CN101147864A - A kind of method for preparing novel catalytic reduction dechlorination agent - Google Patents
A kind of method for preparing novel catalytic reduction dechlorination 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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- Prior art keywords
- dechlorination
- catalytic reduction
- nano
- dechlorination agent
- agent
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- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910003271 Ni-Fe Inorganic materials 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 241000080590 Niso Species 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims 2
- 238000006042 reductive dechlorination reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 230000000382 dechlorinating effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021065 Pd—Fe Inorganic materials 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
本发明的目的是提供一种制备新型催化还原脱氯剂的方法，它是制备纳米Ni－Fe双金属复合催化还原脱氯剂的方法。该脱氯剂能够在纳米Fe0表面生成NiB非晶态合金团簇，进而提高了纳米Fe0的脱氯性能。本发明的特点在于所研制的纳米Ni－Fe双金属复合催化还原脱氯剂中，NiB非晶态合金均匀分布在纳米Fe0表面，在促进Fe0与反应物进行反应的同时，又不会将纳米Fe0的活性表面覆盖，保证Fe0能够充分与反应物接触，使脱氯反应效率大大提高。The purpose of the present invention is to provide a method for preparing a novel catalytic reduction dechlorination agent, which is a method for preparing a nanometer Ni-Fe bimetal composite catalytic reduction dechlorination agent. The dechlorination agent can generate NiB amorphous alloy clusters on the surface of nano-Fe 0 , thereby improving the dechlorination performance of nano-Fe 0 . The feature of the present invention is that in the developed nano-Ni-Fe bimetallic composite catalytic reduction dechlorination agent, the NiB amorphous alloy is evenly distributed on the surface of nano-Fe 0 , which promotes the reaction between Fe 0 and the reactant, and does not Covering the active surface of nano-Fe 0 ensures that Fe 0 can fully contact with reactants, so that the efficiency of dechlorination reaction is greatly improved.
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100598373A CN100500284C (en) | 2007-10-12 | 2007-10-12 | A kind of method for preparing catalytic reduction dechlorination agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100598373A CN100500284C (en) | 2007-10-12 | 2007-10-12 | A kind of method for preparing catalytic reduction dechlorination agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101147864A true CN101147864A (en) | 2008-03-26 |
| CN100500284C CN100500284C (en) | 2009-06-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100598373A Expired - Fee Related CN100500284C (en) | 2007-10-12 | 2007-10-12 | A kind of method for preparing catalytic reduction dechlorination agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100500284C (en) |
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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Granted publication date: 20090617 Termination date: 20131012 |