CN103657587A - Preparation method of triazine ramification inserting layer laminated clay heavy metal catching agent and application - Google Patents
Preparation method of triazine ramification inserting layer laminated clay heavy metal catching agent and application Download PDFInfo
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Abstract
The invention relates to a preparation method of triazine ramification inserting layer laminated clay heavy metal catching agent and an application. The preparation method comprises the steps of firstly displacing potassium ions in laminated clay by using inorganic acid or quaternary ammonium salt under certain temperature and certain concentration of a displacer; carrying out intercalation on the laminated clay of the potassium ions after displacing, carrying out reaction on the primary amine in the laminated clay after intercalation and cyanuric chloride, and thus preparing triazine intercalation ramification ramification layer laminated clay; carrying out reaction on the triazine intercalation ramification ramification layer laminated clay and sodium sulfide so as to obtain sulfhydrylation triazine ramification inserting layer laminated clay heavy metal catching agent. The sulfhydrylation triazine ramification inserting layer laminated clay is singly applied in heavy metal sewage treatment or is applied by combining with the existing schwertmannite and has remarkable effect. The preparation method of the triazine ramification inserting layer laminated clay heavy metal catching agent and the application provided by the invention have the outstanding characteristics that compared with the existing processing agent, the removal rate of ions such as heavy metal lead, arsenic and cadmium in the water can achieve more than 96.3% without filtering, and the purposes that the labor is saved and the time is saved are achieved in the industrial application of processing the sewage containing heavy metal.
Description
Technical field
The present invention be belong to layered clay mineral modification particularly illite intercalation modifying as the inorganic agent technical field of heavy metal in sewage, be specifically related to a kind of preparation method and application of pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent.
Background technology
The pollution source of heavy metal is mainly by atmosphere, soil and water, and in water, heavy metal pollution is the topmost source of harm humans.Heavy metal mainly refers to lead, mercury, chromium, cadmium, zinc, nickel, arsenic, copper, iron, barium, antimony, beryllium, thallium, 14 kinds of elements such as barium.Heavy metal pollution is mainly derived from industry the exploitation of heavy metal is smelted to processing and business manufacturing activities, increasing.Heavy metal pollution is all listed in first pollution thing in countries in the world, show thus to administer heavy metal pollution, has become instant world subject.
Heavy Metal Pollution Control method is a lot, be broadly divided into two classes, one class is to make deliquescent heavy metal contaminants change insoluble matter into, from water, separate, as alkaline chemical precipitation method, sulfhydryl compound complexometry, efficient adsorption method, another kind of is the chemical form that does not change heavy metal, by physical method concentrating and separating, as hyperfiltration, electroosmose process, ion-exchange, evaporation concentration method, all there is the deficiencies such as cost is high, use inconvenience in these methods.The stable special graceful stone of showing severity as prepared by US2006088464, can bear long term storage or transportation, and has higher to arsenic adsorption capacity.CN102114401 Chinese Academy of Sciences ecological environment combines cubic sulfate lepidocrocite with high polymer binder, the absorption property of the arsenic-removing adsorption agent particle of invention is high, arsenic in drinking water is had to height adsorptive selectivity, and adsorption capacity is high, no matter adsorption particle is in drying regime or large in its intensity of dampness, during use, Particle Breakage rate is low, there is no the stripping of adsorbent, is suitable for long-term and uses in the situation that water flow pressure changes greatly.US5880060 is adopting montmorillonite or illite polyeletrolyte chelating agent, is added to the water the rear filtration of absorption, can remove the iodine of 100mg with one gram of inorganic agent, strontium, and caesium, clearance can reach 92%-99%.US2012261609 has reported the natural or synthetic clay of consisting of of removing heavy metal in water, diethylamino ethyl, season the composition such as amino-ethyl resin, quaternary ammonium salt, imidazole salts, mercaptan, can remove the heavy metal below 10000ppm, clearance reaches > 75%, in an example, adopt 48.7 grams of two (hydrogenated tallow) alkyl dimethyl ammonium chlorides to mix with 61.6 grams of bentonites, mixture is mixed and pulverized with mortar; Next, 4.63 grams of lauryl mercaptans (5%w/w's) join in above-mentioned fine powder, and fully mix, 1 gram of this mixture is put into (50 ml water) beaker of the arsenic that contains 110ppm, fully stir after this mixture, by inductively coupled plasma (ICP), analyze arsenic concentration, result shows, arsenic concentration level after processing is lower than detectable limit, lower than 0.008/1000000th ICP.CN101757885 is two carbaminothioic acid intercalated montmorillonite heavy metal chelating agents in addition, although have, the alumen ustum of cheap and easy to get, stable performance, generation is large and heavy, settling velocity is fast, but also need separately to add polyacrylamide flocculant, the about 100ppm of middle copper and cadmium concentration can dispose of sewage, after processing, still need to filter, the scope of application is less.CN1556894 adopts dithiocar-bamate and thiuram applied in any combination, can make the concentration of Ag drop to below 10ppm from 2000ppm, also still needs to filter after processing.Based on the above results, can find out that above-mentioned inorganic agent forms more complicated, after processing, all need by filtering.
Derivative intercalation lamellar clay, particularly intercalation illite and the cubic sulfate lepidocrocite of triazine of the present invention are used in combination, or adopt separately the derivative intercalation lamellar clay of triazine to process containing heavy metal containing sewage, without filtering, just can reach discharge standard.One of object of the present invention is too complicated in order to overcome the heavy metal chelating agent composition adopting in conventional art, and adds various flocculation and chelation agent, still needs the drawbacks such as filtration after processing; Two of the object of the invention is to adopt large molecule intercalation lamellar clay, and the larger sinking speed of having accelerated of alumen ustum of generation has been simplified sewage disposal program; Three of the object of the invention is to reduce costs, and efficient removal heavy metal pollutes.
Summary of the invention
Realize the technical scheme of goal of the invention:
A preparation method for pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent, preparation process is:
(1) first the potassium ion in lamellar clay is cemented out under uniform temperature and displacer concentration with inorganic acid or quaternary ammonium salt;
(2) lamellar clay after displacement is carried out to intercalation with primary amine;
(3) primary amine layer after intercalation being closed in clay reacts with Cyanuric Chloride, is prepared into triazine intercalation derivative intercalation lamellar clay;
(4) the triazine intercalation derivative intercalation lamellar clay of step (3) is reacted with vulcanized sodium and obtains sulfhydrylation pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent.
The lamellar clay that the present invention adopts can be natural or synthetic lamellar clay, natural clay can comprise kaolinite, illite, chlorite, smectite or their combination, this class lamellar clay is 2:1 type lamellar clay, interlayer has calcium, magnesium, potassium ion, adopt ion-exchanger, can from interlayer by these ion exchanges out, increase its interlamellar spacing, be convenient to intercalator to insert wherein, the intercalation thing obtaining is like this more stable.
The preferred illite of laminate clay of the present invention, in illite, the displacement of potassium ion has two kinds of methods, by mineral acid treatment, potassium ion is replaced out, or replace potassium ion with the agent of quaternary ammonium salt proton exchange, the latter's quaternary ammonium salt price is higher, process after washing and relatively bother, preferably adopt inexpensive acid to process, by suitable acid concentration, obtained in suitable temperature the result being satisfied with.
Intermediate ion exchange displacement potassium of the present invention acid used can be sulfuric acid, hydrochloric acid, nitric acid or other inorganic acids.The weight concentration of acid can be 20%-70%, is 20%-50% preferably, and that best is 20%-30%.The temperature that displacement potassium adopts is 50 ℃-140 ℃, preferably 50 ℃-100 ℃, is preferably 50 ℃-70 ℃.Displacement nak response time 1h-10h, preferably 3h-7h, is preferably 5h-7h.
Illite after displacement potassium washes with water to pH=5-7, then filters, and filter cake adopts methylamine, ethamine, and the various water-soluble primary amine such as ethylenediamine, diethyl triamine, trientine carry out intercalation.During intercalation, illitic weight concentration, between 1%-50%, is better between 5%-30%, preferably between 5%-10%.Intercalation temperature is 20 ℃-70 ℃, preferably 20 ℃-50 ℃, and preferably 30 ℃-40 ℃.Intercalation time 2h-20h is better 5h-10h, preferably 7h-10h.Illite is with filtering after primary amine intercalation, and to join weight concentration be in 50% aqueous acetone solution, after cooling to 0 ℃-5 ℃, Cyanuric Chloride and acetone suspension are slowly added dropwise to wherein, after adding, be warmed up to 60 ℃, and at this temperature insulation reaction 4h-6h, then filter, to obtain 4, 6-bis-chloro-[1, 3, 5] the amine intercalation illite that-triazine radical replaces, if the amine using is ethylenediamine, by products obtained therefrom, be N, N,-bis--(4, 6-bis-chloro-[1, 3, 5]-triazine radical)-ethylenediamine intercalation illite, then by deionized water, be washed till without chlorion and filter.
Above-mentioned gained filter cake is added to water and be made into suspension, add adjusting PH with base=9-11, then add vulcanized sodium at 30 ℃-70 ℃, better temperature is 40 ℃-60 ℃, is preferably in 45 ℃-50 ℃, reaction 1h-3h, then acid adding adjusts pH to < 5, filters, and obtains yellow filter cake.This filter cake is the made sulfhydrylation pyrrolotriazine derivatives intercalation illite heavy metal chelating agent of the present invention after drying, and this heavy metal chelating agent all has very strong capturing ability to various heavy.
The intercalation lamellar clay that the present invention narrates is not limited to illite, also can comprise imvite, serpentine, chlorite, smectite or their combination.
Sulfhydrylation pyrrolotriazine derivatives structural formula of the present invention is:
Pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent, in the middle application of disposing of sewage, adds pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent in sewage and stirs 30 minutes, controls pH=6, standing 20 minutes.
Sulfhydrylation pyrrolotriazine derivatives intercalation lamellar clay of the present invention, can apply separately also and can be used in combination with other heavy metal chelating agents.
The effect of invention
Sulfhydrylation pyrrolotriazine derivatives intercalation illite of the present invention is being compared aspect processing with much money with the existing special graceful stone of showing severity, there is significant effect, without filtering, can make metallic lead in water, arsenic, cadmium plasma clearance reach more than 96.91%, after filtration, reach 99.48%, when processing the waste water that contains heavy metal, can not need like this to filter.And filter clearance with the special graceful stone of showing severity at a processing huge sum of money, do not only have 85.61%.
Accompanying drawing explanation
Fig. 1 different time is changed the XRD figure after potassium with sulfuric acid to illite
The specific embodiment
By specific embodiment, the present invention is done to more detailed narration below, but do not form, the present invention is not limited.
Example 1:
The illitic preparation of sulfhydrylation pyrrolotriazine derivatives intercalation
1. take 800 order illite breeze 30g, put into 250ml three-necked bottle, three-necked bottle is with whipping temp meter and condenser, and add 40% sulfuric acid, sulfuric acid: water=40:60 (W/W) 80g, be warmed up to 115 ℃, insulation reaction 5 hours, filtered water filter wash cake is till PH=6, after oven dry from elementary analysis, in illite, the content of potassium drops to 3.05% by 7.5%, do XRD diffraction analysis, from diffraction pattern, it is complete that illite crystal structure keeps simultaneously, but interlamellar spacing obviously increases, as shown in Figure 1.
2. the illite 10g after potassium that carries that takes above-mentioned preparation, puts into the three-necked bottle with whipping temp meter and condenser, adds 90ml water, under stirring condition, be warmed up to 40 ℃, and slowly drip 4.5g ethylenediamine, after dripping, be warmed up to 50 ℃, insulation reaction 7h, completes ethylenediamine intercalation.
3. the suspension of 27g Cyanuric Chloride and 100ml acetone is slowly added in the reactant liquor of cooling 0 ℃-5 ℃ (2), after adding, is warmed up to 60 ℃, and at this temperature insulation reaction 6h, filter filter cake vacuum drying at 60 ℃.
4. by the pyrrolotriazine derivatives intercalation illite obtaining in 3, add water 120ml, be made into suspension, and under PH=10.5 condition, adding vulcanized sodium 8.1g, 50 ℃ of reaction 1h, adjust pH=2 with hydrochloric acid, filtering drying obtains final products, i.e. sulfhydrylation pyrrolotriazine derivatives intercalation illite.
Example 2:
The illitic application experiment of sulfhydrylation pyrrolotriazine derivatives intercalation
Plumbi nitras is mixed with to leaded 10ppm, 20ppm, 40ppm, 80ppm, 160ppm, each takes out 50ml, the sulfhydrylation oxazine derivatives intercalation illite 0.5g that adds respectively above-mentioned preparation, pH is transferred to 8.5-9 simultaneously, fully stirs at normal temperatures static filtration after 30 minutes, with ICP instrument, detect, result is that plumbum ion concentration is within being less than 80ppm time, lead concentration after processing is all less than detectable limit, and it is 0.225ppm that the lead solution of 160ppm is processed rear detected value, and clearance reaches 97.18%.
Example 3:
Sulfhydrylation pyrrolotriazine derivatives intercalation illite and the special graceful stone contrast application of showing severity
Get two parts of solution 50ml that are 8ppm containing plumbum ion concentration that prepared, add respectively sulfhydrylation pyrrolotriazine derivatives intercalation illite of the present invention and the commercially available special graceful stone inorganic agent 0.5g that shows severity, be contrast experiment.Standing 1h stir 30min under the condition of pH=10 after, filters respectively and does not filter, and contrast detects.Testing result table 1:
Table 1 sulfhydrylation pyrrolotriazine derivatives intercalation illite and the special graceful stone of showing severity remove the effect of lead ion
Table 1 finds out that sulfhydrylation pyrrolotriazine derivatives intercalation illite of the present invention does not filter successful higher than the unfiltered special graceful stone treatment fluid of showing severity thus, after filtration still higher than the special graceful stone treatment fluid of showing severity, this shows that intercalation illite sinking speed is apparently higher than the special graceful stone of showing severity of routine, the industrial applications so this inorganic agent is more convenient for.
Example 4:
Agent for capturing of the present invention is processed Henan large-scale metallurgical enterprise sewage
The sewage 400ml of Qu Gai enterprise, sewage, containing arsenic 0.34mg/L, plumbous 2.013mg/L, cadmium 0.552mg/L, first filters with manganese sand, remove suspension, then add 15% NaOH 0.7ml, 30% hydrogen peroxide 0.1ml, air aeration 30 minutes, now reacting liquid temperature is 40 ℃, pH=8.Thing 0.125g of the present invention is joined in above-mentioned sewage and stirred 30 minutes, PH=6 now, standing 20 minutes, with ICP instrument, detect, result is as shown in the table, by known this water quality of sewage detection after processing, meets China's sewage drainage standard.
Table 2 agent for capturing of the present invention carries out result to Henan large-scale metallurgical enterprise sewage
By above-mentioned example, can obviously find out that heavy metal treatment agent of the present invention has treatment effect obvious, sinking speed is fast.
Known heavy metal chelating agent of the present invention still can reach discharge standard without filtering after having the fast sedimentation of sinking speed based on the above results, and can with other heavy metal treatment agent applied in any combination, effect is better, in heavy metal pollution water treatment, reaches saving of work and time, saves efficient object.
Above example is for explanation the present invention, does not limit the present invention.
Claims (10)
1. a preparation method for pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent, preparation process is:
(1) first the potassium ion in lamellar clay is cemented out under uniform temperature and displacer concentration with inorganic acid or quaternary ammonium salt;
(2) lamellar clay after displacement potassium ion is carried out to intercalation with primary amine;
(3) primary amine in the lamellar clay after intercalation is reacted with Cyanuric Chloride, be prepared into pyrrolotriazine derivatives intercalation lamellar clay;
(4) the pyrrolotriazine derivatives intercalation lamellar clay of step (3) is reacted with vulcanized sodium again and obtain sulfhydrylation pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent.
2. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 1, it is characterized in that described lamellar clay is natural or synthetic lamellar clay, natural clay comprises kaolinite, illite, chlorite, smectite or their combination, this class lamellar clay is 2:1 type lamellar clay, interlayer has calcium, magnesium, potassium ion, adopts ion-exchanger, can be from interlayer by these ion exchanges out, increase its interlamellar spacing, be convenient to intercalator to insert wherein.
3. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 1, it is characterized in that described lamellar clay is illite, in illite, the displacement of potassium ion has two kinds of methods, with acid treatment, potassium ion is replaced out, or replace potassium ion with the agent of quaternary ammonium salt proton exchange.
4. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 3, it is characterized in that the acid used of described illite ion-exchange displacement potassium can be sulfuric acid, hydrochloric acid, nitric acid or other inorganic acids; The weight concentration of acid is 20%-70%, and the temperature that displacement potassium adopts is 50 ℃-140 ℃; Displacement nak response time 1h-10h.
5. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 3, after it is characterized in that described displacement potassium, illite washes with water to pH=5-7, then filter, filter cake adopts methylamine, ethamine, ethylenediamine, diethyl triamine, the water-soluble primary amine of trientine to carry out intercalation; During intercalation, illitic weight concentration is between 1%-50%, and intercalation temperature is 20 ℃-70 ℃, intercalation time 2h-20h; Illite is with filtering after primary amine intercalation, and to join weight concentration be in 50% aqueous acetone solution, after cooling to 0 ℃-5 ℃, Cyanuric Chloride and acetone suspension are slowly added dropwise to wherein, after adding, be warmed up to 60 ℃, and at this temperature insulation reaction 4h-6h, then filter, will obtain 4,6-bis-chloro-[1,3,5] the amine intercalation illite that-triazine radical replaces, is then washed till without chlorion and filters by deionized water.
6. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 5, it is characterized in that described primary amine is for being ethylenediamine, by products obtained therefrom, be N, N '-bis--(4,6-bis-chloro-[1,3,5]-triazine radical)-ethylenediamine intercalation illite, is then washed till without chlorion and filters by deionized water.
7. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 5, it is characterized in that gained filter cake is added to water is made into suspension, add adjusting PH with base=9-11, then add vulcanized sodium at 30 ℃-70 ℃, reaction 1h-3h, then acid adding adjusts pH to < 5, filters, obtain yellow filter cake, this filter cake is sulfhydrylation pyrrolotriazine derivatives intercalation illite heavy metal chelating agent after drying.
8. according to the preparation method of the pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 7, it is characterized in that the structural formula of sulfhydrylation pyrrolotriazine derivatives is:
9. the arbitrary pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent of claim 1-8, in the application of disposing of sewage, adds pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent in sewage and stirs 30 minutes, controls pH=6, standing 20 minutes.
10. pyrrolotriazine derivatives intercalation lamellar clay heavy metal chelating agent is according to Claim 8 in the application of disposing of sewage, and sulfhydrylation pyrrolotriazine derivatives intercalation lamellar clay and other heavy metal chelating agents that it is characterized in that are used in combination.
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Cited By (3)
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| CN104798773A (en) * | 2015-05-08 | 2015-07-29 | 青岛海纳生物科技有限公司 | Pesticide slow release speed-control film and preparing method thereof |
| CN107556941A (en) * | 2016-06-30 | 2018-01-09 | 比亚迪股份有限公司 | A kind of bonding agent and application and composite article and its preparation method and application |
| CN108928880A (en) * | 2018-08-10 | 2018-12-04 | 南华大学 | A kind of processing method of the waste water containing radioactive element |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104798773A (en) * | 2015-05-08 | 2015-07-29 | 青岛海纳生物科技有限公司 | Pesticide slow release speed-control film and preparing method thereof |
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| CN107556941A (en) * | 2016-06-30 | 2018-01-09 | 比亚迪股份有限公司 | A kind of bonding agent and application and composite article and its preparation method and application |
| CN107556941B (en) * | 2016-06-30 | 2019-09-13 | 比亚迪股份有限公司 | A kind of bonding agent and application and composite article and its preparation method and application |
| CN108928880A (en) * | 2018-08-10 | 2018-12-04 | 南华大学 | A kind of processing method of the waste water containing radioactive element |
| CN108928880B (en) * | 2018-08-10 | 2021-07-09 | 南华大学 | Method for treating wastewater containing radioactive elements |
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Application publication date: 20140326 |