CN108912328A - Preparation method of heavy metal ion chelating agent - Google Patents
Preparation method of heavy metal ion chelating agent Download PDFInfo
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- CN108912328A CN108912328A CN201810865052.3A CN201810865052A CN108912328A CN 108912328 A CN108912328 A CN 108912328A CN 201810865052 A CN201810865052 A CN 201810865052A CN 108912328 A CN108912328 A CN 108912328A
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- polyethyleneimine
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- chelating agent
- heavy metal
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- 239000002738 chelating agent Substances 0.000 title claims abstract description 51
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000013067 intermediate product Substances 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 64
- 150000002500 ions Chemical class 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 230000003252 repetitive effect Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 10
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- 229960004756 ethanol Drugs 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012990 dithiocarbamate Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- XTUNVEMVWFXFGV-UHFFFAOYSA-N [C].CCO Chemical compound [C].CCO XTUNVEMVWFXFGV-UHFFFAOYSA-N 0.000 description 4
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- WKQLTZBJJOLGCH-UHFFFAOYSA-N ethanol;methanedithione Chemical compound CCO.S=C=S WKQLTZBJJOLGCH-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- XVIWVTWNQQUGQI-UHFFFAOYSA-L disodium;sulfanylidenemethanediolate Chemical compound [Na+].[Na+].[O-]C([O-])=S XVIWVTWNQQUGQI-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a preparation method of a heavy metal ion chelating agent. The preparation method comprises the following steps: (1) reacting polyethyleneimine and carbon disulfide serving as raw materials and alcohol and/or ether serving as a solvent to generate a solid intermediate product; (2) and reacting the solid intermediate product with alkali to obtain the heavy metal ion chelating agent. The invention takes alcohol and/or ether as solvent, can form homogeneous reaction system, is helpful for full contact reaction of polyethyleneimine and carbon disulfide, and shortens reaction time; alcohol and ether can be recycled more conveniently, so that the production cost is reduced; the alkali is introduced after the reaction of the polyethyleneimine and the carbon disulfide, so that the side reaction of the carbon disulfide and the alkali is avoided, and the yield of the product is improved.
Description
Technical field
The invention belongs to chelating agent technical fields, and in particular to a kind of preparation method of heavy metal ion chelating agent.
Background technique
It is heavy metal-polluted to have a finger in every pie the environmental pollution as caused by heavy metal or its compound.Mainly by mining, exhaust gas discharge, sewage
It irrigates and using caused by the human factors such as heavy metals exceeding standard product.Heavy metal pollution is different from the pollution of other organic compounds,
Many organic compounds can make harmfulness reduce or release by nature physics itself, chemical or biological purification,
And heavy metal has enriching, is difficult to degrade in the environment.General processing heavy metal wastewater thereby method has method physically or chemically.
Currently, most common process for treating heavy-metal waste water is chemical precipitation method.This method is will be in chelating agent and waste water
Heavy metal ion combine, generate not soluble in water, chelate that property is stable, which is usually with precipitating or suspension
Form exist.This method for separating heavy metal from waste water can effectively achieve the purpose of control heavy metal.
Heavy metal chelant can be divided into two class of small molecule and macromolecule according to molecular weight difference；Small molecule chelators and metal
Ions binding generates the chelate of suspension, needs just settle down by the way that flocculant is added.High-molecular chelating agent has heavy
The good feature of performance drops.
Currently, in order to efficiently, economically control heavy metal pollution problem, need to develop on the basis of existing one kind it is high-quality
The macromolecular heavy metal chelating agent of amount, low cost.There are two ways to synthesizing macromolecular heavy metal chelating agent：One is polymerizeing
Chelate structure is introduced or formed on object skeleton with various methods, another kind is led to using small molecule complexing agent or chelating agent as raw material
Cross the preparation of producing high-molecular method.
In recent years, the macromolecule dithiocar-bamate chelating agent synthesized using polyethyleneimine as skeleton becomes weight
The hot spot of metal ion wastewater treatment industry concern.
The preparation method of existing dithiocar-bamate chelating agent, such as CN 101081827A, CN 103965471A
It with CN 105084502A, takes water as a solvent, first mixes polyethyleneimine with sodium hydroxide solution, two sulphur are then added dropwise
Change carbon aqueous solution to be reacted, obtains Chinese red product.But this preparation method is long there are the reaction time, product yield compared with
It is low, and there are the by-products such as Chinese red sodium thiocarbonate, limit dithiocar-bamate large-scale production and
Using having much room for improvement.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of preparation of heavy metal ion chelating agent
Method.This method can reduce side reaction, shorten the reaction time, improve the yield of chelating agent, reduce cost.
For this purpose, the present invention uses following technical scheme：
The present invention provides a kind of preparation method of heavy metal ion chelating agent, includes the following steps：
(1) using polyethyleneimine and carbon disulfide as raw material, alcohol and/or ether are solvent, and reaction is generated and produced among solid
Object；
(2) solid intermediate product is reacted with alkali, obtains the heavy metal ion chelating agent.
Inventors discovered through research that preparing the process of macromolecule dithiocar-bamate chelating agent using existing method
In, raw material can be layered, and form heterogeneous system.Wherein, lower layer is carbon disulfide, and middle layer is sodium hydrate aqueous solution,
Upper layer is aq. polyethyleneimine.During the reaction, carbon disulfide is difficult to come into full contact with polyethyleneimine, needs to carry out
Long agitation, and carbon disulfide easily reacted with sodium hydroxide generate Chinese red sodium thiocarbonate, cause product yield compared with
It is low.
The present invention uses alcohol and/or ether for solvent, can form homogeneous reaction system, polyethyleneimine and carbon disulfide can
Reaction is come into full contact with, helps to shorten the reaction time；The solid intermediate product that reaction generates does not dissolve in pure and mild ether, by simple
Filtering is i.e. separable, then the solid intermediate product of the drying is reacted with alkali, and pistac dithiocarbamates can be obtained
Formates chelating agent avoids carbon disulfide and contacts with alkali, reduce side reaction, improves product yield.Moreover, pure and mild ether ratio
Utilization is recovered more easily in water, helps to reduce production cost.
As the preferred technical solution of the present invention, the preparation method includes the following steps：
(1) using alcohol and/or ether as solvent, polyethylenimine solution is added drop-wise in carbon disulfide solution, is reacted, consolidate
Body intermediate product；
(2) solid intermediate product is dissolved in lye, reaction obtains the heavy metal ion chelating agent.
As the preferred technical solution of the present invention, mole of the repetitive unit of the polyethyleneimine and the carbon disulfide
Than for 0.3-0.8:1；Such as it can be 0.3:1,0.32:1,0.35:1,0.38:1,0.4:1,0.42:1,0.45:1,0.48:
1、0.5:1、0.52:1、0.55:1、0.58:1、0.6:1、0.62:1、0.65:1、0.68:1、0.7:1、0.72:1、0.75:1、
0.78:1 or 0.8:1 etc..
As the preferred technical solution of the present invention, the number-average molecular weight of the polyethyleneimine is 1000-100000；Such as
Can be 1000,1500,2000,3000,5000,6000,8000,10000,15000,20000,30000,40000,50000,
60000,70000,80000,90000 or 100000 etc..
Inventors discovered through research that the molecular weight of polyethyleneimine is bigger in water phase, with alkali, carbon disulfide
Lamination is just more obvious, and side reaction accounting is more, and product yield is lower.Therefore, method provided by the invention is especially suitable for using
In preparation using macromolecule (such as 2000 or more) polyethyleneimine as the chelating agent of raw material.
As the preferred technical solution of the present invention, the concentration of the polyethylenimine solution is 80-125g/L；Such as it can be with
It is 80g/L, 100g/L, 105g/L, 110g/L, 115g/L, 120g/L or 125g/L etc..
Preferably, the concentration of the carbon disulfide solution is 200-250g/L；Such as can be 200g/L, 210g/L,
220g/L, 230g/L, 240g/L or 250g/L etc..
As the preferred technical solution of the present invention, the temperature of reaction described in step (1) is 5-40 DEG C；Such as it can be 5
℃、6℃、8℃、10℃、12℃、13℃、15℃、16℃、18℃、20℃、22℃、23℃、25℃、26℃、28℃、30℃、
32 DEG C, 33 DEG C, 35 DEG C, 36 DEG C, 38 DEG C or 40 DEG C etc.；More preferably 5-20 DEG C.
Preferably, the time of reaction described in step (1) is 1-3h；Such as can be 1h, 1.2h, 1.3h, 1.5h,
1.6h, 1.8h, 2h, 2.2h, 2.3h, 2.5h, 2.6h, 2.8h or 3h etc..
It should be noted that polyethyleneimine starts to react with carbon disulfide due to during dropwise addition, because
This, the time of above-mentioned reaction referred to from the time for starting adding raw materials to reaction end.
As the preferred technical solution of the present invention, the alcohol is ethyl alcohol.
Preferably, the ether is ether.
As the preferred technical solution of the present invention, step (1) further includes：It is separated by solid-liquid separation and is washed after the completion of reaction
It washs.
The present invention is not particularly limited the method for the separation of solid and liquid and washing, illustratively, can choose and uses alcohol
And/or ether is washed, the method for suction filtration is separated by solid-liquid separation.
Preferably, the molar ratio of the repetitive unit of the alkali and the polyethyleneimine is 1:(1-1.5)；Such as it can be
1:1.0,1:1.1,1:1.2,1:1.3,1:1.4 or 1:1.5 waiting.
As the preferred technical solution of the present invention, the alkali is sodium hydroxide and/or potassium hydroxide, preferably hydroxide
Sodium.
As the preferred technical solution of the present invention, the preparation method includes the following steps：
(1) controlled at 5-40 DEG C, using alcohol and/or ether as solvent, polyethylenimine solution is added drop-wise to carbon disulfide
It is reacted in solution, the repetitive unit of polyethyleneimine and the molar ratio of carbon disulfide are 0.3-0.8:1, from starting to be added drop-wise to
The time that reaction terminates is 1-3h, is separated by solid-liquid separation and obtains solid intermediate product after washing；
(2) solid intermediate product is dissolved in sodium hydroxide solution, the repetition list of sodium hydroxide and polyethyleneimine
The molar ratio of member is 1:(1-1.5), reaction obtain the heavy metal ion chelating agent.
It is to exist in form of an aqueous solutions by heavy metal ion chelating agent obtained by the above method, those skilled in the art
It can be according to actual needs by water removal (as being dried in vacuo), to obtain solid product.
Compared with prior art, the invention has the advantages that：
The present invention is capable of forming homogeneous reaction system, facilitates polyethyleneimine and curing using alcohol and/or ether as solvent
Carbon comes into full contact with reaction, shortens the reaction time；And pure and mild ether can be recycled more easily, reduce production cost；
Alkali introduces after polyethyleneimine and carbon disulfide reaction, avoids the side reaction of carbon disulfide and alkali, the yield of product reaches
To 90-95%.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of heavy metal ion chelating agent, include the following steps：
(1) curing of polyethyleneimine diethyl ether solution (number-average molecular weight 1000) and 250g/L of 125g/L is prepared respectively
Carbon diethyl ether solution；
(2) polyethyleneimine diethyl ether solution is added drop-wise in carbon disulfide diethyl ether solution and carries out instead at 5 DEG C by control temperature
It answers, the repetitive unit of polyethyleneimine and the molar ratio of carbon disulfide are 0.8:1, be from the time for starting to be added drop-wise to reaction end
1.5h is filtered after reaction, and is washed with ether, and solid intermediate product is obtained；
It (3) is 1 by the molar ratio of sodium hydroxide and the repetitive unit of polyethyleneimine:1, the solid that step (2) is obtained
Intermediate product is dissolved in sodium hydroxide solution, is obtained pistac heavy metal ion chelating agent solution, is obtained solid weight after dry
Metal ion chelation agent.
Preparation method provided in this embodiment can reduce side reaction, shorten the reaction time, improve the yield of chelating agent
(90.7%), cost is reduced.
Embodiment 2
The present embodiment provides a kind of preparation methods of heavy metal ion chelating agent, include the following steps：
(1) curing of polyethyleneimine ethanol solution (number-average molecular weight 5000) and 250g/L of 125g/L is prepared respectively
Carbon ethanol solution；
(2) polyethyleneimine ethanol solution is added drop-wise in carbon disulfide ethanol solution and carries out instead at 10 DEG C by control temperature
It answers, the repetitive unit of polyethyleneimine and the molar ratio of carbon disulfide are 0.7:1, be from the time for starting to be added drop-wise to reaction end
2h is filtered after reaction, and is washed with dehydrated alcohol, and solid intermediate product is obtained；
It (3) is 1 by the molar ratio of sodium hydroxide and the repetitive unit of polyethyleneimine:1.2, consolidate what step (2) obtained
Body intermediate product is dissolved in sodium hydroxide solution, is obtained pistac heavy metal ion chelating agent solution, is obtained solid after dry
Heavy metal ion chelating agent.
Preparation method provided in this embodiment can reduce side reaction, shorten the reaction time, improve the yield of chelating agent
(91.4%), cost is reduced.
Embodiment 3
The present embodiment provides a kind of preparation methods of heavy metal ion chelating agent, include the following steps：
(1) curing of polyethyleneimine ethanol solution (number-average molecular weight 10,000) and 200g/L of 125g/L is prepared respectively
Carbon ethanol solution；
(2) controlled at 15 DEG C, polyethyleneimine ethanol solution is added drop-wise in carbon disulfide ethanol solution and is carried out instead
It answers, the repetitive unit of polyethyleneimine and the molar ratio of carbon disulfide are 0.5:1, be from the time for starting to be added drop-wise to reaction end
2h is filtered after reaction, dry, obtains solid intermediate product；
It (3) is 1 by the molar ratio of sodium hydroxide and the repetitive unit of polyethyleneimine:1.3, consolidate what step (2) obtained
Body intermediate product is dissolved in sodium hydroxide solution, obtains pistac heavy metal ion chelating agent, and a solid huge sum of money is obtained after dry
Belong to ion chelating agent.
Preparation method provided in this embodiment can reduce side reaction, shorten the reaction time, improve the yield of chelating agent
(93.5%), cost is reduced.
Embodiment 4
The present embodiment provides a kind of preparation methods of heavy metal ion chelating agent, include the following steps：
(1) curing of polyethyleneimine ethanol solution (number-average molecular weight 30,000) and 200g/L of 125g/L is prepared respectively
Carbon ethanol solution；
(2) controlled at 20 DEG C, polyethyleneimine ethanol solution is added drop-wise in carbon disulfide ethanol solution and is carried out instead
It answers, the repetitive unit of polyethyleneimine and the molar ratio of carbon disulfide are 0.4:1, be from the time for starting to be added drop-wise to reaction end
2.5h is filtered after reaction, and is washed with dehydrated alcohol, and solid intermediate product is obtained；
It (3) is 1 by the molar ratio of sodium hydroxide and the repetitive unit of polyethyleneimine:1, the solid that step (2) is obtained
Intermediate product is dissolved in sodium hydroxide solution, is obtained pistac heavy metal ion chelating agent solution, is obtained solid weight after dry
Metal ion chelation agent.
Preparation method provided in this embodiment can reduce side reaction, shorten the reaction time, improve the yield of chelating agent
(94.0%), cost is reduced.
Embodiment 5
The present embodiment provides a kind of preparation methods of heavy metal ion chelating agent, include the following steps：
(1) curing of polyethyleneimine ethanol solution (number-average molecular weight 100,000) and 200g/L of 100g/L is prepared respectively
Carbon ethanol solution；
(2) controlled at 40 DEG C, polyethyleneimine ethanol solution is added drop-wise in carbon disulfide ethanol solution and is carried out instead
It answers, the repetitive unit of polyethyleneimine and the molar ratio of carbon disulfide are 0.3:1, be from the time for starting to be added drop-wise to reaction end
1h is filtered after reaction, and is washed with dehydrated alcohol, and solid intermediate product is obtained；
It (3) is 1 by the molar ratio of sodium hydroxide and the repetitive unit of polyethyleneimine:1.5, consolidate what step (2) obtained
Body intermediate product is dissolved in sodium hydroxide solution, is obtained pistac heavy metal ion chelating agent solution, is obtained solid after dry
Heavy metal ion chelating agent.
Preparation method provided in this embodiment can reduce side reaction, shorten the reaction time, improve the yield of chelating agent
(94.1%), cost is reduced.
The embodiment 1-5 heavy metal ion chelating agent provided is configured to the aqueous solution of 50mg/mL, for use.Prepare 10mg/
The Pb of L2+、Ni2+、Cu2+、Cd2+Each 100mL of solution, as simulated wastewater.It is 2 according to chelating agent and metal ion molar ratio:1
Above-mentioned heavy metal ion chelating agent aqueous solution is added in ratio, adjusts pH value while stirring to acid (pH=5.0-5.5), stands
15min, filtering.With ICP-MS (inductivity coupled plasma mass spectrometry) measure the heavy metal of supernatant after the processing of each simulated wastewater from
Various removal of heavy metal ions rates are calculated in sub- concentration.Each metal ion removal rate is as shown in table 1 below：
Table 1
| Pb2+ | Ni2+ | Cu2+ | Cd2+ | |
| Embodiment 1 | 99.8% | 99.8% | 99.9% | 99.7% |
| Embodiment 2 | 99.6% | 99.7% | 99.9% | 99.8% |
| Embodiment 3 | 99.9% | 99.8% | 99.8% | 99.9% |
| Embodiment 4 | 99.8% | 99.5% | 99.9% | 99.8% |
| Embodiment 5 | 99.8% | 99.9% | 99.9% | 99.8% |
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of heavy metal ion chelating agent, which is characterized in that the preparation method includes the following steps：
(1) using polyethyleneimine and carbon disulfide as raw material, alcohol and/or ether are solvent, and reaction generates solid intermediate product；
(2) solid intermediate product is reacted with alkali, obtains the heavy metal ion chelating agent.
2. preparation method according to claim 1, which is characterized in that the preparation method includes the following steps：
(1) using alcohol and/or ether as solvent, polyethylenimine solution is added drop-wise in carbon disulfide solution, reacts, obtains in solid
Between product；
(2) solid intermediate product is dissolved in lye, reaction obtains the heavy metal ion chelating agent.
3. preparation method according to claim 1 or 2, which is characterized in that the repetitive unit of the polyethyleneimine and institute
The molar ratio for stating carbon disulfide is 0.3-0.8:1.
4. preparation method according to claim 1-3, which is characterized in that the equal molecule of the number of the polyethyleneimine
Amount is 1000-100000.
5. according to the described in any item preparation methods of claim 2-4, which is characterized in that the concentration of the polyethylenimine solution
For 100-125g/L；
Preferably, the concentration of the carbon disulfide solution is 200-250g/L.
6. preparation method according to claim 1-5, which is characterized in that the temperature of reaction described in step (1)
It is 5-40 DEG C；
Preferably, the time of reaction described in step (1) is 1-3h.
7. preparation method according to claim 1-6, which is characterized in that the alcohol is ethyl alcohol；
Preferably, the ether is ether.
8. preparation method according to claim 1-7, which is characterized in that step (1) further includes：Terminate in reaction
After be separated by solid-liquid separation and washed；
Preferably, the molar ratio of the repetitive unit of the alkali and the polyethyleneimine is 1:(1-1.5).
9. preparation method according to claim 1-8, which is characterized in that the alkali is sodium hydroxide and/or hydrogen
Potassium oxide, preferably sodium hydroxide.
10. -9 described in any item preparation methods according to claim 1, which is characterized in that the preparation method includes following step
Suddenly：
(1) controlled at 5-20 DEG C, polyethylenimine solution is added drop-wise in carbon disulfide solution and is reacted, polyethyleneimine
The repetitive unit of amine and the molar ratio of carbon disulfide are 0.3-0.8:1, it is 1-3h from the time for starting to be added drop-wise to reaction end, Gu
Solid intermediate product is obtained after liquid separation and washing；
(2) solid intermediate product is dissolved in sodium hydroxide solution, the repetitive unit of sodium hydroxide and polyethyleneimine
Molar ratio is 1:(1-1.5), reaction obtain the heavy metal ion chelating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810865052.3A CN108912328B (en) | 2018-08-01 | 2018-08-01 | Preparation method of heavy metal ion chelating agent |
Applications Claiming Priority (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110354819A (en) * | 2019-08-15 | 2019-10-22 | 广州大学 | A kind of plant cellulose absorption sponge, preparation method and its application |
| CN112853390A (en) * | 2020-12-31 | 2021-05-28 | 武汉度美迪新能源科技有限公司 | Oxygen reduction catalyst and preparation method thereof |
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| JPS5036366A (en) * | 1973-08-02 | 1975-04-05 | ||
| GB2117752A (en) * | 1982-03-29 | 1983-10-19 | Secr Defence | Metal ion extraction process |
| US20030083456A1 (en) * | 2001-10-04 | 2003-05-01 | Foster Alvie L. | Polydithiocarbamate resin |
| CN104445564A (en) * | 2014-12-18 | 2015-03-25 | 淄博金鼎光电科技有限公司 | Synthesis method of heavy metal chelating agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036366A (en) * | 1973-08-02 | 1975-04-05 | ||
| GB2117752A (en) * | 1982-03-29 | 1983-10-19 | Secr Defence | Metal ion extraction process |
| US20030083456A1 (en) * | 2001-10-04 | 2003-05-01 | Foster Alvie L. | Polydithiocarbamate resin |
| CN104445564A (en) * | 2014-12-18 | 2015-03-25 | 淄博金鼎光电科技有限公司 | Synthesis method of heavy metal chelating agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354819A (en) * | 2019-08-15 | 2019-10-22 | 广州大学 | A kind of plant cellulose absorption sponge, preparation method and its application |
| CN110354819B (en) * | 2019-08-15 | 2022-05-03 | 广州大学 | Plant cellulose adsorption sponge, preparation method and application thereof |
| CN112853390A (en) * | 2020-12-31 | 2021-05-28 | 武汉度美迪新能源科技有限公司 | Oxygen reduction catalyst and preparation method thereof |
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