CN104178177B - A kind of macromolecule chromium stabilizer and preparation method thereof and its application - Google Patents
A kind of macromolecule chromium stabilizer and preparation method thereof and its application Download PDFInfo
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- CN104178177B CN104178177B CN201410396402.8A CN201410396402A CN104178177B CN 104178177 B CN104178177 B CN 104178177B CN 201410396402 A CN201410396402 A CN 201410396402A CN 104178177 B CN104178177 B CN 104178177B
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- 239000011651 chromium Substances 0.000 title claims abstract description 78
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 68
- 239000003381 stabilizer Substances 0.000 title claims abstract description 49
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002689 soil Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003814 drug Substances 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000012264 purified product Substances 0.000 claims description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000006641 stabilisation Effects 0.000 abstract description 7
- 238000011105 stabilization Methods 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000013522 chelant Substances 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000003068 static effect Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002920 hazardous waste Substances 0.000 description 7
- 230000007774 longterm Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- -1 i.e. Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 210000003238 esophagus Anatomy 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a kind of macromolecule chromium stabilizer, preparation method and applications.The present invention prepares using alkyl polyoxyethylene ether and succinic anhydride as raw material and contains alkyl, ether, four kinds of functional groups of ester group and carboxyl in a kind of macromolecule chromium stabilizer of without phosphorus nitrogen-free environmental protection, its molecular structure.Wherein, ester group and carboxyl have very excellent effect to chelating heavy metal chromium ion, and alkyl and ether can promote the combination of chelate and soil particle, play good static stabilization.The invention also discloses the application method of the stabilizer, by being used with slag cheap and easy to get, bed mud and diatom earth cooperation, using slag reduction of hexavalent chromium, using bed mud and the further Adsorption of Chromium of diatomite, the repairing effect for first reducing and stablizing afterwards is reached.
Description
Technical field：
Field is repaired the invention belongs to the heavy metal in environment remediation, and in particular to a kind of macromolecule chromium stabilizer and its system
Preparation Method and application.
Technical background：
Chromium and its related compound are a kind of important source materials in inorganic salts industry, are widely used in metallurgical, printing and dyeing, skin
A variety of industries such as leather, medicine and plating.The pollution of environment, especially soil pollution are also result in while chromium industrial development.Soil
Chromium in earth is mainly derived from raw and auxiliary material containing chromium and chromium product in transportation, because run, emit caused by mismanagement,
Drop, leakage, and waste gas, waste water and the waste residue discharged in chromium production process.These pollutants can also pass through atmospheric sedimentation, underground water
The approach such as migration and stacking leaching enters Soil Surrounding.Cr VI (Cr6+) it is universally acknowledged poisonous carcinogenic substance, human body directly connects
It can cause after touch allergic, and esophagus, respiratory tract be caused damage, Cr6+It can also be absorbed by plants, by food chain in human body
Interior enrichment, triggers a series of lesions, seriously threatens human health.Therefore, soil Cr pollution amelioration problem receives much concern.
《Chromium slag contaminated Environment control protection technique specification》(provisional) clear stipulaties, the removing toxic substances of chromium slag is exactly will with reducing agent
Hexavalent chrome reduction in chromium slag is trivalent chromium, recycles stabilizer to stabilize it solidification.In current stable curing method, commonly use
The stabilizers such as sulphite, phosphate, organic phosphonate, a large amount of uses of these medicaments can cause the secondary pollution of soil, its
In phosphorous nitrogen substance can be migrated with underground water, so as to cause that edaphon is exceeded and the phenomenon such as earth's surface water eutrophication.
Therefore, reparation chromium-polluted soil is realized without causing secondary pollution, and one of its approach is exactly that research and development are a kind of without phosphorus
Nitrogen-free has the stabilizer of stable metal chromium ability again, and current, and the research to this respect is also seldom.
The content of the invention：
In order to solve the above problems, first purpose of the invention is to provide a kind of macromolecule chromium stabilizer and its preparation
Method.The without phosphorus nitrogen-free of the stabilizer, environmental protection has very excellent effect to chelated mineral chromium ion, and its chelate can be inhaled
Invest in soil, reduce the migration of chromium.
Second object of the present invention is the application method for providing above-mentioned macromolecule chromium stabilizer, by with it is cheap and easy to get
Slag, bed mud and diatom earth cooperation use, reach the repairing effect of stable curing chromium.
In order to realize first purpose, the present invention is adopted the technical scheme that：
A kind of macromolecule chromium stabilizer, it is characterised in that the structural formula of the compound is as follows：
Wherein：R is the C in addition to normal-butyl12~C16Any one in straight or branched alkyl, n is between 6~16
Number.
The preparation method of above-mentioned macromolecule chromium stabilizer, the method includes the steps of：
1) it is 1 by mol ratio：1.1~5 alkyl polyoxyethylene ether and succinic anhydride is added in reactor, is added certain
The catalyst of amount, at normal pressure, 50~90 DEG C, reacts 2~6 hours, obtains product A；
2) by step 1) in obtained product A be cooled to room temperature, extracted with 10~30 times of ether of product A volumes,
Filter, remove excessive succinic anhydride, filtrate is evaporated and reclaimed, finally obtain purified product B, i.e. described macromolecule chromium stable
Agent.
As a further improvement, described step 1) described in the structural formula of alkyl polyoxyethylene ether be：
Wherein：R is the C in addition to normal-butyl12~C16Any one in straight or branched alkyl, n is between 6~16
Number.
As a further improvement, described step 1) described in catalyst for DMAP, aluminium chloride,
At least one of sulfuric acid, catalyst amount is the 0.1~8% of alkyl polyoxyethylene ether and succinic anhydride gross mass.
As a further improvement, described step 1) in, after catalyst is added, nitrogen conduct is passed through toward reactor
Protect gas.
The macromolecule chromium stabilizer of the present invention carries out esterification by ring opening anti-using alkyl polyoxyethylene ether and succinic anhydride as raw material
Should, its reaction equation is：
Both raw materials can not only provide the chelation group of excellent performance, and all containing only hydrocarbon three kinds of elements of oxygen, reaction
Process no coupling product is produced, and meets the environmental protection concept of Green Chemistry.Wherein, DMAP, aluminium chloride and sulfuric acid are esters
Change the economic benefit preferably catalyst commonly used in reaction.In product molecule, alkyl chain is lipophilic group, and carbon chain lengths R's is big
The small binding ability for determining stabilizer in soil with solid particle, this binding ability causes the chelating of stabilizer and chromium ion
Product can be adsorbed in soil, play static stabilization.Epoxy vinyl is hydrophilic radical, and number of repeat unit n determines stabilizer
Ion transport in soil, stabilizer is free in soil in the form of an ion, and this ion transport enables stabilizer
Widely chelating is free on the chromium ion in soil.Ester group and carboxyl are active function groups, can be chelated with metal ion
Effect, so as to reach the effect of stabilizing heavy metal.Except primary product in product A, also a small amount of unreacted succinic anhydride, wherein
The content of stabilizer is between 60~90%.In order to improve the purity of stabilizer, in step 2) in it is carried with ether
Pure, the content of stabilizer is 98% after purification.
In order to realize second purpose, the present invention is adopted the technical scheme that：
The application method of above-mentioned macromolecule chromium stabilizer, it is characterised in that application method is as follows：
1) macromolecule chromium stabilizer is mixed with slag, bed mud and diatomite, stirred, obtain confection C；
2) medicament C is mixed with chromium-polluted soil stirring, while carrying out spray operation, controls soil moisture, stir
Conserve 5~30 days afterwards.
As a further improvement, described step 1) in confection C according to mass fraction meter, including 5~20 parts
Macromolecule chromium stabilizer, 20~50 parts of slags, 30~60 parts of bed muds and 10~40 parts of diatomite, the moisture content of each component are no more than
2%.
As a further improvement, described step 2) in confection C consumption for chromium-polluted soil quality
0.01-0.1 times.
As a further improvement, described step 2) in soil moisture be 10%~30%.
The macromolecule chromium stabilizer of the present invention is used after being mixed with slag, bed mud and diatomite, the property of its reduction of hexavalent chromium
Can be very notable.The biological silicalite that diatomite is made up of the siliceous remains of diatom and other microorganisms, with huge ratio
Surface area and powerful surface adsorption property, it is used in combination with bottom mud in lake, plays the solidification of heavy metal chelate,
To reduce the migration of chromium of the absorption in soil.Macromolecule chromium stabilizer acts synergistically with slag, bed mud and diatomite, effectively
The Cr VI and total chrome content that reduce in soil, while solidify contaminated soil, prevent contaminant transportation.
The present invention is as a result of above-mentioned technical scheme, relative to prior art, with advantages below：
1) the preparation course of reaction of macromolecule stabilizer is designed according to green chemical reaction, with Atom economy
Feature, that is to say, that the reactant of this process is all transformed into reaction product, and no coupling product produce, reaction overall process without
Phosphorus nitrogen-free, meets the requirement of environmental protection.
2) solidification is carried out using steel factory waste residue, bed mud and diatomite cheap and easy to get, turned waste into wealth, effectively
Reduce rehabilitation cost.
3) macromolecule stabilizer of the invention is very excellent to the effect of reduction and stable chromium, and with long-term effect.
4) method of the present invention is simple to operate, easy construction.
Embodiment
The present invention is illustrated with reference to embodiment, but the embodiment is not limited to the scope of the invention.
Embodiment 1：
By 0.5mol alkylpolyoxyethylenes (n=6, Mr=450g/mol, chemistry it is pure), 0.55mol succinic anhydrides
(Mr=100g/mol, chemistry it is pure) and 0.28g (mass ratio 0.1%) DMAP be sequentially loaded into three-necked flask,
50 DEG C are heated under nitrogen protection, stirring reaction terminates for 2 hours.Brown is obtained at the end of reaction is in thick material, i.e.,
Product A.Product A is poured into beaker, is extracted in the ether for adding 10 times of its volume, is filtered to remove excessive succinic acid
Acid anhydride, filtrate is finally evaporated reclaim, and obtains purified product B about 262g, i.e. described macromolecule chromium stabilizer, calculating yield is
93.6%.
Prepare the Polluted Soil that 1Kg chromium concns are 3000mg/Kg standby.Take 5 grams of product B, 20 grams of slags, 30 grams of bed muds and 10
Gram diatomite, is mixed evenly, obtains totally 65 grams of mixture medicament C.10 grams of (0.01 times) medicament C are taken to stir mixed with contaminated soil
Close uniform, while spraying suitable quantity of water, it is 10% to keep soil moisture content.After maintenance 5 days, rehabilitating soil is sampled, with reference to HJ/
T299-2007《Solid waste-Leaching leaching method-sulfonitric method》Toxicity (total chromium) leaching is carried out to the soil after stabilization
Go out experiment, total chromium, Cr VI leaching concentration press standard GB5085.3-2007《Hazardous waste judging standard-leaching characteristic identification》
In measure.Total chromium, Cr VI leaching concentration and remediation efficiency are shown in Table one.Meanwhile, in order to further detect the length of stablizing effect
Effect property, using MEP be repeated several times leaching experiment (EPA use be used for examine the permanent standard method of repairing effect
One of, EPA method1320) long-term leaching test is carried out to the chromium-polluted soil after this stabilizer treatment, by determining, surely
Leaching concentration≤5.2mg/L of total chromium after fixed, according to《Hazardous waste judging standard leaching characteristic identification》(GB5085.3-
2007) judging standard of total chromium in, contaminated soil is unhazardous waste after processing.
Embodiment 2：
By 0.5mol Sodium Trideceths (n=10, Mr=640g/mol, chemistry it is pure), 1.0mol succinic anhydrides
(Mr=100g/mol, chemistry it is pure) and 2.1g (mass ratio 0.5%) aluminium chloride be sequentially loaded into three-necked flask, under nitrogen protection
60 DEG C are heated to, stirring reaction terminates for 3 hours.That brown is obtained at the end of reaction is in thick material, i.e. product A.Will production
Thing A is poured into beaker, is extracted in the ether for adding 20 times of its volume, is filtered to remove excessive succinic anhydride, finally will filter
Liquid evaporation is reclaimed, and obtains purified product B about 394g, i.e. described macromolecule chromium stabilizer, and it is 93.3% to calculate yield.
Prepare the Polluted Soil that 1Kg chromium concns are 3000mg/Kg standby.Take 10 grams of product B, 30 grams of slags, 45 grams of bed muds and
25 grams of diatomite, are mixed evenly, and obtain totally 110 grams of mixture medicament C.50 grams of (0.05 times) medicament C are taken to be stirred with contaminated soil
Mix well mixed, while spraying suitable quantity of water, it is 15% to keep soil moisture content.After maintenance two weeks, rehabilitating soil is sampled, reference
HJ/T299-2007《Solid waste-Leaching leaching method-sulfonitric method》Toxicity is carried out to the soil after stabilization (total
Chromium) leaching test, total chromium, Cr VI leaching concentration press standard GB5085.3-2007《Hazardous waste judging standard-Leaching
Differentiate》In measure.Total chromium, Cr VI leaching concentration and remediation efficiency are shown in Table one.Meanwhile, in order to further detect stablizing effect
Long-term effect, using MEP be repeated several times leaching experiment (EPA use be used for examine the permanent standard of repairing effect
One of method, EPA method1320) long-term leaching test is carried out to the chromium-polluted soil after this stabilizer treatment, by surveying
It is fixed, leaching concentration≤4.3mg/L of total chromium after stabilization, according to《Hazardous waste judging standard leaching characteristic identification》(GB5085.3-
2007) judging standard of total chromium in, contaminated soil is unhazardous waste after processing.
Embodiment 3：
By 0.5mol ceteths (n=16, Mr=946g/mol, chemistry it is pure), 2.5mol succinic anhydrides
(Mr=100g/mol, chemistry it is pure) and 57.84g (mass ratio 8%) sulfuric acid be sequentially loaded into three-necked flask, under nitrogen protection add
Heat is to 90 DEG C, and stirring reaction terminates for 6 hours.That brown is obtained at the end of reaction is in thick material, i.e. product A.By product A
Pour into beaker, extracted in the ether for adding 30 times of its volume, be filtered to remove excessive succinic anhydride, finally steam filtrate
Receipts are beamed back, purified product B about 735g, i.e. described macromolecule chromium stabilizer is obtained, it is 94.1% to calculate yield.
Prepare the Polluted Soil that 1Kg chromium concns are 3000mg/Kg standby.Take 20 grams of product B, 50 grams of slags, 60 grams of bed muds and
40 grams of diatomite, are mixed evenly, and obtain totally 170 grams of mixture medicament C.100 grams of (0.1 times) medicament C are taken to be stirred with contaminated soil
Mix well mixed, while spraying suitable quantity of water, it is 20% to keep soil moisture content.After maintenance one month, rehabilitating soil is sampled, ginseng
According to HJ/T299-2007《Solid waste-Leaching leaching method-sulfonitric method》Toxicity is carried out to the soil after stabilization (total
Chromium) leaching test, total chromium, Cr VI leaching concentration press standard GB5085.3-2007《Hazardous waste judging standard-Leaching
Differentiate》In measure.Total chromium, Cr VI leaching concentration and remediation efficiency are shown in Table one.Meanwhile, in order to further detect stablizing effect
Long-term effect, using MEP be repeated several times leaching experiment (EPA use be used for examine the permanent standard of repairing effect
One of method, EPA method1320) long-term leaching test is carried out to the chromium-polluted soil after this stabilizer treatment, by surveying
It is fixed, leaching concentration≤4.2mg/L of total chromium after stabilization, according to《Hazardous waste judging standard leaching characteristic identification》(GB5085.3-
2007) judging standard of total chromium in, contaminated soil is unhazardous waste after processing.
The total chromium of the embodiment of table one, Cr VI leaching concentration and remediation efficiency
* normative reference is《Hazardous waste judging standard leaching characteristic identification》(GB5085.3-2007)
Macromolecule chromium stabilizer is can be seen that to reducing and the effect of stable chromium is very excellent by the data of table one, is had
Long-term effect, has broad application prospects.
Claims (8)
1. a kind of preparation method of macromolecule chromium stabilizer, it is characterised in that this method comprises the following steps：
1) it is 1 by mol ratio：1.1~5 alkyl polyoxyethylene ether and succinic anhydride is added in reactor, adds catalyst,
At normal pressure, 50~90 DEG C, react 2~6 hours, obtain product A；
2) by step 1) in obtained product A be cooled to room temperature, extracted, filtered with 10~30 times of ether of product A volumes,
Excessive succinic anhydride is removed, filtrate is evaporated and reclaimed, purified product B, i.e. described macromolecule chromium stabilizer is finally obtained；
Described macromolecule chromium stabilizer, its structural formula is as follows：
Wherein：R is C12~C16Any one in straight or branched alkyl, n is the number between 6~16.
2. the preparation method of macromolecule chromium stabilizer according to claim 1, it is characterised in that step 1) described in alkane
The structural formula of base APEO is：
Wherein：R is C12~C16Any one in straight or branched alkyl, n is the number between 6~16.
3. the preparation method of macromolecule chromium stabilizer according to claim 1, it is characterised in that step 1) described in urge
Agent is at least one of DMAP, aluminium chloride, sulfuric acid, and catalyst amount is alkyl polyoxyethylene ether and fourth two
The 0.1~8% of acid anhydrides gross mass.
4. the preparation method of macromolecule chromium stabilizer according to claim 1, it is characterised in that step 1) in urged in addition
After agent, nitrogen is passed through as protection gas toward reactor.
5. a kind of application method of macromolecule chromium stabilizer as claimed in claim 1, it is characterised in that its application method is such as
Under：
1) macromolecule chromium stabilizer is mixed with slag, bed mud and diatomite, stirred, obtain confection C；
2) medicament C is mixed with chromium-polluted soil stirring, while carrying out spray operation, controls soil moisture, supported after stirring
Shield 5~30 days.
6. the application method of macromolecule chromium stabilizer according to claim 5, it is characterised in that step 1) in mixing medicine
Agent C is according to mass fraction meter, including 5~20 parts of macromolecule chromium stabilizers, 20~50 parts of slags, 30~60 parts of bed muds and 10~40
Part diatomite, the moisture content of each component is no more than 2%.
7. the application method of macromolecule chromium stabilizer according to claim 5, it is characterised in that step 2) in mixing medicine
Agent C consumption is 0.01-0.1 times of chromium-polluted soil quality.
8. the application method of macromolecule chromium stabilizer according to claim 5, it is characterised in that step 2) in soil it is wet
Spend for 10%~30%.
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| CN102083557A (en) * | 2008-06-23 | 2011-06-01 | 三菱瓦斯化学株式会社 | Agent for purifying soil and/or underground water and purification method |
| CN102206494A (en) * | 2011-03-30 | 2011-10-05 | 云南省农业科学院质量标准与检测技术研究所 | Modifying agent capable of passivating vegetable garden soil heavy metal and preparation method and applying method thereof |
| CN102220136A (en) * | 2011-03-30 | 2011-10-19 | 中国科学院亚热带农业生态研究所 | Soil heavy metal composite passivator with humic acid minerals and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102083557A (en) * | 2008-06-23 | 2011-06-01 | 三菱瓦斯化学株式会社 | Agent for purifying soil and/or underground water and purification method |
| CN102206494A (en) * | 2011-03-30 | 2011-10-05 | 云南省农业科学院质量标准与检测技术研究所 | Modifying agent capable of passivating vegetable garden soil heavy metal and preparation method and applying method thereof |
| CN102220136A (en) * | 2011-03-30 | 2011-10-19 | 中国科学院亚热带农业生态研究所 | Soil heavy metal composite passivator with humic acid minerals and preparation method thereof |
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| Butanedioic acid, mono(3,6,9,12,15,18-hexaoxatriacont-1-yl) ester (9CI);CA;《STN》;20041119;结构式 * |
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