CN102031118A - Heavy metal chelating agent and preparation method thereof - Google Patents
Heavy metal chelating agent and preparation method thereof Download PDFInfo
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- CN102031118A CN102031118A CN2010102954567A CN201010295456A CN102031118A CN 102031118 A CN102031118 A CN 102031118A CN 2010102954567 A CN2010102954567 A CN 2010102954567A CN 201010295456 A CN201010295456 A CN 201010295456A CN 102031118 A CN102031118 A CN 102031118A
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- heavy metal
- chelating agent
- metal chelating
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- silica gel
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Abstract
The invention discloses a heavy metal chelating agent. The heavy metal chelating agent has a structural formula which is shown in the specification. A preparation method of the heavy metal chelating agent of the structural formula comprises the following steps of: adding solution of formaldehyde at concentration of 30 percent and polyethyleneimine silica gel into a flask in which a stirrer, a dropping funnel and a thermometer are arranged in turn; simultaneously, dropwise adding aqueous solution of diacetoxyl imine at concentration of between 10 and 20 percent during cooling of an ice bath; controlling dropping speed to keep temperature in the flask to be less than or equal to 25 DEG C; and stirring reaction solution for at least 12 hours and filtering to obtain colloidal particles, namely the required heavy metal chelating agent. The heavy metal chelating agent has the advantages of high chelating capacity and thermal stability, reusability and the like.
Description
Technical field
The present invention relates to chemical field, specifically relate to a kind of heavy metal chelant and preparation method thereof.
Background technology
Heavy metal generally extensively is present in occurring in nature with natural concentration, but because human exploitation, smelting, processing and commercial manufacturing activities to metal increasing caused plurality of heavy metal such as lead, chromium, cadmium, arsenic enters soil.Will retain, accumulate after the heavy metal that exists with various chemical forms enters soil, cause the pollution of soil, the simultaneous migration produces food chain and concentrates, and causes the harm to the mankind and other biological.
Repair used reagent at heavy-metal contaminated soil in the market and mainly contain biological species and chemical classes two class materials.Biological species has: herbaceous plant, active sludge, biology and microbial bacterial; The common material of chemical classes then is: EDTA and sodium sulphite.Though relatively environmental protection of the technology that biological species reagent adopts, shortcoming is that repairing efficiency is long, the immature laboratory level that only limits to of technology.For example herbaceous plant applies to the mechanism of soil remediation and is: absorbed to reach by plant materials by heavy metal and reduce heavy metal in soil content, the processing cycle is oversize; When active sludge and other microbial bacterials carried out soil remediation, the discontinuous distribution of pollutent can be blocked self and produce, easily inactivation; And EDTA has very strong metal chelating ability in the chemical classes, but molecular weight is less, and the inner complex of formation is gone into water body in that acidic solution (PH=4.5-5) drip washing is dirty easily, causes secondary pollution.And the defective of sodium sulphite is to have stench, is not suitable on a large scale as environmental pollution treatment field.
Summary of the invention
The object of the present invention is to provide that sequestering power is strong, Heat stability is good and repeatedly used heavy metal chelant, and the preparation method of this heavy metal chelant.
A kind of heavy metal chelant has following structural formula:
A kind of preparation method who prepares aforesaid heavy metal chelant, comprise the steps: in the flask that stirring, dropping funnel, thermometer are housed, to add successively 30% formaldehyde solution and polymine silica gel, drip 10%～20% oxalic acid imines aqueous solution simultaneously in the ice bath cooling, the control rate of addition, make the interior temperature of flask be no more than 25 ℃, stirring reaction liquid at least 12 hours, the micelle that obtains after the filtration is required heavy metal chelant.
Further, count in molar ratio, the feed ratio of described formaldehyde solution and polymine silica gel is 1～1.2: 1.
Further, count in molar ratio, the charging capacity of the described oxalic acid imines aqueous solution is 1～2 times of polymine silica gel.
Among the above-mentioned preparation method, the heavy metal chelant that makes is washed into silica gel particle with pure water again, under 60～65 ℃ temperature condition, vacuum-drying is to moisture＜10%, and the heavy metal chelate sealing that obtains is preserved towards nitrogen.
In above-mentioned, the structural formula of polymine silica gel is:
Reaction formula of the present invention is:
Beneficial effect of the present invention is: because the matrix that the present invention adopts is commercially available polymine silica gel (structural formula as above), polymine silica gel be excellent performance be used to dig up mine the mineral substance extraction agent of industry, it has following characteristic: itself does not have swelling property resin, to Na
+ 1, K
+ 1, Ca
+ 2Substantially there is not stowage capacity etc. environmentally friendly ion; PH can well load Cu in 3～10 scopes
+ 2, Ni
+ 2, Co
+ 2, Zn
+ 2, Pd
+ 2, Fe
+ 2, Fe
+ 3, Mn
+ 2, Al
+ 3Plasma, simultaneously, the present invention has adopted polymine silica gel and the oxalic acid imines aqueous solution raw material as reaction, be because the group of oxalic acid imines is the group of the two carboxylic acid structures of similar ethylenediamine tetraacetic acid (EDTA) (EDTA), and the very strong sequestrant of sequestering power that EDTA is everybody to be known, polymine metal stowage capacity and kind in the presence of the oxalic acid imines is wider, has greatly improved metal-chelating performance of the present invention.And polymine can go out institute's chelated metal ion by wash-out under the effect of sulfuric acid, nitric acid, use so repeatedly 3000 times, and its stowage capacity only reduces by 10%, even less than 10%.Polymine has superpower thermostability, even still has good loading effect when envrionment temperature reaches 110 ℃, utilize polymine be matrix of the present invention everybody improved people's stability of product of the present invention.
To sum up, the present invention has following advantage:
1, sequestering power is strong: have the metal stowage capacity of polymine silica gel and the metal-chelating ability of the similar group of EDTA concurrently, can catch various heavy and transition metal ion effectively, and the sequestering power of different metal reaches 10mg/g at least.
2, good stability: in pH value 3～10 scopes, can stablize the material of residence chelating, not produce the free of metal ion.
3, Heat stability is good: the rising along with surface temperature does not produce the free of metal ion.
4, can use repeatedly; Institute's chelated metal ion can be eluted by sulfuric acid and salpeter solution, reaches the collection metal ion, recycles the purpose of metal chelator.
Embodiment
Below in conjunction with concrete embodiment, the present invention is done detailed description.
Embodiment 1
The invention provides a kind of heavy metal chelant, its structural formula is as follows:
The outward appearance of sequestrant of the present invention is a white particle, and the order number is 350-650um.
The preparation method of above-mentioned heavy metal chelant is as follows:
Embodiment 1
In being equipped with the flask of mechanical stirring, dropping funnel, thermometer, 500ml adds 10g (0.1mol) 30% formaldehyde solution, polymine silica gel 35g (0.1mol), under the ice bath cooling, reaction mixture drips the 70g 20% oxalic acid imines aqueous solution while stirring, the control rate of addition, make temperature be no more than 25 ℃, reaction solution stirs 12 hours after-filtration, obtains heavy metal chelant, and with the pure water washed twice of 200ml.The heavy metal chelant silica gel particle of gained, temperature are under 65 ℃ of conditions, and vacuum-drying is to moisture＜10%, and the product sealing is preserved towards nitrogen, and after testing, mass yield is 100%.
Embodiment 2
In being housed, the 2L flask of mechanical stirring, dropping funnel, thermometer adds 110g (1.1mol) 30% formaldehyde solution, polymine silica gel 350g (1mol), under the ice bath cooling, reaction mixture drips the aqueous solution of 800g 17% oxalic acid imines while stirring, the control rate of addition, make temperature be no more than 25 ℃, reaction solution stirred 18 hours after-filtration, heavy metal chelant, and with twice of 2L pure water washing crude product.The heavy metal chelant silica gel particle of gained, temperature are under 65 ℃ of conditions, and vacuum-drying is to moisture＜10%, and the product sealing is preserved towards nitrogen, and after testing, mass yield is 98%.
Metal-chelating aptitude tests method:
Below be metal-chelating aptitude tests of the present invention, reach 10mg/g at different heavy metals and transition metal sequestering power, concrete data are as follows:
Implementation step: prewired 3 groups of 150ML mixture-metal solions, the metal ion type is: Cu
2+, Zn
2+, Cr
2+, Cd
2+, As
3+, Pb
2+Ionic concn is: 3.0g/L.Testing each metal ion content with the spectral element analytical procedure is C
0(ppm); Modified silica-gel to be measured is filled the direct 1cm that packs into, and column volume is 9.4cm
3Post in; With the heavy metal solution of pre-assigned 150ml 3.0g/L with the flow velocity of 0.15BV/min by the modified silica-gel post, effluent liquid is tested to such an extent that each metal ion content is C once more
x(ppm), the result gets the mean value of three groups of experiments.
Silica gel loading capacity L (mg/g)=(C
0-C
x) * 0.15/W
W: modified silica-gel weight to be measured
Following table is the metal-chelating test result of heavy metal chelant
Claims (4)
1. a heavy metal chelant is characterized in that, has following structural formula:
2. preparation method who prepares heavy metal chelant as claimed in claim 1, it is characterized in that: in the flask that stirring, dropping funnel, thermometer are housed, add 30% formaldehyde solution and polymine silica gel successively, drip 10%～20% oxalic acid imines aqueous solution simultaneously in the ice bath cooling, the control rate of addition, make the interior temperature of flask be no more than 25 ℃, stirring reaction liquid at least 12 hours, the micelle that obtains after the filtration is required heavy metal chelant.
3. preparation method according to claim 2 is characterized in that: count in molar ratio, the feed ratio of described formaldehyde solution and polymine silica gel is 1～1.2: 1.
4. preparation method according to claim 2 is characterized in that: count in molar ratio, the charging capacity of the described oxalic acid imines aqueous solution is 1～2 times of polymine silica gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102954567A CN102031118A (en) | 2010-09-29 | 2010-09-29 | Heavy metal chelating agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102954567A CN102031118A (en) | 2010-09-29 | 2010-09-29 | Heavy metal chelating agent and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102031118A true CN102031118A (en) | 2011-04-27 |
Family
ID=43884587
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| CN2010102954567A Pending CN102031118A (en) | 2010-09-29 | 2010-09-29 | Heavy metal chelating agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933696A (en) * | 2014-03-19 | 2014-07-23 | 上海鼓华生态科技有限公司 | Curing agent for curing and stabilization of poisonous and harmful solid waste |
| CN114773243A (en) * | 2022-04-28 | 2022-07-22 | 成都中科绿生环境科技有限公司 | Heavy metal chelating agent |
| CN115925153A (en) * | 2022-11-11 | 2023-04-07 | 广东水清环保科技有限公司 | Electronic wastewater treatment process capable of stably achieving three-class water standard of ground |
-
2010
- 2010-09-29 CN CN2010102954567A patent/CN102031118A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933696A (en) * | 2014-03-19 | 2014-07-23 | 上海鼓华生态科技有限公司 | Curing agent for curing and stabilization of poisonous and harmful solid waste |
| CN114773243A (en) * | 2022-04-28 | 2022-07-22 | 成都中科绿生环境科技有限公司 | Heavy metal chelating agent |
| CN114773243B (en) * | 2022-04-28 | 2023-08-22 | 成都中科绿生环境科技有限公司 | Heavy metal chelating agent |
| CN115925153A (en) * | 2022-11-11 | 2023-04-07 | 广东水清环保科技有限公司 | Electronic wastewater treatment process capable of stably achieving three-class water standard of ground |
| CN115925153B (en) * | 2022-11-11 | 2024-01-23 | 广东水清环保科技有限公司 | Electronic wastewater treatment process capable of stably achieving three types of water standards on earth surface |
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Owner name: CHANGZHOU JASON CHONG ENVIRONMENTAL SCIENCE AND TE Free format text: FORMER OWNER: LI XIAOPING Effective date: 20120723 |
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Free format text: CORRECT: ADDRESS; FROM: 200062 PUTUO, SHANGHAI TO: 213022 CHANGZHOU, JIANGSU PROVINCE |
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Effective date of registration: 20120723 Address after: 213022 A, building 436, innovation and technology building, Xinbei hi tech park, Jiangsu, Changzhou Applicant after: Changzhou Jason Chong Environmental Science and Technology Co., Ltd. Address before: 200062 room 32, No. 1030, Lane 1001, Shanghai, West Yan'an Road Applicant before: Li Xiaoping |
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Application publication date: 20110427 |