CN105664836B - It is heat-treated hydro-thermal predecessor and obtains WS2/WO3The method of tiny balloon - Google Patents

It is heat-treated hydro-thermal predecessor and obtains WS2/WO3The method of tiny balloon Download PDF

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CN105664836B
CN105664836B CN201610011495.7A CN201610011495A CN105664836B CN 105664836 B CN105664836 B CN 105664836B CN 201610011495 A CN201610011495 A CN 201610011495A CN 105664836 B CN105664836 B CN 105664836B
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predecessor
tiny balloon
hydro
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heat
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CN105664836A (en
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楚学影
周敬博
都秉龙
李金华
徐铭泽
金芳军
王晓华
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Changchun 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
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0218—Compounds of Cr, Mo, W
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

It is heat-treated hydro-thermal predecessor and obtains WS2/WO3The method of tiny balloon belongs to composite nano materials technical field.Prior art processes complexity, process hazard, influence factor are more.Present invention be characterized in that first, prepare reaction solution：Tungsten chloride, thioacetamide are added in deionized water, stirring, while are passed through O2；Secondly, hydro-thermal method prepares WS2/WO3Predecessor：In autoclave, at a temperature of 230~240 DEG C, 20~30h of reaction solution described in hydro-thermal process, tiny balloon shape WS is obtained2/WO3Predecessor；Finally, it is heat-treated the WS2/WO3Predecessor：At a temperature of 470~520 DEG C, in N2The WS is heat-treated in protective atmosphere2/WO30.5~1.5h of predecessor, obtain product WS2/WO3Tiny balloon.Prepared product can quickly, thoroughly adsorb the dyestuffs such as rhodamine B, methyl orange, methylene blue, available for treatment of dyeing wastewater.

Description

It is heat-treated hydro-thermal predecessor and obtains WS2/WO3The method of tiny balloon
Technical field
The present invention relates to one kind heat treatment hydro-thermal predecessor to obtain WS2/WO3The method of tiny balloon, prepared product are made For a kind of composite, the dyestuffs such as rhodamine B, methyl orange, methylene blue can quickly, be thoroughly adsorbed, available for dyeing waste water Processing, belongs to composite nano materials technical field.
Background technology
Organic dyestuff is complicated, difficult degradation, has genotoxic potential, and dyeing wastewater through organic matter content is high, colourity is high, composition Complexity, to avoid Dying Wastewater Treatment ＆ environment, it is necessary to its purified treatment.High-specific surface area of the nano material because of its own, work The features such as surface-active of jump and higher surface energy, become a kind of effective sorbing material.WS2/WO3Composite nano materials Be it is a kind of have to dyestuffs such as rhodamine B, methyl orange, methylene blues quick adsorption act on material, the place for dyeing waste water It is satisfactory to manage effect.
There is a kind of WS in the prior art2/WO3Photochemical catalyst, pass through H2The high temperature vulcanized WO of S3And prepare.For example, by powder Shape WO3It is put into silica crucible, is placed in quartz tube furnace, H is slowly introducing with 150mL/min flow velocity under 300 DEG C of furnace temperature2S Gas reaction 1 hour, stopping are passed through H2S, after furnace temperature naturally cools to room temperature, the ground product of taking-up is the WS2/ WO3Photochemical catalyst finished product.The prior art does not provide product microscopic appearance, is not directed to the absorption property of finished product yet.The preparation H used in method2S is a kind of hazardous gas, is mixed with air and meets naked light, high fever meeting combustion explosion, with concentrated nitric acid, oleum Sour or other strong oxidizer vigorous reactions explode, H2S gases are heavier than air, and can be bled around in lower, and meeting naked light can draw Rise and strile-back.
There is one kind to prepare WS in current technology2/WO3The method of porous hollow shell nanometer anode material, that is, it is a kind of Using carbonaceous mesophase spherules (McMB) assisting sol -- cryogenic vacuum thermal reduction.The preparation process of this method includes：1st, by six Valency tungsten salt is added in the Sol A comprising carbonaceous mesophase spherules, stirs and sol B is made, and the step makes WO using carbosphere as template3 It is grown on carbosphere；2nd, the sol B for preparing step 1 is dry, grinds, and insulation 0.5~2 is small at 200~500 DEG C afterwards When, obtain porous hollow shell WO3It is nanocrystalline；3rd, the porous hollow shell WO for preparing step 23Nanocrystalline and sulphur powder it is separated In vacuum tube furnace, it is -0.01~-0.1MPa to control vacuum, and temperature is 200~500 DEG C, is reacted 0.5~3 hour, porous Hollow shell WO3Part WO in nanocrystalline3Vulcanize as WS2, finally give WS2/WO3Porous hollow shell is nanocrystalline, and the material can Used as a kind of negative material.However, carbosphere template used in this method, its preparation, the control of carbosphere size, adds Entering the grasp of amount and template efficiency all makes the increase of preparation difficulty, directly affects product quality.In addition, reversion process is present Danger, it is high temperature vulcanized more dangerous；The dosage of sulphur turns into the factor of another influence product quality, and excessive sulphur can also pollute ring Border.It can be seen that the factor that this method influences product pattern is more, complex process, it is difficult to control.Certainly, the nanoporous of the product Hollow shell morphology is not only suitable for, as negative material, also being suitable as sorbing material.
The content of the invention
In order to simplicity, safely prepare the WS with powerful adsorption capacity and steady quality2/WO3Composite, I Invented a kind of heat treatment hydro-thermal predecessor and obtain WS2/WO3The method of tiny balloon.
The heat treatment hydro-thermal predecessor of the present invention obtains WS2/WO3The method of tiny balloon is characterized in that, first, prepare Reaction solution：Tungsten chloride, thioacetamide are added in deionized water, stirring, while are passed through O2；Secondly, hydro-thermal method prepares WS2/ WO3Predecessor：In autoclave, at a temperature of 230~240 DEG C, 20~30h of reaction solution described in hydro-thermal process, sky is obtained Heart microspheroidal WS2/WO3Predecessor；Finally, it is heat-treated the WS2/WO3Predecessor：At a temperature of 470~520 DEG C, in N2Protection The WS is heat-treated in atmosphere2/WO30.5~1.5h of predecessor, obtain product WS2/WO3Tiny balloon.
The present invention it has technical effect that, tiny balloon shape WS is disposably obtained using the hydro-thermal method of routine2/WO3Forerunner Thing, as shown in figure 1, obtaining final product WS through calcining again2/WO3Tiny balloon, as shown in Fig. 2 yardstick is 1 μm, and size Uniformly, specific surface area is up to 50.626m2/g.The present invention obtains tiny balloon shape WS using hydro-thermal method2/WO3Predecessor, it is not required to Any template is used, not only eliminates an influence factor, moreover, simplifying preparation process.N is used in heat treatment process2Protect Shield atmosphere is heat-treated, and safety coefficient is higher.It can be seen that the methods experiment step of the present invention is simple, influence factor is few, safety system Number is higher.In addition, in hydro-thermal method step, reaction temperature meets the requirement of reactor inner bag heatproof, no in the range of 230~240 DEG C Can only reaction be normally carried out, and the service life of reactor inner bag can be extended.
The method of the present invention is passed through O into reaction solution2, its effect is to improve product WS2/WO3WO in tiny balloon3 Crystalline quality.As shown in figure 3, O is passed through into reaction solution2Increase oxygen content, compared to obstructed O2, or even it is passed through N2, WS2's Diffraction maximum does not change really, still, with pure WO3Compare, as shown in curve in figure 1, although WO3(- 112), (140) two The diffraction maximum of crystal face varies less, if is passed through O2、N2Have little to no effect, but, WO3(002), (020), (200) three Therefore the diffraction maximum of individual crystal face occurs significantly different, be passed through O2, product WS2/WO3WO in tiny balloon3Diffraction maximum it is obvious, As shown in curve 2 in figure, illustrate WO3Crystalline quality it is good, and obstructed O2, or even it is passed through N2, WO3Diffraction maximum it is flat, in figure Shown in curve 3, curve 4, illustrate WO3Crystalline quality it is poor.
The product WS of the present invention2/WO3As a kind of sorbing material, its adsorption effect can be used to printing and dyeing useless tiny balloon from it See in the processing of water.By product WS2/WO3Tiny balloon is added separately to stir in rhodamine B, methylene blue, methyl orange solution Mix, and take lucifuge measure, such as use tinfoil shading, form the absorption environment of dark, exclude photocatalysis and dyestuff itself light drop Solution is to judging the interference of adsorption effect.
As shown in figure 4, it was found from the visible absorption spectrum figure of rhodamine B solution, its absworption peak is located at 550nm, sees song Shown in line 1, when to rhodamine B solution add WS2/WO3After tiny balloon, over time, absworption peak gradually weakens, and sees Shown in curve 2,3, after 3h, absworption peak disappears, and as shown in curve 4, shows due to WS2/WO3The absorption of tiny balloon, in solution Rhodamine B concentration has become very low.
As shown in figure 5, it was found from the uv-visible absorption spectroscopy figure of methylene blue, it respectively has in 289nm and 664nm One absworption peak, as shown in curve 1, when to methylene blue solution add WS2/WO3After tiny balloon, elapse, absorb over time Peak gradually weakens, and as shown in curve 2,3, after 15min, two absworption peaks substantially reduce, and adsorption rate now reaches 94.22%, From the aspect of adsorption rate and adsorption time two, WS2/WO3Tiny balloon not only has excellent adsorption effect to methylene blue, and Also it is better than the adsorption effect to rhodamine B.
As shown in fig. 6, it was found from the uv-visible absorption spectroscopy figure of methyl orange, its absworption peak is located at 504nm, sees song Shown in line 1, when to methyl orange solution add WS2/WO3After tiny balloon, over time, absworption peak gradually weakens, and sees Shown in curve 2~5, after 3h, absworption peak substantially reduces, as shown in curve 5, adsorption rate now close to 96.2%, show due to WS2/WO3The absorption of tiny balloon, the methyl orange concentration in solution have become very low.
Brief description of the drawings
Fig. 1 is the product WS of the present invention2/WO3The SEM pictures of tiny balloon.
Fig. 2 is the product WS of the present invention2/WO3The XRD of tiny balloon.2 θ=14.320 °, 33.575 °, 39.541 °, The diffraction maximum occurred at 58.424 ° corresponds respectively to WS2(002), (101), (104), (110) crystal face, with normal structure WS2 Diffraction maximum is completely the same (JCPDS card 08-0237)；2 θ=23.119 °, 23.586 °, 24.380 °, 28.615 °, The diffraction maximum occurred at 49.948 ° corresponds respectively to WO3(002), (020), (200), (- 112), (140) crystal face, with standard Structure WO3Diffraction maximum is completely the same (JCPDS card 43-1035).View picture figure illustrates the production obtained using the method for the present invention Its material of thing is WS2/WO3。
Fig. 3 is one group of XRD, and the figure is used as Figure of abstract simultaneously.Curve 1 is pure WO in figure3XRD；Curve 2 in figure For the product WS of the present invention2/WO3The XRD of tiny balloon；Curve 3 is the method using the present invention in figure, still, not to reaction Liquid is passed through O2, the product WS that obtains in this case2/WO3The XRD of tiny balloon；Curve 4 is using the present invention's in figure Method, still, not only O is not passed through it to reaction solution2, it is passed through N to reaction solution on the contrary2, the product WS that obtains in this case2/ WO3The XRD of tiny balloon.
Fig. 4~6 are the abosrption spectrogram tested using ultraviolet-visible spectrophotometer.
Fig. 4 is the WS with the method acquisition using the present invention2/WO3The rhodamine B adsorption test that tiny balloon is done is relevant Visible absorption spectrum figure.Curve 1 is the abosrption spectrogram of rhodamine B solution in figure, and absworption peak is located at 550nm；It is bent in figure Line 2,3,4 is to add the WS2/WO3The abosrption spectrogram of rhodamine B solution after tiny balloon, wherein：Curve 2 is to add Enter rear 5min abosrption spectrogram, curve 3 is the abosrption spectrogram of 15min after addition, and curve 4 is the absorption spectrum of 3h after adding Figure.
Fig. 5 is the WS with the method acquisition using the present invention2/WO3The methylene blue adsorption number experiment that tiny balloon is done is relevant Uv-visible absorption spectroscopy figure.Curve 1 is the abosrption spectrogram of methylene blue solution in figure, and two absworption peaks distinguish position In 289nm and 664nm；Curve 2,3 is to add the WS in figure2/WO3The absorption light of methylene blue solution after tiny balloon Spectrogram, wherein：Curve 2 is the abosrption spectrogram of 5min after addition, and curve 3 is the abosrption spectrogram of 15min after adding.
Fig. 6 is the WS with the method acquisition using the present invention2/WO3The Adsorption of Methyl Orange experiment that tiny balloon is done is relevant Uv-visible absorption spectroscopy figure.Curve 1 is the abosrption spectrogram of methyl orange solution in figure, and absworption peak is located at 463nm；In figure Curve 2,3,4 is to add the WS2/WO3The abosrption spectrogram of methyl orange solution after tiny balloon, also, absworption peak moves 504nm is moved, wherein：Curve 2 is the abosrption spectrogram of 5min after addition, and curve 3 is the abosrption spectrogram of 15min after adding, Curve 4 is the abosrption spectrogram of 3h after adding.
Embodiment
The heat treatment hydro-thermal predecessor that the present invention is exemplified below obtains WS2/WO3The method of tiny balloon.
Example one：
The first step, prepare reaction solution：Weighed respectively with electronic balance 1.19055g tungsten hexachloride and 1.125g it is thio Acetamide, it is added in 80mL deionized water, magnetic agitation 30min, is passed through O therebetween210min。
Second step, hydro-thermal method prepare WS2/WO3Predecessor：The reaction solution is added in reactor inner bag, addition is anti- The 2/3 of kettle inner bag volume is answered, in autoclave, at a temperature of 235 DEG C, reaction solution 24h described in hydro-thermal process, is obtained hollow Microspheroidal WS2/WO3Predecessor.
3rd step, it is heat-treated the WS2/WO3Predecessor：At a temperature of 500 DEG C, in N2In protective atmosphere described in heat treatment WS2/WO3Predecessor 1h, obtain product WS2/WO3Tiny balloon.
Example two：
The first step, prepare reaction solution：Weighed respectively with electronic balance 1.19055g tungsten hexachloride and 1.125g it is thio Acetamide, it is added in 80mL deionized water, magnetic agitation 25min, is passed through O therebetween215min。
Second step, hydro-thermal method prepare WS2/WO3Predecessor：The reaction solution is added in reactor inner bag, addition is anti- The 2/3 of kettle inner bag volume is answered, in autoclave, at a temperature of 230 DEG C, reaction solution 30h described in hydro-thermal process, is obtained hollow Microspheroidal WS2/WO3Predecessor.
3rd step, it is heat-treated the WS2/WO3Predecessor：At a temperature of 470 DEG C, in N2In protective atmosphere described in heat treatment WS2/WO3Predecessor 1.5h, obtain product WS2/WO3Tiny balloon.
Example three：
The first step, prepare reaction solution：Weighed respectively with electronic balance 1.19055g tungsten hexachloride and 1.125g it is thio Acetamide, it is added in 80mL deionized water, magnetic agitation 35min, is passed through O therebetween25min。
Second step, hydro-thermal method prepare WS2/WO3Predecessor：The reaction solution is added in reactor inner bag, addition is anti- The 2/3 of kettle inner bag volume is answered, in autoclave, at a temperature of 240 DEG C, reaction solution 20h described in hydro-thermal process, is obtained hollow Microspheroidal WS2/WO3Predecessor.
3rd step, it is heat-treated the WS2/WO3Predecessor：At a temperature of 520 DEG C, in N2In protective atmosphere described in heat treatment WS2/WO3Predecessor 0.5h, obtain product WS2/WO3Tiny balloon.

Claims (2)

1. one kind heat treatment hydro-thermal predecessor obtains WS2/WO3The method of tiny balloon, it is characterised in that first, prepare reaction Liquid：Tungsten hexachloride, thioacetamide are added in deionized water, stirring, while are passed through O2；Secondly, hydro-thermal method prepares WS2/WO3 Predecessor：In autoclave, at a temperature of 230~240 DEG C, 20~30h of reaction solution described in hydro-thermal process, obtain hollow micro- Spherical WS2/WO3Predecessor；Finally, it is heat-treated the WS2/WO3Predecessor：At a temperature of 470~520 DEG C, in N2Protective atmosphere The middle heat treatment WS2/WO30.5~1.5h of predecessor, obtain product WS2/WO3Tiny balloon.
2. heat treatment hydro-thermal predecessor according to claim 1 obtains WS2/WO3The method of tiny balloon, it is characterised in that In reaction solution step is prepared, 25~35min of magnetic agitation, O is passed through therebetween25~15min.
CN201610011495.7A 2016-01-08 2016-01-08 It is heat-treated hydro-thermal predecessor and obtains WS2/WO3The method of tiny balloon Expired - Fee Related CN105664836B (en)

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