fig. 1 ~ 5(due in original flying dust the leaching of Cu, Ni, Zn less than GB, therefore do not list).
Owing to the Comparison of experiment results of the complex stabilizer of embodiment 1,2,3 gained is close, better than conventional stabilizer sodium sulfide and thiourea, therefore trimethylolpropane core carbodithioic acid sodium functionalization star dissaving polymer and the complex stabilizer (TMPTA/HDA-9CSSNa+2.0 of hexamethylene diamine four carbodithioic acid sodium of embodiment 1 gained is listed in Fig. 1 ~ 5
HAD-4CSSNa), in figure, pH is leachate pH rather than digestion agent pH, in order to the acid-proof alkaline of the medicament of the present invention is better described.
As can be seen from the results, flying dust after the complex stabilizer stabilizing treatment of the present invention, anti acid alkali performance can be excellent, as leachate pH 1.25 ~ 6.45, flying dust after the complex stabilizer stabilizing treatment of the present invention, the leaching concentration of its As, Cd, Cr, Hg, Ni, Pb is minimum, the Leaching of Heavy Metals concentration specified less than " household refuse landfill sites Environmental capacity standard (GB16889-2008) ", and the flying dust after conventional stabilizer sodium sulfide stabilizing treatment, the leaching of heavy metal is then higher than GB limit value.As leachate pH > 12.16, flying dust after the complex stabilizer stabilizing treatment of the present invention, the leaching concentration of its Pb is minimum, the Leaching of Heavy Metals concentration specified less than " household refuse landfill sites Environmental capacity standard (GB16889-2008) ", and the flying dust after conventional stabilizer sodium sulfide stabilizing treatment, the leaching of heavy metal is then higher than GB limit value.
Therefore the complex stabilizer being made up of trimethylolpropane core dithionate's functionalization star dissaving polymer and Alkylenediamine four dithionate of the present invention, there is excellent anti acid alkali performance energy, improve the safety under long-term natural environment of the flying dust of stabilisation.
Claims (5)
1. the Compound Heavy Metals stabilizer containing carbodithioic acid functionalization star-like super-branched polymer, it is characterized in that described complex stabilizer is made up of, wherein dithionate's functionalization star dissaving polymer that trimethylolpropane is core and Alkylenediamine four dithionate: described trimethylolpropane is dithionate's functionalization star dissaving polymer of core and the mol ratio of Alkylenediamine four dithionate is 1:1.0 ~ 3.0；The preparation method of Compound Heavy Metals stabilizer specifically comprises the following steps that
(1) by Alkylenediamine H2NCH2(CH2)nCH2NH2, n is the positive integer between 0 ~ 10, and methanol add with stirring, reflux condensing tube and thermometer four-hole boiling flask in, then less than 10 DEG C, under nitrogen protection and stirring condition, be slowly added dropwise trimethylolpropane trimethacrylate (C2H5C(CH2OOCHC=CH2)3) alcoholic solution, and control rate of addition, make temperature be less than 10 DEG C；Dripping and finish, heat up, at 25 ~ 30 DEG C, react 20 ~ 48 hr, obtain trimethylolpropane core Alkylenediamine end group star dissaving polymer and the mixture of Alkylenediamine, reaction equation is as follows:
In formula, n is the positive integer between 0 ~ 4；Trimethylolpropane trimethacrylate, the mol ratio of Alkylenediamine are 1:4.0 ~ 6.0；
(2) in the trimethylolpropane core Alkylenediamine end group star dissaving polymer prepared to step (1) and the mixture of Alkylenediamine, being slowly added to alkaline solution, control rate of addition, making reaction mixture temperature is 5 ~ 10 DEG C；Then drip the alcoholic solution of Carbon bisulfide, control rate of addition and make reaction mixture temperature be 5 ~ 10 DEG C；After dropping, in the conditioned response 2 ~ 5 hours of 5 ~ 10 DEG C；Then, rise to 25 DEG C, continue reaction 3 ~ 5 hours；Reaction mixture is stood overnight, white precipitate is i.e. had to separate out, after filtration, clean with alcohol, refilter, obtaining target product trimethylolpropane trimethacrylate core dithionate's functionalization star dissaving polymer and the complex stabilizer of Alkylenediamine four dithionate, trimethylolpropane trimethacrylate core Alkylenediamine end group star dissaving polymer and Alkylenediamine mixture (counting with NH), Carbon bisulfide, the mol ratio of alkali are (NH:CS2: MOH) it is 1:1.25 ~ 1.50:1.25 ~ 1.50；Reaction equation is as follows:
。
Compound Heavy Metals stabilizer the most according to claim 1, it is characterised in that described trimethylolpropane is that the chemical formula of dithionate's functionalization star dissaving polymer of core is: CH3CH2C[CH2OCOCH2CH2N(CSSM)
CH2 (CH2)nCH2N(CSSM)2]3, in formula, n is the positive integer between 0 ~ 10, and its structural formula is:
In formula, n is the positive integer between 0 ~ 10, and M is Na+、K+Or NH4 +In any one.
Compound Heavy Metals stabilizer the most according to claim 1, it is characterised in that the chemical formula of described Alkylenediamine four dithionate is: (NaSSC)2NCH2(CH2)nCH2N
(CSSNa)2, its structural formula is:
In formula, n is the positive integer between 0 ~ 10, and M is Na+、K+Or NH4 +In any one.
4. the preparation method of a Compound Heavy Metals stabilizer as claimed in claim 1, it is characterised in that specifically comprise the following steps that
(1) by Alkylenediamine H2NCH2(CH2)nCH2NH2, n is the positive integer between 0 ~ 10, and methanol add with stirring, reflux condensing tube and thermometer four-hole boiling flask in, then less than 10 DEG C, under nitrogen protection and stirring condition, be slowly added dropwise trimethylolpropane trimethacrylate (C2H5C(CH2OOCHC=CH2)3) alcoholic solution, and control rate of addition, make temperature be less than 10 DEG C；Dripping and finish, heat up, at 25 ~ 30 DEG C, react 20 ~ 48 hr, obtain trimethylolpropane core Alkylenediamine end group star dissaving polymer and the mixture of Alkylenediamine, reaction equation is as follows:
In formula, n is the positive integer between 0 ~ 4；Trimethylolpropane trimethacrylate, the mol ratio of Alkylenediamine are 1:4.0 ~ 6.0；
(2) in the trimethylolpropane core Alkylenediamine end group star dissaving polymer prepared to step (1) and the mixture of Alkylenediamine, being slowly added to alkaline solution, control rate of addition, making reaction mixture temperature is 5 ~ 10 DEG C；Then drip the alcoholic solution of Carbon bisulfide, control rate of addition and make reaction mixture temperature be 5 ~ 10 DEG C；After dropping, in the conditioned response 2 ~ 5 hours of 5 ~ 10 DEG C；Then, rise to 25 DEG C, continue reaction 3 ~ 5 hours；Reaction mixture is stood overnight, white precipitate is i.e. had to separate out, after filtration, clean with alcohol, refilter, obtaining target product trimethylolpropane trimethacrylate core dithionate's functionalization star dissaving polymer and the complex stabilizer of Alkylenediamine four dithionate, trimethylolpropane trimethacrylate core Alkylenediamine end group star dissaving polymer and Alkylenediamine mixture (counting with NH), Carbon bisulfide, the mol ratio of alkali are (NH:CS2: MOH) it is 1:1.25 ~ 1.50:1.25 ~ 1.50；Reaction equation is as follows:
。
5. stablize the using method of the complex stabilizer of heavy metal in incineration of refuse flyash as claimed in claim 1 for one kind, it is characterised in that specifically comprise the following steps that
Compound Heavy Metals stabilizer water being prepared as solution, is then added in flying ash, addition is the 0.5 ~ 5% of flying dust weight, continuously stirred 15 ~ 30 minutes, is then dried under the conditions of gravity-flow ventilation, is flying ash stabilizing product.
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| CN111100052B (en) * | 2019-12-02 | 2021-01-12 | 同济大学 | Ethoxylated trimethylolpropane core hyperbranched polymer with dithio carboxylate as side group and end group and application of ethoxylated trimethylolpropane core hyperbranched polymer to chelated metal |
| CN111072985B (en) * | 2019-12-02 | 2021-09-21 | 同济大学 | Ethoxylated pentaerythritol core hyperbranched polymer with dithio-carboxylate as side group and end group and application of ethoxylated pentaerythritol core hyperbranched polymer in heavy metal chelation |
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| CN112851282A (en) * | 2021-01-27 | 2021-05-28 | 中钢集团马鞍山矿山研究总院股份有限公司 | Gelling agent for solidifying heavy metal ions in tailings and application method thereof |
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