CN101147864A - Method for preparing novel catalytic reduction dechlorinating agent - Google Patents
Method for preparing novel catalytic reduction dechlorinating agent Download PDFInfo
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- CN101147864A CN101147864A CNA2007100598373A CN200710059837A CN101147864A CN 101147864 A CN101147864 A CN 101147864A CN A2007100598373 A CNA2007100598373 A CN A2007100598373A CN 200710059837 A CN200710059837 A CN 200710059837A CN 101147864 A CN101147864 A CN 101147864A
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Abstract
The present invention provides a method for preparing new-type catalytic reduction antichlor. It is a method for preparing nano Ni-Fe dimetal composite catalytic reduction antichlor. It is characterized by that said antichlor can form NiB amorphous alloy cluster on the nano ferric oxide surface so as to raise antichloration property of ferric oxide.
Description
Technical field
The present invention relates to a kind of preparation method of novel catalytic reduction dechlorinating agent, and a kind of preparation of saying so more specifically has the method for the chemical machining nano Ni-Fe composite catalyzing reduction dechlorination agent of high dechlorination efficiency.
Background technology
Chlorine-containing organic compounds is of a great variety, is again important chemical material, intermediate and organic solvent, thereby is widely used in industries such as chemical industry, medicine, process hides, machinery, wood preservation.They use by volatilization, container leakage, discharge of wastewater, agricultural chemicals and pesticide and the approach such as burning of chlorinated organics finished product enter environment, severe contamination atmosphere, soil, underground water and surface water.Nearly all chlorinated aromatic hydrocarbons and derivative thereof are all toxic and be difficult to degraded, and wherein many chlorinated organics are listed in U.S. EPA environment priority pollutants.Especially persistence organic pollutant (Persistent Organic Pollutant, be called for short POPs) has " three cause " effect and the genetoxic of " carcinogenic, teratogenesis, mutagenesis "; Simultaneously, because a lot of chlorinated organics have high volatile volatile and class ester thing solubility, easily human body is caused serious harm by absorption such as skin, mucous membrane.Therefore, contamination with chlorinated organics has caused national governments, academia, industrial quarters and the public's extensive concern, becomes a global environmental problem.In recent years, along with the development of nanometer technology, at nanometer Fe
0Become the new focus that organic chlorine degradation is studied with nanometer M-Fe bimetallic system (M=Ni, Pt, Pd, Cu, Ag etc.).Nanometer Fe
0With the specific surface of nanometer M-Fe bimetallic system and surface reaction all than the common iron powder height.As, the BET specific area of nanometer Pd/Fe is 33.5m
2/ g, and the BET specific area of Fe powder is 0.9m
2/ g; The specific rate of reaction constant (kSA) of nanoscale Pd/Fe is that tens times of commodity Fe powder arrive hundred times.In addition, nanoscale Fe particulate can be injected into contaminated soil, deposit or aquifer and carry out the original position reparation, the method for administering after extracting out with alternative conventional iron reaction wall or with underground water.
At present, CN1868913 has reported that a kind of ferro-silicium powder and almag powder remove the method for chlorinated organics in the water body as the dechlorination material.Such antichlor can be degraded fast and be eliminated chlorinated organics in the water body.CN1837106 has then reported the method for a kind of ultrasonic organic chloride through metal reduction assisted and strengthened thing dechlorination.Choose zero-valent metal or metal alloy as reducing agent, establish supersonic generator in consersion unit, supersonic generator is launched ultrasonic wave to water body, strengthens the reduction dechlorination process of reducing agent to the organochlorine in the waste water.In addition, lot of documents report bimetallic catalyst has incomparable hydrogenation activity of single-metal reforming catalyst and selectivity.CN1831197 and CN1183316 have reported that distinct methods prepares the agent of Pd-Fe composite catalyzing reduction dechlorination and removes the organic process of water containing chlorine.And because costing an arm and a leg of precious metals pd influenced the extensive use of this antichlor.So, use transition metal to substitute noble metal and have Practical significance.2002, Thomas E.Mallouk reported a kind of Ni-Fe bimetallic catalyst chlorinatedorganic remove application in the reaction (Chem.Mater.2002,14,5140-5147).The author uses KBH
4Reduction Ni
2+And Fe
2+Mixed solution, obtain the agent of chemical machining nano Ni-Fe composite catalyzing reduction dechlorination.The author thinks, Fe
0Play the effect of reducing agent, be deposited on Fe
0The Ni on surface plays the effect of catalysis.And because the restriction of experimental technique is difficult to avoid Fe
0To the coating of Ni, make part Ni not to be utilized.Therefore, seek a kind of nanometer Ni uniform deposition that can make in nanometer Fe
0The method for preparing the bimetallic antichlor on surface is to have important in theory and practical significance.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing novel catalytic reduction dechlorinating agent, it is the method for preparing the agent of chemical machining nano Ni-Fe bimetallic composite catalyzing reduction dechlorination, and this antichlor can be in nanometer Fe
0The surface generates NiB amorphous alloy cluster, and then has improved nanometer Fe
0The dechlorination performance.
In the chemical machining nano Ni-Fe bimetallic composite catalyzing reduction dechlorination agent that characteristics of the present invention are to be developed, the NiB amorphous alloy is evenly distributed on nanometer Fe
0The surface is promoting Fe
0When reacting with reactant, again can be with nanometer Fe
0Active surface cover, guarantee Fe
0Can fully contact with reactant, Ni account for antichlor gross weight 1%～45%.
The preparation process of catalytic reduction dechlorinating agent is as follows:
Nanometer Fe with the chemical reduction method preparation
0(5～200nm) join in 5～350ml NiB chemical plating fluid, stir 5～120min down at 20～90 ℃.Product to neutral, is used absolute ethyl alcohol flush away residual moisture through the deionized water washing again.Product can be used for the dechlorination reaction of the chlorobenzene aqueous solution after drying.
Described nanometer Fe
0Size is in 5～200nm, and preferred cluster is of a size of the 60nm nanometer Fe
0
The NiB chemical plating fluid volume that adds in the described reaction is 5～350ml, preferred 220ml.
Described reaction temperature is 20～90 ℃, preferred 40 ℃.
The specific embodiment
Comparative Examples 1
The preparation process of this Comparative Examples explanation catalytic reduction dechlorinating agent.
Embodiment 1～10
These embodiment illustrate Ni-Fe bimetallic composite catalyzing reduction dechlorination agent process.
With the 1.0g yardstick is the nanometer Fe of 60nm
0Mix with 70ml NiB chemical plating fluid, stir 10min down at 35 ℃.Product to neutral, is used absolute ethyl alcohol flush away residual moisture through the deionized water washing again.Product obtains antichlor A after drying.Wherein the NiB chemical plating fluid consists of NiSO
46H
2O, ethylenediamine, NaOH, KBH
4And deionized water.
The same with antichlor A preparation process, with the nanometer Fe about 60nm
0Make the 5nm nanometer Fe into
0, the 100nm nanometer Fe
0With the 200nm nanometer Fe
0, obtain antichlor B-D.
The same with antichlor A preparation process, the consumption of change NiB chemical plating fluid, control Ni accounts for 1% and 45% of antichlor gross weight, obtains antichlor E and F.
The same with antichlor A preparation process, reaction temperature is changed into 20 ℃ and 90 ℃ by 35 ℃, obtain antichlor G and H.
The same with antichlor A preparation process, the reaction time is changed into 5min and 120min by 10min, obtain antichlor I and J.
Comparative Examples 2
This Comparative Examples is used for illustrating the catalytic performance of catalyst at chlorobenzene aqueous solution dechlorination reaction, reaction is carried out in the 250ml three-necked bottle, and reaction condition is: 25 ℃ of temperature, chlorobenzene solution concentration are 200mg/L, the antichlor consumption is 1: 400 (weight ratio), reaction 8h.
Table 1
| Catalyst | Dechlorination rate (%) |
| NiB | 1.3 |
| Nanometer Fe 0 | 8.7 |
| A | 85.1 |
| B | 71.3 |
| E | 30.2 |
| F | 78.6 |
| H | 20.6 |
| J | 58.3 |
Claims (8)
1. the purpose of this invention is to provide a kind of method for preparing novel catalytic reduction dechlorinating agent, it is the method for preparing the agent of chemical machining nano Ni-Fe bimetallic composite catalyzing reduction dechlorination, and this antichlor can be in nanometer Fe
0The surface generates NiB amorphous alloy cluster, and then has improved the dechlorination performance of antichlor.
In the chemical machining nano Ni-Fe bimetallic composite catalyzing reduction dechlorination agent that characteristics of the present invention are to be developed, the NiB amorphous alloy is evenly distributed on nanometer Fe
0The surface is promoting Fe
0When reacting with reactant, again can be with nanometer Fe
0Active surface cover, guarantee Fe
0Can fully contact with reactant, Ni account for antichlor gross weight 1%～45%.
The preparation of catalytic reduction dechlorinating agent:
Nanometer Fe with the chemical reduction method preparation
0(5～200nm) join in 5～350ml NiB chemical plating fluid, stir 5～120min down at 20～90 ℃.Product to neutral, is used absolute ethyl alcohol flush away residual moisture through the deionized water washing again.Product can be used for the dechlorination reaction of the chlorobenzene aqueous solution after drying.
2. according to the described nanometer Fe of claim 1
0Size is in 5～200nm, and preferred cluster is of a size of the 60nm nanometer Fe
0
3. be 5～350ml according to the NiB chemical plating fluid volume that adds in the described reaction of claim 1, preferred 220ml.
4. according to the NiSO that consists of of the described NiB chemical plating fluid of claim 1
46H
2O, ethylenediamine, NaOH, KBH
4And deionized water.
5. be 20～90 ℃ according to the described reaction temperature of claim 1, preferred 40 ℃.
6. be 5～120min according to the described mixing time of claim 1, preferred 10min.
7. according in the agent of the described chemical machining nano Ni-Fe bimetallic of claim 1 composite catalyzing reduction dechlorination, Ni account for catalyst gross weight 1%～45%, preferred 21.7%.
8. the catalytic reduction dechlorinating agent of claim 1 preparation is applied to the reaction of chlorobenzene reduction dechlorination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100598373A CN100500284C (en) | 2007-10-12 | 2007-10-12 | Method for preparing catalytic reduction dechlorinating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100598373A CN100500284C (en) | 2007-10-12 | 2007-10-12 | Method for preparing catalytic reduction dechlorinating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101147864A true CN101147864A (en) | 2008-03-26 |
| CN100500284C CN100500284C (en) | 2009-06-17 |
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ID=39248631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100598373A Expired - Fee Related CN100500284C (en) | 2007-10-12 | 2007-10-12 | Method for preparing catalytic reduction dechlorinating agent |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824718A (en) * | 2012-09-07 | 2012-12-19 | 桂林市产品质量监督检验所 | Compound catalytic dechlorinating agent |
| CN104722774A (en) * | 2015-03-09 | 2015-06-24 | 武汉科技大学 | Nano-iron/nickel self-assembly particle reduction/catalyst and preparation method thereof |
| CN107398271A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院大连化学物理研究所 | Charcoal carries gold atom cluster catalyst and its application in glucose catalyticing oxidation |
| CN117282431A (en) * | 2023-09-22 | 2023-12-26 | 上海园林绿化建设有限公司 | Amorphous Co-Ni-Fe hydrodechlorination catalyst and preparation method and application thereof |
-
2007
- 2007-10-12 CN CNB2007100598373A patent/CN100500284C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824718A (en) * | 2012-09-07 | 2012-12-19 | 桂林市产品质量监督检验所 | Compound catalytic dechlorinating agent |
| CN102824718B (en) * | 2012-09-07 | 2015-04-15 | 桂林市产品质量监督检验所 | Compound catalytic dechlorinating agent |
| CN104722774A (en) * | 2015-03-09 | 2015-06-24 | 武汉科技大学 | Nano-iron/nickel self-assembly particle reduction/catalyst and preparation method thereof |
| CN107398271A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院大连化学物理研究所 | Charcoal carries gold atom cluster catalyst and its application in glucose catalyticing oxidation |
| CN107398271B (en) * | 2016-05-19 | 2020-05-05 | 中国科学院大连化学物理研究所 | Carbon-supported gold cluster catalyst and application thereof in catalytic oxidation of glucose |
| CN117282431A (en) * | 2023-09-22 | 2023-12-26 | 上海园林绿化建设有限公司 | Amorphous Co-Ni-Fe hydrodechlorination catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100500284C (en) | 2009-06-17 |
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