CN106492745A - N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion method for preparing modified bentonite - Google Patents
N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion method for preparing modified bentonite Download PDFInfo
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- bentonite
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- mercaptoethyls
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Abstract
The invention discloses a kind of N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion method for preparing modified bentonite.It is mainly by N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamides and Ca2+The complex ion of formation prepares modified alta-mud for column-supporting agent.There is physical absorption or chemisorbed with molecule-type or ion-type organic pollution in a large amount of active sites of modified alta-mud interlayer of the present invention, heavy metal ion and organic pollution are dispelled simultaneously can, compared with organic macromolecule modifying agent, adsorption capacity increases, and it is stable firm, energy permanent locking heavy metal ion, sustainable time are longer, have saved cost to a certain extent.
Description
Technical field
The invention belongs to field of environment protection, and in particular to a kind of N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamides
Calcium complex ion method for preparing modified bentonite.
Background technology
Bentonite can make binding agent, suspending agent, thixotropic agent, stabilizer, net due to good physical and chemical performance
Change decolorising agent etc. and be widely used in the fields such as agricultural, light industry, chemical industry and environmental protection.Bentonite is a kind of of many uses
Natural minerals, the application in chemical industry and field of Environment Protection mainly uses which and is catalyzed and absorption property, but natural
Bentonite does not have good application performance, is modified process to which and can substantially improve its interlayer structure and suction
Attached performance.
Bentonitic main active is aqueous layer aluminosilicate mineral, clips one by two-layer silicon-oxy tetrahedron
Layer alumina octahedral is constituted, and belongs to 2：1 type three-layer clay mineral, such as Fig. 1.Bentonite has stronger ion exchange
Ability, under certain physical and chemical condition, can and Fe3+、Ca2+、Mg2+、Na+、K+Etc. being exchanged with each other.
After cation-modified, bentonite specific surface area is big, absorption property is good, can effectively remove the pollutant in waste water.
Conventional inorganic cation mainly has multi-nuclear metal cation and polymerization hydroxy metal cation etc., conventional organic sun
Ion includes alkyl quaternary ammonium saltss, alkyl quaternary salt, hydrochlorate of alkylamine etc..Modified bentonite, its interlayer
Away from obtaining different degrees of raising, its adsorption capacity be improved significantly.
CN200910248679.5 organic modified bentonites and preparation method thereof；CN201010121822.7 is organic to be changed
Property preparation method for bentonite；The method that a kind of utilization organobentonites of CN201110307128.9 process waste water, with
Upper patent describes organic modifiers and processes bentonitic technology, but for modified alta-mud, although due to modifying agent
Pillared effect increased interlamellar spacing and adsorption capacity, but occupied due to the agent that has been modified of ion activity point, so changing
The absorption of property Bentonite is mainly changed into weaker quiet from the electrostatic interaction of original moderate strength
Electric interactions, adsorption substantially weaken, and do not reach the purpose of permanent locking heavy metal ion, and easily make
Into secondary pollution.The present invention uses N, and N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ions are used as post
Support modifying agent is used for modified alta-mud, because heavy metal ion belongs to transition metal, all there is the internal layer d rails of sky
Road, can form metastable coordination compound, N, N with part '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamides are
One good part, the sulphur atom and nitrogen-atoms above which can easily occupy the unoccupied orbital of metal ion, real
The now coordination between metal ion.Simultaneously it is also a kind of excellent pi-electron acceptor, can easily with gold
Category ion forms stable two key of feedback, and in the form of covalent bond, the macromolecule stable with central ion complex functionality is matched somebody with somebody
Compound.With this coordination compound ion as modifying agent, equally interlamellar spacing can be improved greatly, improve its interlayer knot
Structure and adsorption capacity, and change the height of the bentonite stability after surname, can permanent locking heavy metal ion.
Content of the invention
It is an object of the invention to provide N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion bentones
The preparation method of soil.
Realization the technical scheme is that：
A kind of N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamides calcium complex ion method for preparing modified bentonite, bag
Include following steps：
(1) bentonite original soil (raw ore) is processed：Take a certain amount of bentonite original soil to dry at 100 DEG C -120 DEG C, by which
Crush, grinding is sieved for subsequent use；
(2) preparation of bentonite suspension：By above-mentioned bentonite and water in mass ratio 1：(10-35) mix, be heated to
60-100 DEG C of stirring obtains suspension no less than 60min；
(3) preparation of sodium bentonite：Na is added in bentonite suspension2CO3Solution, by which at 60-100 DEG C
Under be heated with stirring to mix homogeneously, obtain sodium bentonite suspension；
(4) preparation of N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ions：Under nitrogen protection, with chloroform
It is acid-binding agent for solvent, triethylamine, adds mercaptoethylamine hydrochloride, under ice bath stirring, be slowly added dropwise isophthalic diformazan again
Acyl chlorides so that mercaptoethylamine hydrochloride is 2 with the mol ratio of m-phthaloyl chloride:8, after persistently stirring, use water extraction
2-3 time, organic layer distillation aqueous solvent is dried, by products therefrom wiring solution-forming, CaCl is added2After solution is sufficiently stirred for
Obtain N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide complex ion solution, set aside for use；
(5) the complex ion solution described in step (4) is pressed volume with the sodium bentonite suspension described in step (3)
Than 1：5 mixing, and stir in 60-100 DEG C of water bath with thermostatic control, centrifugal drying, grinding sieve, and obtain target product
Thing.
In step (1), ground 100-200 mesh sieves.
In step (3), Na2CO3The concentration of solution is 0.1mol/L, bentonite suspension and Na2CO3Solution
Volume ratio is 20:1, the agitating heating time is not less than 60min.
In step (4), CaCl2Solution and N, N '-bis- (2- mercaptoethyls) -1,3- phenyl-diformyl amine aqueous solutions concentration equal
For 0.01mol/L, its volume ratio 1：1.
In step (4), triethylamine is 1.37 with the mass ratio of mercaptoethylamine hydrochloride：1.
In step (5), the agitating heating time is no less than 60min, not higher than 120 DEG C of centrifugal drying temperature, grinding
100-200 mesh sieve is crossed afterwards.
Compared with prior art, it is an advantage of the invention that：
(1) N prepared by the present invention, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion modified alta-muds go
Removing heavy metals ionic nature is more excellent, uses it in the with serious pollution waste water of heavy metal ion, its heavy metal from
The clearance of son is larger.
(2) N prepared by the present invention, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion bentone soil layers
Between a large amount of active sites and molecule-type or ion-type organic pollution there is physical absorption or chemisorbed, can dispel simultaneously
Removing heavy metals ion and organic pollution, compared with organic macromolecule modifying agent, adsorption capacity increases, and stable jail
Gu, energy permanent locking heavy metal ion, sustainable time are longer, have saved cost to a certain extent.
(3) preparation process is simple of the present invention, easy to operate, and cost is relatively low.
Description of the drawings
Fig. 1 is the structural representation of active component in prior art bentonite.
Fig. 2 be N of the present invention, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion pillared modified montmorillonite structures
Schematic diagram.
Fig. 3 is process chart prepared by the present invention.
Specific embodiment
Fig. 2 be N of the present invention, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ions pillared modified montmorillonite knot
Structure schematic diagram, in Fig. 2, the N of weak steady, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ions are used as post
Support agent carries out pillared modification to bentonite, in the effect with heavy metal ion, due to the internal layer d of heavy metal ion
Track participates in hydridization, and the coordination compound energy for being generated is lower, stability more preferable, and therefore heavy metal ion will be with first wife
The central ion Ca of compound2+Generation exchange reaction, generates new heavy metal ion coordination compound, heavy metal ion thus
Adsorbed and locking, a large amount of active sites of modified alta-mud interlayer and molecule-type or ion-type organic pollution are sent out in addition
Raw physical absorption or chemisorbed, can dispel heavy metal ion and organic pollution simultaneously.
Such as Fig. 3, a heavy metal species permanent locking agent of the present invention are prepared by following steps：
Embodiment 1：
50g bentonite original soil is taken in 105 DEG C of drying in oven, then crushed, ground, after 100 mesh with ball mill
Sieve, the product for being obtained and water in mass ratio 1：15 mixing, are heated to 80 DEG C, are sufficiently stirred for suspension is obtained.
10mL, the Na of 0.1mol/L is added in 200mL suspensions2CO3Solution mix homogeneously, by which in 80 DEG C of water
In bath, agitating heating 60min obtains sodium bentonite suspension.
Under nitrogen protection in there-necked flask, mercaptoethylamine hydrochloride is added as solvent with chloroform, plus triethylamine is applied
Sour agent, slowly Deca m-phthaloyl chloride again under ice bath stirring so that mercaptoethylamine hydrochloride and m-phthaloyl chloride
Mol ratio be 2:8, persistently after stirring 5h, deionized water is extracted 2-3 time, suitably dries organic layer distilled water
Solvent, you can obtain white product NBMIPA, is made into the NBMIPA solution of 0.01mol/L.Take 20mL
20mL, the CaCl of 0.01mol/L is added in NBMIPA solution obtained above2Solution, obtains after being sufficiently stirred for
N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamides calcium complex ion solution, set aside for use.
By N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ions solution is with sodium bentonite suspension by weight
Amount compares 1：12 mixing after, agitating heating 60min in 80 DEG C of water-baths, then centrifugal drying, ground 100
Mesh sieve, makes product.
Comparison example 1
From Wuxi plating company waste water, Zn is measured2+Concentration 5.14mg/L, Ni2+Concentration 4.88mg/L, Cr6+
Concentration 4.91mg/L, is separately added into tetramethyl-ammonium modified alta-mud, the lauryl sulphate acid of 5g in every liter of waste water
Product in sodium and embodiment 1, stir speed (S.S.) 30r/min, mixing time 10min measure the dense of heavy metal ion
Degree and the ion concentration after placement half a year are shown in Table 1.After adding 1 product of example, heavy metal ion reaches country's discharge mark
Quasi- GB8978-1996 (the maximum blowdown flow rates that country allows：Primary standard Zn2+2.0mg/L,Ni2+1.0mg/L,Cr6+
0.5mg/L), and be long placed in rear concentration of heavy metal ion and not do not increase, illustrate locking heavy metal ion sustainable when
Between longer.
The concentration of 1 heavy metal ion of table and place half a year after ion concentration
| Material 1 | Material 2 | Example 1 | |
| Zn2+/(mg/L) | 1.12 | 0.99 | 0.82 |
| Ni2+/(mg/L) | 0.98 | 0.93 | 0.68 |
| Cr6+/(mg/L) | 0.68 | 0.50 | 0.35 |
| Zn after half a year2+/(mg/L) | 1.43 | 1.09 | 0.82 |
| Ni after half a year2+/(mg/L) | 1.06 | 0.96 | 0.69 |
| Cr after half a year6+/(mg/L) | 0.75 | 0.54 | 0.35 |
Comparison example 2：
From the board wastewater of Suzhou company, Cu is measured2+Concentration 127.70mg/L, pH are 5.2, at per liter
Product in tetramethyl-ammonium modified alta-mud, sodium lauryl sulphate and the embodiment 1 of 10g is separately added in waste water,
Stirred with 30r/min speed, stood after reaction 10min, Cu in above-mentioned clear liquid2+Concentration and Cu after being long placed in half a year2+
Concentration is shown in Table 2, finds Cu using product in example2+Concentration reaches discharging standards GB8978-1996 (country
The maximum blowdown flow rate of permission：Primary standard Cu2+2.0mg/L), and rear Cu is long placed in2+Concentration is not significantly increased.
Table 2 adds Cu in waste water ion concentration and the change for standing copper ion concentration after half a year after material
| Material 1 | Material 2 | Example 1 | |
| Cu2+/(mg/L) | 1.75 | 1.43 | 0.25 |
| Cu after half a year2+/(mg/L) | 3.78 | 2.56 | 0.26 |
Comparison example 3：
From the production waste water of Nanjing cell manufacturer, Zn is measured2+Concentration 6.23mg/L, Mn2+Concentration
5.41mg/L, Hg2+Concentration 1.67mg/L, in every liter of waste water add 10g tetramethyl-ammonium modified alta-mud, ten
Product in sodium dialkyl sulfate and embodiment 1, is stirred with 30r/min speed, stands, survey after reaction 10min
After obtaining effects of ion concentration and being long placed in half a year, ion concentration is shown in Table 3.Using heavy metal in product wastewater in example 1
Ion reaches discharging standards GB8978-1996 (the maximum blowdown flow rate that country allows：Primary standard Zn2+2.0
mg/L,Mn2+2.0mg/L,Hg2+0.05mg/L), and it is long placed in rear concentration of heavy metal ion and is not significantly increased.
The concentration of 3 heavy metal ion of table and place half a year after ion concentration
| Material 1 | Material 2 | Example 1 | |
| Zn2+/(mg/L) | 1.18 | 0.99 | 0.86 |
| Mn2+/(mg/L) | 0.76 | 0.63 | 0.41 |
| Hg2+/(mg/L) | 0.68 | 0.51 | 0.35 |
| Zn after half a year2+/(mg/L) | 1.43 | 1.09 | 0.87 |
| Mn after half a year2+/(mg/L) | 1.06 | 0.77 | 0.41 |
| Hg after half a year2+/(mg/L) | 0.75 | 0.63 | 0.36 |
Claims (6)
1. a kind of N, the preparation side of N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion modified alta-muds
Method, it is characterised in that comprise the steps：
(1) bentonite original soil is processed：The bentonite original soil for taking is dried at 100 DEG C -120 DEG C, crushed,
Grinding is sieved for subsequent use；
(2) preparation of bentonite suspension：By above-mentioned bentonite and water in mass ratio 1：(10-35) mix, plus
Heat obtains suspension to 60-100 DEG C of stirring no less than 60min；
(3) preparation of sodium bentonite：Na is added in bentonite suspension2CO3Solution, by its
Mix homogeneously is heated with stirring at 60-100 DEG C, sodium bentonite suspension is obtained；
(4) preparation of N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ions：Under nitrogen protection, with
Chloroform is solvent, triethylamine is acid-binding agent, adds mercaptoethylamine hydrochloride, between being slowly added dropwise under ice bath stirring again
Phthalyl chloride so that mercaptoethylamine hydrochloride is 2 with the mol ratio of m-phthaloyl chloride:8, after persistently stirring,
With water extraction 2-3 time, organic layer distillation aqueous solvent is dried, by products therefrom wiring solution-forming, CaCl is added2Molten
Liquid obtains N, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide complex ion solution, set aside for use after being sufficiently stirred for；
(5) the complex ion solution described in step (4) is pressed with the sodium bentonite suspension described in step (3)
Volume ratio 1：5 mixing, and stir in 60-100 DEG C of water bath with thermostatic control, centrifugal drying, grinding sieve, obtain
Arrive target product.
2. N as claimed in claim 1, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion are modified
Preparation method for bentonite, it is characterised in that in step (1), ground 100-200 mesh sieves.
3. N as claimed in claim 1, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion are modified
Preparation method for bentonite, it is characterised in that in step (3), Na2CO3The concentration of solution is
0.1mol/L, bentonite suspension and Na2CO3The volume ratio of solution is 20:1, the agitating heating time is not
It is less than 60min.
4. N as claimed in claim 1, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion are modified
Preparation method for bentonite, it is characterised in that in step (4), CaCl2Solution and N, N '-bis- (2-
Mercaptoethyl) concentration of -1,3- phenyl-diformyl amine aqueous solutions is 0.01mol/L, its volume ratio 1：1.
5. N as claimed in claim 1, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion are modified
Preparation method for bentonite, it is characterised in that in step (4), triethylamine and mercaptoethylamine hydrochloride
Mass ratio be 1.37：1.
6. N as claimed in claim 1, N '-bis- (2- mercaptoethyls) -1,3- benzenedicarboxamide calcium complex ion are modified
Preparation method for bentonite, it is characterised in that in step (5), agitating heating time are no less than 60min,
Not higher than 120 DEG C of centrifugal drying temperature, crosses 100-200 mesh sieves after grinding.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092255A (en) * | 2018-09-07 | 2018-12-28 | 湖州市道场乡资产经营有限公司 | A kind of preparation method of corn straw modification adsorbent |
| CN114853026A (en) * | 2022-03-30 | 2022-08-05 | 哈工大机器人集团(杭州湾)国际创新研究院 | Preparation method of high-performance lithium bentonite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012018422A1 (en) * | 2010-08-03 | 2012-02-09 | Ferro Corporation | Polymer composite foams |
| CN102974305A (en) * | 2012-11-20 | 2013-03-20 | 天津工业大学 | Method for high-efficiency removal of heavy metal ions in water |
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- 2015-09-07 CN CN201510563661.XA patent/CN106492745B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012018422A1 (en) * | 2010-08-03 | 2012-02-09 | Ferro Corporation | Polymer composite foams |
| CN102974305A (en) * | 2012-11-20 | 2013-03-20 | 天津工业大学 | Method for high-efficiency removal of heavy metal ions in water |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092255A (en) * | 2018-09-07 | 2018-12-28 | 湖州市道场乡资产经营有限公司 | A kind of preparation method of corn straw modification adsorbent |
| CN114853026A (en) * | 2022-03-30 | 2022-08-05 | 哈工大机器人集团(杭州湾)国际创新研究院 | Preparation method of high-performance lithium bentonite |
| CN114853026B (en) * | 2022-03-30 | 2023-08-08 | 哈工大机器人集团(杭州湾)国际创新研究院 | Preparation method of high-performance lithium bentonite |
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