CN110270302A - One kind is for adsorbing S in industrial wastewater2-Material preparation method - Google Patents

One kind is for adsorbing S in industrial wastewater2-Material preparation method Download PDF

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CN110270302A
CN110270302A CN201910622581.5A CN201910622581A CN110270302A CN 110270302 A CN110270302 A CN 110270302A CN 201910622581 A CN201910622581 A CN 201910622581A CN 110270302 A CN110270302 A CN 110270302A
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zno
fecl
solution
nano
preparation
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CN110270302B (en
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李芬
葛宝财
丁为民
孟繁竹
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Compounds Of Iron (AREA)

Abstract

The invention belongs to industrial wastewater field of material preparation, and in particular to S in a kind of adsorbable industrial wastewater2‑ZnO@FeOOH material preparation method.This method is by FeCl3Solution, lauryl sodium sulfate (SDS) solution, nano ZnO particles and NaOH solution are put into hydrothermal reaction kettle after being mixed in a certain ratio reacts, and obtains final products after sediment in kettle is filtered, washed, is dried after reaction.It is an advantage of the invention that raw material is cheap and easy to get, technical process is simple, and product has absorption S well2‑Performance, as S in water2‑When concentration is 5-200mg/L, when the additive amount of product is 1g/L, to S2‑Removal rate can be widely applied to field of industrial waste water treatment up to 80%-99%.

Description

One kind is for adsorbing S in industrial wastewater2-Material preparation method
Technical field
The invention belongs to industrial wastewater adsorbent material preparation fields, and in particular to a kind of adsorbable S2-ZnO@FeOOH material Preparation method for material.
Background technique
The industries such as oil refining, petrochemical industry, pharmacy and process hides can all generate a large amount of sulfur-containing waste water in process of production, such waste water In S2-Metal material can be corroded, human body is poisoned, release foul gas, high risks are caused to environment.At present for useless The removal of Sulfide in water mostly uses bioanalysis and precipitation method etc..Bioanalysis is to S2-Removal rate is not suitable for height close to 100% Concentration waste water, and the sulfate generated easily causes secondary pollution to environment；The precipitation method mainly pass through Fe2+With S2-Effect forms FeS Precipitating, by S2-Removal, although this technology is industrially using relatively generally, spininess is to wastewater with high concentration of sulfide, due to sinking for generation Shallow lake particle is less than normal, not easily settled, and the problems such as introducing other anion, is rarely used in the sulfur-containing waste water improvement of middle low concentration. It comparing with above-mentioned technology, adsorption technology has stable, and anti-shock loading is strong, the advantages of not introducing other interfering ions, But industry sulfur-containing waste water is administered at present, is lacked for S2-Adsorbent material, therefore develop it is cheap and easy to get, be suitable for S2-It intakes dense Degree, which fluctuates big sulfur removal material, just becomes particularly important；
Chinese patent 201610674614.7
Chinese patent 201510772205.6
Chinese patent 201410444573.3
Chinese patent 201410755660.0
Chinese patent 201811617006.8
Chinese patent 201620116413.0
Summary of the invention
The object of the present invention is to provide a kind of adsorbable S2-ZnO@FeOOH material, this method raw material is cheap and easy to get, technique Process is easily achieved, and product has absorption S well2-Performance can be widely applied to environment protection field.
To achieve the above object, preparation method of the present invention is with FeCl3And nano-ZnO is raw material, whole preparation sides Method is made of following steps:
Step 1 configures the FeCl of 0.8-1.3mol/L3Solution, weighs a certain amount of nano-ZnO, and nano-ZnO is placed in FeCl3 In solution, FeCl is made3With nano-ZnO mixed liquor；
Step 2, by the CH of 0.2-0.4mol/L3(CH2)11OSO3Na solution is added drop-wise to step 1 institute with the speed of 3-6ml/min The FeCl of system3In nano-ZnO mixed liquor, it is prepared into FeCl3, nano-ZnO and CH3(CH2)11OSO3Process is added dropwise in Na mixed liquor Solution persistently stirs；
Step 3, the step of NaOH solution of 1.0-1.5mol/L is added drop-wise to lasting stirring two made FeCl3, nano-ZnO And CH3(CH2)11OSO3In Na mixed liquor, after thering is precipitating to occur, drops to when mixed solution pH value is 9.0-12.0 and stop titration, after Solution with precipitating is transferred in reaction kettle by continuous stirring 40-80min, reaction kettle is placed in 100-115 DEG C of baking ovens, instead Taking-up is cooled to room temperature after answering 8.0-12h；
Step 4 filters the solidliquid mixture in reaction kettle, washing, and dry 18-26h, drying temperature is 50-70 DEG C, Obtain ZnO FeOOH material.
Wherein, preparation method described in step 1, FeCl3Solution concentration is preferably 1.0mol/L, the grain of the nano-ZnO Diameter is between 10-50nm.
Wherein preparation method described in step 2, CH3(CH2)11OSO3Na solution concentration is preferably 0.25-0.35mol/L, FeCl3, nano-ZnO and CH3(CH2)11OSO3Na the mass ratio of the material is 4:1:1.2.
The concentration prior of wherein preparation method described in step 3, NaOH solution is 1.2mol/L, and it is preferential to be titrated to pH value Stop titration when for 9.0-10.5, continues mixing time and pay the utmost attention to as 40-50min, the temperature prioritised of baking oven is set as 105-110 DEG C, the reaction time is preferably 8.0-10h.
Wherein in preparation method described in step 4, drying time is preferably 20-24h, and drying temperature is preferably 55-65 ℃。
Advantages of the present invention is as follows:
This material preparation process raw material is cheap and easy to get, and technical process is easily achieved, and is suitable for industrial-scale production；Product has very Good absorption S2-Performance, be suitable for S2-Influent concentration fluctuates big Industrial Wastewater Treatment, can be widely applied to oil refining, petrochemical industry, The fields such as pharmacy and process hides.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of ZnO@FeOOH；
Fig. 2 is the XRD diagram of ZnO@FeOOH.
Specific embodiment
Embodiment 1:
By 5.40gFeCl3·6H2O and 1.728gCH3(CH2)11OSO3Na is dissolved in respectively in the deionized water of 20ml, magnetic agitation Device stirring and dissolving, after completely dissolution to FeCl30.40g nano-ZnO is added in solution to be uniformly mixed, CH3(CH2)11OSO3Na is molten Liquid is added drop-wise to the FeCl of lasting stirring with 5ml/min3, persistently stir 15min in nano-ZnO mixed solution, by 1.5mol/L's NaOH solution is added drop-wise to the FeCl of lasting stirring3, nano-ZnO and CH3(CH2)11OSO3In Na mixed liquor, after thering is precipitating to occur, drop To mixed solution pH value be 12.0 when stop titration, continue stir 60min will with precipitating solution be transferred in reaction kettle, will Reaction kettle is placed in 110 DEG C of baking oven, and taking-up is cooled to room temperature after hydro-thermal 10h.Sediment in reaction kettle is filtered, is washed It washs, 60 DEG C of dryings obtain ZnO FeOOH material for 24 hours.By the infrared spectroscopy of Fig. 1 as it can be seen that wave number is in 787cm-1, 895cm-1 The absorption peak of left and right belongs to the vibration peak between the Fe-O-H of FeOOH, 601cm-1There is the stretching vibration peak for being Fe-O；Pass through The XRD diffraction pattern of Fig. 2 is as it can be seen that be to have diffraction maximum appearance at 35.3 ° in 2 θ, it was demonstrated that there are FeOOH for material surface.Due to nanometer ZnO is wrapped in inside FeOOH, therefore does not detect that nano-ZnO exists；
It takes containing S2-The waste water 1L of 100mg/L launches 1g desulfurizing agent, and after adsorbing 1h, water sampling, which carries out detection, can obtain S2-Removal rate is 98.2%.
Embodiment 2:
By 8.10gFeCl3·6H2O and 2.592gCH3(CH2)11OSO3Na is dissolved in respectively in the deionized water of 30ml, magnetic agitation Device stirring and dissolving, after completely dissolution to FeCl30.60g nano-ZnO is added in solution to be uniformly mixed, CH3(CH2)11OSO3Na is molten Liquid is added drop-wise to the FeCl of lasting stirring with 3ml/min3, persistently stir 15min in nano-ZnO mixed solution, by 1.0mol/L's NaOH solution is added drop-wise to the FeCl of lasting stirring3, nano-ZnO and CH3(CH2)11OSO3In Na mixed liquor, after thering is precipitating to occur, drop To mixed solution pH value be 11.0 when stop titration, continue stir 70min will with precipitating solution be transferred in reaction kettle, will Reaction kettle is placed in 108 DEG C of baking oven, and taking-up is cooled to room temperature after hydro-thermal 9h.Sediment in reaction kettle is filtered, is washed It washs, 70 DEG C of dry 20h obtain ZnO FeOOH；
It takes containing S2-The waste water 1L of 200mg/L launches 1g desulfurizing agent, and after adsorbing 1h, water sampling, which carries out detection, can obtain S2-Removal rate is 90.6%.

Claims (7)

1. one kind is for adsorbing S in industrial wastewater2-ZnO@FeOOH material preparation method, it is characterised in that with FeCl3And nanometer ZnO is raw material, is prepared using hydro-thermal method, and preparation method is made of following steps:
Step 1 configures the FeCl of 0.8-1.3mol/L3Solution, weighs a certain amount of nano-ZnO, and nano-ZnO is placed in FeCl3 In solution, FeCl is made3With nano-ZnO mixed liquor；
Step 2, by the CH of 0.2-0.4mol/L3(CH2)11OSO3Na solution is added drop-wise to step 1 institute with the speed of 3-6ml/min The FeCl of system3In nano-ZnO mixed liquor, it is prepared into FeCl3, nano-ZnO and CH3(CH2)11OSO3Process is added dropwise in Na mixed liquor Solution persistently stirs；
Step 3, the step of NaOH solution of 1.0-1.5mol/L is added drop-wise to lasting stirring two made FeCl3, nano-ZnO and CH3(CH2)11OSO3In Na mixed liquor, after thering is precipitating to occur, drops to when mixed solution pH value is 9.0-12.0 and stop titration, continue Solution with precipitating is transferred in reaction kettle by stirring 40-80min, and reaction kettle is placed in 100-115 DEG C of baking oven, is reacted 8.0-12h taking-up is cooled to room temperature after;
Step 4 filters the solidliquid mixture in reaction kettle, washing, and dry 18-26h, drying temperature is 50-70 DEG C, Obtain ZnO FeOOH material.
2. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that FeCl in step 13Solution concentration It is preferably 1.0mol/L.
3. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that nanometer described in step 1 The partial size of ZnO is between 10-50nm.
4. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that CH in step 23(CH2)11OSO3Na solution concentration is preferably 0.25-0.35mol/L, FeCl3, nano-ZnO and CH3(CH2)11OSO3Na the mass ratio of the material is 4:1:1.2。
5. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that NaOH solution is dense in step 3 Degree is preferably 1.2mol/L, is titrated to and stops titration when pH value is preferably 9.0-10.5, and continuing mixing time is preferably 40- 50min, the temperature prioritised of baking oven are set as 105-110 DEG C, and the reaction time is preferably 8.0-10h.
6. the preparation method of ZnO@FeOOH according to claim 1, it is characterised in that drying time is preferential in step 4 For 20-24h, drying temperature is preferably 55-65 DEG C.
7. material is suitable for containing S2-Concentration is in the industrial wastewater of 5-200mg/L.
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Cited By (1)

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CN114669304A (en) * 2021-12-31 2022-06-28 山东庚辰环保新材料有限公司 Desulfurization catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114669304A (en) * 2021-12-31 2022-06-28 山东庚辰环保新材料有限公司 Desulfurization catalyst and preparation method thereof
CN114669304B (en) * 2021-12-31 2023-11-03 山东庚辰环保新材料有限公司 Desulfurization catalyst and preparation method thereof

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