CN102614896A - Preparation method of surface modified nano palladium/iron catalytic reducing agent - Google Patents
Preparation method of surface modified nano palladium/iron catalytic reducing agent Download PDFInfo
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- CN102614896A CN102614896A CN2012100588071A CN201210058807A CN102614896A CN 102614896 A CN102614896 A CN 102614896A CN 2012100588071 A CN2012100588071 A CN 2012100588071A CN 201210058807 A CN201210058807 A CN 201210058807A CN 102614896 A CN102614896 A CN 102614896A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 184
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 86
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 81
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 76
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- 229920002472 Starch Polymers 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- 229920002907 Guar gum Polymers 0.000 claims description 12
- 229960002154 guar gum Drugs 0.000 claims description 12
- 235000010417 guar gum Nutrition 0.000 claims description 12
- 239000000665 guar gum Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
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- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
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- 238000000576 coating method Methods 0.000 abstract description 2
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
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- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000006298 dechlorination reaction Methods 0.000 description 18
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
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- 239000003054 catalyst Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention relates to a preparation method of a surface modified nano palladium/iron catalytic reducing agent. The nano palladium/iron catalytic reducing agent is prepared by using a liquid-phase deposition method; and by adding a surface modifier and coating the surface modifier on the outer layer of the catalytic reducing agent, hard agglomeration of the nano palladium/iron catalytic reducing agent in water is reduced. The nano palladium/iron catalytic reducing agent modified by the surface modifier has no flocculation phenomenon in water and higher dispersion degree. Compared with the normal nano palladium/iron catalytic reducing agent, the modified nano palladium/iron catalytic reducing agent prepared by the invention has the advantages of high particle purity, no oxidative inactivation phenomenon, small particle size, high catalytic reduction reaction activity and capability of increasing the removal rate for various chlorinated organic compounds in water by 9-24 percent compared with the unmodified nano palladium/iron catalytic reducing agent.
Description
Technical field
The present invention relates to the preparation method of a kind of surface modified nanometer palladium/iron catalytic reducer, particularly, belong to nanometer environment functional material and water-treatment technology field the preparation method of the catalytic reducer of chlorinatedorganic degraded in the water.
Background technology
The most strong toxicities of chlorinatedorganic (COCs), difficult degradation, in certain environment, bioaccumulation property is arranged, water environment and human health have been caused direct destruction and potential threat.Chlorinatedorganic is of a great variety, is important chemical material, intermediate and organic solvent, thereby is widely used in many industries.They use through volatilization, container leakage, discharge of wastewater, agricultural chemicals and pesticide and the approach such as burning of chlorinated organics finished product get into environment; The intermediate product that causes producing in a large amount of chlorinatedorganics and the building-up process thereof is discharged in the environment in large quantities, severe contamination atmosphere, soil, particularly underground water and surface water.Improvement method about chlorinatedorganic mainly contains at present: physics method, chemical method, bioanalysis etc.The physics method mainly contains gas method, extraction, active carbon adsorption etc., is applicable to the chloride organic wastewater that contains higher concentration.Bioanalysis because chlorinatedorganic all has very big toxic action to most microorganism, therefore has certain limitation in the utilization process.Chemical method mainly is the chlorinated organics in the catalytic degradation waste water, promptly uses certain catalyst, and the degradating chloro organic matter makes it become the littler or avirulent organic matter of toxicity.
In recent years, get more and more because zero-valent iron particle applies to remove the research of the chlorinated organics in the waste water, and obtained certain achievement, so researchers' research center of gravity is all tended to the research of zero-valent iron particle.Especially nanoscale zero-valent iron particle, to have a grain diameter little because of it, advantage such as the big reactivity of specific area is strong and receive extensive concern.But because fe reduction dechlorination speed is very slow, and can not all chlorinatedorganics of deoxidization, degradation, so researchers to improve activity of such catalysts, improve dechlorination reaction speed with adding second kind of metal in the nano iron particles.Such as He Xiaojuan etc. studied the Ni/Fe catalytic reducer to the influence factor of PCE dechlorination (referring to He Xiaojuan etc.; The Ni/Fe catalytic reducer is to tetrachloro-ethylene (PCE) dechlorination Study on influencing factors; Geoscience-China University of Geosciences's journal, 2003,28 (3): 337-340).Wu Deli etc. studied the Fe/Cu catalytic reduction method handle the Analysis on Mechanism of chlorinatedorganic (referring to: Wu Deli etc., the Fe/Cu catalytic reduction method is handled the Analysis on Mechanism of chlorinatedorganic, water technology, 2005,31 (5): 30-33).Precious metal palladium is proved to be and is best hydrogenation catalyst, and palladium/iron double metal particle is higher than other iron-based bimetal granule such as nickel/iron, copper/iron to the dechlorination rate of chlorinatedorganic.Discover that the catalytic reducer grain diameter that adopts the micron order iron powder to make is bigger, specific surface is little, therefore can influence dechlorination rate.Thereby existing Zero-valent Iron dechlorination technology adopts the nanoscale catalytic reducer that specific area is big, reactivity is high more, and dechlorination rate improves rapidly.
The ubiquitous problem of nano-level iron bimetallic granule technology is: the reunion between (1) nano particle causes seed activity to reduce.Owing to have polarity between the iron-based nano particle, cause particle in the aqueous solution, to be easy to reunite, and be unfavorable for reclaiming repeated use, these a series of problems all can reduce the speed of catalyst dechlorination reaction in water.(2) the aerial inactivation of nano particle.Because the strong reducing property of iron, when the iron-based nano particle with very easily oxidized after airborne oxygen contacts, cause the reduction of its reactivity.
Based on above present situation; The present invention is intended to through nanometer palladium/iron double metal particle is carried out surface modification; Mainly be to prepare the bigger nanometer palladium/iron catalytic reducer of degree of scatter, improving its clearance to chlorinatedorganic in the water, and through the coating of surface modifier to nanometer palladium/iron particle; The stability of enhanced granule prevents the reduction of its reactivity in air.
Summary of the invention
The present invention provides a kind of preparation method of nanometer palladium/iron catalytic reducer of surface modifier modification; This method prepares nanometer palladium/iron catalytic reducer through liquid phase deposition; And in the preparation process of palladium/iron catalytic reducer, add an amount of surface modifier; Utilize the sterically hindered effect of polymer long-chain in aqueous medium that nanometer palladium/iron catalytic reducer is disperseed modification; With problems such as the flocculation of solution nano-catalytic reducing agent, reunions, and strengthen the aerial stability of reducing agent, improve dechlorination efficiency.
The concrete technological process of the present invention is following:
(1) compound concentration is 0.8mol/L-1.0 mol/L FeCl
3Solution adds surface modifier, and stirs in solution in process for preparation;
(2) under nitrogen atmosphere, be 2.5mol/L-3.5mol/L sodium borohydride (NaBH with concentration
4) drips of solution adds the FeCl be added with surface modifier
3In the solution, stir, (be assurance FeCl until sodium borohydride solution while dripping
3Fully and NaBH
4Reaction adds excessive N aBH according to reaction equation
4Solution) dropwise continued and stir 10min-20min, the solution that reacts completely is filtered, deionized water drip washing 2-3 all over after drain;
(3) nano iron particles after will draining is positioned in the palladium liquid and carry out palladiumization, and the palladium time is 20min-30min, behind the suction filtration, in grinding behind the dry 5h-6h under 100 ℃ of-107 ℃ of vacuum, promptly gets modified Nano palladium/iron catalytic reducer.
Surface modifier is a kind of in commercially available polyethylene glycol (PEG), soluble starch, the guar gum among the present invention.
The addition of polyethylene glycol and soluble starch is FeCl among the present invention
3The 0.1%-1.5% of solution quality.
The addition of guar gum is FeCl among the present invention
3The 0.01%-0.15% of solution quality.
Palladium liquid is the potassium chloropalladate KPdCl of 0.2g/L-0.4g/L concentration among the present invention
6Solution.
The catalytic reducer that modified Nano palladium of the present invention/preparation method of iron catalytic reducer makes can be applicable to chlorinatedorganic in the degradation water.
Nanometer palladium/iron catalytic reducer preparating mechanism:
Fe
2++2BH
4ˉ+6H
2O?→?Fe+2B(HO)
3+7H
2
Compare advantage and good effect that the present invention has with known technology:
1, in the process of preparation catalytic reducer, the surface modifier that adds the certain mass ratio improves the degree of scatter of nano particle, and degree of aggregation is low, stability is high and have the more nanometer palladium/iron catalytic reducer of high reaction activity to obtain.
2, technical process is simple.The present invention prepares modified particles with liquid phase deposition, and the realization of whole particle surface modification only needs at preparation FeCl
3Get final product to wherein adding certain density surface modifier in the solution process.
3, energy consumption is low.Whole process of preparation is carried out at normal temperatures and pressures, no extra energy resource consumption.
Description of drawings
Fig. 1 is modified Nano palladium/iron catalytic reducer and the common nanometer palladium/iron catalytic reducer transmission electron microscope photo comparative result sketch map that the present invention prepares; Wherein Fig. 1 (a) is nanometer palladium/iron catalytic reducer after the guar gum surface modification, and Fig. 1 (b) is unmodified preceding nanometer palladium/iron catalytic reducer.
Fig. 2 is modified Nano palladium/iron catalytic reducer and the common nanometer palladium/iron catalytic reducer XRD spectra comparative result sketch map that the present invention prepares; Wherein Fig. 2 (a) is nanometer palladium/iron catalytic reducer after the soluble starch surface modification, and Fig. 2 (b) is unmodified preceding nanometer palladium/iron catalytic reducer.
The specific embodiment
Through accompanying drawing and embodiment the present invention is done further explain below, but protection domain of the present invention is not limited to said content.
Embodiment 1: the preparation method of guar gum modified Nano palladium/iron catalytic reducer and to multiple chlorinatedorganic removal effect, and particular content is following:
(1) compound concentration is the FeCl of 1.0mol/L
3Solution adds guar gum, and stirs in this solution, wherein the guar gum addition is FeCl
30.01% of solution quality.
(2) under nitrogen atmosphere, concentration is added dropwise to the FeCl that contains guar gum for the 3.1mol/L sodium borohydride solution
3(be assurance FeCl in the solution
3Fully and NaBH
4Reaction adds excessive N aBH according to reaction equation
4Solution), stir, dropwise continued until sodium borohydride solution and stir 15min while dripping; The solution that reacts completely is filtered through Bush's funnel that 0.22 μ m miillpore filter is housed, drain after the deionized water drip washing 2 times, the nano iron particles after draining is positioned in the 0.3g/L potassium chloropalladate solution carry out palladiumization; The palladium time is 30min; Behind core filter suction filtration, vacuum drying chamber grinds behind the dry 6h down for 100 ℃, promptly gets guar gum modified Nano palladium/iron catalytic reducer.
With the grain shape and the grain diameter of nanometer palladium/iron catalytic reducer after the transmission electron microscope observation modification, the result sees Fig. 1; Can know that by figure the more unmodified catalytic reducer decentralization of nanometer palladium/iron catalytic reducer increases to some extent after the modification, particle is more even, and appearance profile is clear, and the particle diameter diameter is (Fig. 1 (a)) between 20nm – 50 nm; And unmodified nanometer palladium/iron catalytic reducer is assembled owing to the effect of magnetic force between particle and connect into long-chain shape (Fig. 1 (b)).
(3) guar gum modified Nano palladium/iron catalytic reducer is to chlorinatedorganic degraded removal effect in the water
Modified Nano palladium/iron particle input is filled in the reaction bulb of chlorinatedorganic solution; Place speed governing many with carrying out dechlorination reaction on the oscillator reaction bulb, reaction system pH=6.75, particle dosage are 4 g/L; Reaction time is 2 h, with gas Chromatographic Determination chlorinatedorganic concentration.Under same reaction conditions, replace modified Nano palladium/iron catalytic reducer with unmodified nanometer palladium/iron catalytic reducer, chlorinatedorganic in the water is carried out dechlorination reaction, chlorinatedorganic change in concentration before and after relatively reacting, the result sees table 1.Can know that through calculating the chlorinatedorganic clearance nanometer palladium/iron catalytic reducer improves 17.1%-23.5% to chlorinatedorganic clearance in the water than unmodified nanometer palladium/iron catalytic reducer after the modification.
Table 1: guar gum modified Nano palladium/iron catalytic reducer is to the removal effect of chlorinatedorganic
Embodiment 2: the preparation method of soluble starch modified Nano palladium/iron catalytic reducer and to multiple chlorinatedorganic removal effect, and particular content is following:
(1) compound concentration is the FeCl of 0.8mol/L
3Solution adds soluble starch, and stirs in this solution, wherein the soluble starch addition is FeCl
30.15% of solution quality.
(2) under nitrogen atmosphere, concentration is added dropwise to the FeCl that contains soluble starch for the 2.5mol/L sodium borohydride solution
3(be assurance FeCl in the solution
3Fully and NaBH
4Reaction adds excessive N aBH according to reaction equation
4Solution), stir, dropwise continued until sodium borohydride solution and stir 20min while dripping; The solution that reacts completely is filtered through Bush's funnel that 0.22 μ m miillpore filter is housed, drain after the deionized water drip washing 3 times, the nano iron particles after draining is positioned in the 0.2g/L potassium chloropalladate solution carry out palladiumization; The palladium time is 25min; Behind core filter suction filtration, vacuum drying chamber grinds behind the dry 5.5h down for 105 ℃, promptly gets soluble starch modified Nano palladium/iron catalytic reducer.
Soluble starch modified Nano palladium/iron catalytic reducer particle purity is high; Can know (Fig. 2 (a)) from the XRD spectra of modified particles, non-oxidation iron characteristic peak occurs in the granulate preparation process, i.e. Zero-valent Iron non-oxidation phenomenon; The particle surface reaction active site is many, and the particulate catalytic reproducibility is strong.Obvious oxidative phenomena (Fig. 2 (b)) then appears in unmodified common nanometer palladium/iron catalytic reducer particle, and promptly unmodified common nanometer palladium/iron catalytic reducer reactivity reduces because of the oxidized iron of particle surface covers greatly.
(3) soluble starch modified Nano palladium/iron catalytic reducer is to chlorinatedorganic degraded removal effect in the water
Modified Nano palladium/iron particle input is filled in the reaction bulb of chlorinatedorganic solution, place speed governing many reaction bulb with carrying out dechlorination reaction on the oscillator.Reaction system pH=6.75, particle dosage are 3 g/L, and the reaction time is 2 h, with gas Chromatographic Determination chlorinatedorganic concentration.Under same reaction conditions, replace modified Nano palladium/iron catalytic reducer with unmodified nanometer palladium/iron catalytic reducer, chlorinatedorganic in the water is carried out dechlorination reaction, compare dechlorination rate, the result sees table 2.Can know that through calculating the chlorinatedorganic clearance nanometer palladium/iron catalytic reducer improves 9.3%-17.2% to chlorinatedorganic clearance in the water than unmodified nanometer palladium/iron catalytic reducer after the modification.
Table 2: soluble starch modified Nano palladium/iron catalytic reducer is to the removal effect of chlorinatedorganic
Embodiment 3: the preparation method of poly ethyldiol modified nanometer palladium/iron catalytic reducer and to multiple chlorinatedorganic removal effect, and particular content is following:
(1) compound concentration is the FeCl of 0.9mol/L
3Solution adds polyethylene glycol, and stirs in this solution, wherein the polyethylene glycol addition is FeCl
31.5% of solution quality.
(2) under nitrogen atmosphere, concentration is added dropwise to the FeCl that contains polyethylene glycol for the 3.5mol/L sodium borohydride solution
3(be assurance FeCl in the solution
3Fully and NaBH
4Reaction adds excessive N aBH according to reaction equation
4Solution), stir, dropwise continued until sodium borohydride solution and stir 10min while dripping; The solution that reacts completely is filtered through Bush's funnel that 0.22 μ m miillpore filter is housed, drain after the deionized water drip washing 2 times, the nano iron particles after draining is positioned in the 0.4g/L potassium chloropalladate solution carry out palladiumization; The palladium time is 20min; Behind core filter suction filtration, vacuum drying chamber grinds behind the dry 5h down for 107 ℃, promptly gets poly ethyldiol modified nanometer palladium/iron catalytic reducer.
(3) poly ethyldiol modified nanometer palladium/iron catalytic reducer is to chlorinatedorganic degraded removal effect in the water
Modified Nano palladium/iron particle input is filled in the reaction bulb of chlorinatedorganic solution, place speed governing many reaction bulb with carrying out dechlorination reaction on the oscillator.Reaction system pH=6.75, particle dosage are 3 g/L, and the reaction time is 2 h, with gas Chromatographic Determination chlorinatedorganic concentration.Under same reaction conditions, replace modified Nano palladium/iron catalytic reducer with unmodified nanometer palladium/iron catalytic reducer, chlorinatedorganic in the water is carried out dechlorination reaction, compare dechlorination rate, the result sees table 3.Can know that through calculating the chlorinatedorganic clearance nanometer palladium/iron catalytic reducer improves 9%-15% to chlorinatedorganic clearance in the water than unmodified nanometer palladium/iron catalytic reducer after the modification.
Table 3: PEG modified Nano palladium/iron catalytic reducer is to the removal effect of chlorinatedorganic
Claims (6)
1. the preparation method of surface modified nanometer palladium/iron catalytic reducer is characterized in that: prepare in nanometer palladium/iron catalytic reducer process at liquid phase deposition and add surface modifier.
2. according to the preparation method of the said surface modified nanometer palladium of claim 1/iron catalytic reducer, it is characterized in that carrying out as follows:
(1) compound concentration is the FeCl of 0.8-1.0 mol/L
3Solution adds surface modifier, and stirs in process for preparation;
(2) under nitrogen atmosphere, be that 2.5-3.5mol/L sodium borohydride is added dropwise to the FeCl that is added with surface modifier with concentration
3In the solution, stir, dropwise continued until sodium borohydride and stir 10-20min while dripping; The solution that reacts completely is filtered, deionized water drip washing 2-3 all over after drain, the nano iron particles after draining is positioned in the palladium liquid carry out palladiumization; The palladium time is 20-30min; Behind the suction filtration, behind 100-107 ℃ of following vacuum drying 5-6h, grind, promptly get modified Nano palladium/iron catalytic reducer.
3. according to the preparation method of the said surface modified nanometer palladium of claim 2/iron catalytic reducer, it is characterized in that: surface modifier is a kind of in polyethylene glycol, soluble starch, the guar gum.
4. according to the preparation method of the said modified Nano palladium of claim 3/iron catalytic reducer, it is characterized in that: the addition of polyethylene glycol and soluble starch is FeCl
30.1 – 1.5% of solution quality.
5. according to the preparation method of the said modified Nano palladium of claim 3/iron catalytic reducer, it is characterized in that: the addition of guar gum is FeCl
30.01 – 0.15% of solution quality.
6. according to the preparation method of the said modified Nano palladium of claim 3/iron catalytic reducer, it is characterized in that: palladium liquid is the potassium chloropalladate solution of 0.2-0.4g/L concentration.
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