CN110280207A - Alkali salt/g-C3N4The application of composite adsorbing material and its absorption degradation triphenylmethane dye waste water - Google Patents

Alkali salt/g-C3N4The application of composite adsorbing material and its absorption degradation triphenylmethane dye waste water Download PDF

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Publication number
CN110280207A
CN110280207A CN201910591164.9A CN201910591164A CN110280207A CN 110280207 A CN110280207 A CN 110280207A CN 201910591164 A CN201910591164 A CN 201910591164A CN 110280207 A CN110280207 A CN 110280207A
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Prior art keywords
composite adsorbing
adsorbing material
waste water
preparation
triphenylmenthane
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CN201910591164.9A
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Inventor
卢鹏
胡雪利
刘小平
傅敏
贺有周
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Chongqing Technology and Business University
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Chongqing Technology and Business University
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Priority to CN201910591164.9A priority Critical patent/CN110280207A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0259Compounds of N, P, As, Sb, Bi
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041Oxides or hydroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil

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

Abstract

The present invention provides a kind of alkali salt/g-C3N4The preparation method of composite adsorbing material, for handling the composite adsorbing material and processing method of triphenylmenthane substance in waste water.Composite adsorbing material is appealed with BaCO3And C3H6N6For mixed raw material, by raw material mixed preparing be aqueous solution, dry at 60~80 DEG C 1~2h, calcine at 400~700 DEG C 4~6h, cooling grinding and etc. be made.The composite adsorbing material for being used to handle triphenylmenthane substance in waste water is added in waste water when specific processing and is handled.Preparation process of the invention has many advantages, such as that simple and easy to control, easy to operate, at low cost, abundant raw material is easy to get.Composite adsorbing material of the present invention has excellent absorption property to the triphenylmenthane substance in waste water, and adsorption efficiency is high, is up to 92.26% to the degradation rate of crystal violet.It is with important application prospects in terms of handling organic wastewater.

Description

Alkali salt/g-C3N4Composite adsorbing material and its absorption degradation triphenylmethane dye Expect the application of waste water
Technical field
The invention belongs to the synthesis of composite adsorbing material and the absorption degradation technical fields of organic wastewater, and in particular to compound The preparation method of adsorbent material, composite adsorbing material and processing method for handling triphenylmenthane substance in waste water.
Background technique
In recent years, many nitrogenous, phosphorus compounds are largely used to remover, and urea is also commonly used for printing and dyeing various processes, makes Total phosphorus, total nitrogen content increase in waste water, and water eutrophication is made after discharge.It, will if the untreated direct emission of waste water from dyestuff The drinking water source of growing tension can be caused greatly to threaten.Therefore the processing to waste water not only can reduce or avoid environment dirty Dye protects people's health, the water that can also recycle that treated, saves water resource, walks sustainable development road, It is of far-reaching significance great.Common dye waste water treatment method includes solidification, chemical oxidation, filtering, photocatalysis, UF membrane, ion Exchange and absorption.Wherein absorption method is widely used in industry because of simple and easy, at low cost, safety, pollution removal efficiency height In.Environment functional material applied to waste water from dyestuff adsorption treatment mainly include carbonaceous adsorbent material, minerals adsorbent material and Biomass absorbent material etc..And the above material is difficult to realize the selective absorption to waste water from dyestuff.
Since class graphite mould nitrogen carbide has functional group and special two-dimensional layered structure, while having at ambient conditions again Have excellent a chemical stability and thermal stability, environmental-friendly, biocompatibility, it is non-toxic and by adsorbing domain researchers Extensive concern.g-C3N4By the 3-s- triazine (C of high-sequential6N7) unit composition, hydrophobic effect and p-p phase interaction can be passed through It is stacked with light.It is reported that g-C3N4Conjugation p region in plane can adsorb aromatic pollution.In addition, orderly 3- S- 5-triazine units contain several " nitrogen tanks ", and six of them nitrogen lone pair electrons have electronegative functional group, these functional groups can be with Positively charged pollutant interacts.These features make g-C3N4It is possibly realized as adsorbent for wastewater treatment. If to the g-C with functional group3N4Nano material is further modified, then is expected to realize higher absorption property and preferably Environmental applications value.
Summary of the invention
In view of the above shortcomings of the prior art, the technical problem to be solved by the present invention is for inhaling in the prior art Enclosure material is alternative poor, and adsorption efficiency is low, and preparation process is complicated, and regeneration is complicated, leads to the problem of pollution to environment, and provides A kind of alternative high, adsorption efficiency is high, and abundant raw material is easy to get, and preparation is simple, the preparation of environmental-friendly composite adsorbing material Method, composite adsorbing material and processing method for handling triphenylmenthane substance in waste water.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme: a kind of preparation side of composite adsorbing material Method includes the following steps:
1) with BaCO3And C3H6N6For mixed raw material, mixed solution is made by the mixed raw material is soluble in water;Wherein, described BaCO3And C3H6N6Mass ratio be 3:1,2:1,1:1,1:2,1:3;
2) mixed solution that step 1) is prepared is placed in 1 ~ 2 h of drying at 60 ~ 80 DEG C, obtains drying mixing material; ,
3) the drying mixing material for obtaining step 2 calcines 4 ~ 6 h at 400 ~ 700 DEG C, obtains calcined materials;
4) pulverization process is carried out to the calcined materials that step 3) obtains, obtains the composite adsorbing material.
Class graphite type carbon nitride (Graphitic carbon nitride, g-C in the prior art3N4) polymer have with Layer structure as graphite-like is by C on layer3N3Ring or C6N7Ring is constituted, and is connected to form one layer infinitely by N atom between ring The plane of extension is combined by weak Van der Waals force between layers, most of inorganic compounds and inorganic metal from Son can combine or be inserted into g-C3N4In matrix, change its intrinsic property, improves it in catalytic field and use scope, often It is used as absorbent fields.BaCO3It is a kind of extremely common, the cheap minerals being widely present in nature, in electricity The industrial circles such as son, ceramics, coating papermaking, industrially desulfurized, medical, artifical bone are widely used.Art technology so far Personnel are that pay close attention to above-mentioned be g-C3N4The photocatalysis performance and BaCO of material3Application industrially.There is no cross to use Class graphite type carbon nitride and BaCO3The correlative study for preparing composite adsorbing material, also proves without correlative study in the prior art Class graphite type carbon nitride and BaCO3It may be used as adsorbent material and prepare raw material for preparing the compound suction with excellent absorption property Enclosure material.The present invention breaks through BaCO in the prior art3As the conventional understanding that industrial circle uses, in research class graphite mould nitridation Carbon and BaCO3Material obtained, which is chanced on, when two kinds of Material cladding production catalysis materials does not have good photocatalytic Can, but there is absorption property outstanding, research is found based on g-C3N4Layer structure and BaCO3The property having is led to The method for crossing calcining changes the crystalline structure of material, surface group etc., so that the compound system has excellent absorption property, Especially there is good absorption degradation effect to the organic dyestuff in waste water, achieve unexpected absorption degradation effect.
Further, mass volume ratio >=1:10 of the gross mass of mixed raw material described in step 1) and the water.It is such Dosage, can both meet makes mixed raw material spread more evenly across the requirement of mixing in water, and in turn avoiding water consumption excessively causes Too long problem of subsequent drying time.
Further, the mixed raw material is placed in water ultrasonic disperse in step 1) and handles 10 ~ 20 min, it is molten to be made into mixing Liquid.The method handled using ultrasonic disperse, can effectively improve dispersion efficiency, solute is made more sufficiently thoroughly to be dissolved in mixing In solution, mixed performance is more preferable.
Further, BaCO described in step 1)3And C3H6N6Mass ratio be 3:1,2:1,1:1,1:2,1:3.Using Such mass ratio, the composite adsorbing material that can make are more preferable to the absorption degradation of triphenylmenthane substance, to crystal violet Degradation efficiency up to 92.26%, achieve excellent degradation effect.
As optimization, drying mixing material is calcined into 4 h at 600 DEG C in step 3).Using such calcination time and Calcination temperature can make the calcined crystalline structure of composite material be better able to meet the requirement of high degradation efficiency.
It is a kind of for handling the composite adsorbing material of triphenylmenthane substance in waste water, component includes that the above method is made Composite adsorbing material.This composite adsorbing material compared to the prior art in TiO2、SrTiO3Equal adsorbent materials absorption degradation Effect is stronger, especially has efficient degradation effect to the triphenylmenthane substance in waste water, to various in dyeing waste water The triphenylmethanes mass degradation efficiency such as crystal violet is fast, good degrading effect, compared to triphenylmethane object in existing dyeing waste water Matter processing achieves unexpected degradation effect with adsorbent material.
The processing method of triphenylmenthane substance, is used to handle triphenylmenthane substance in waste water for described in a kind of waste water Composite adsorbing material add 15 ~ 120 min of dark processing in waste water;Wherein, the matter of the composite adsorbing material and waste water Amount volume ratio is 0.2 ~ 1.0 g:1000 mL.The triphenylmenthane substance in waste water is inhaled according to such processing method It is good not only to have ensure that degradation treatment effect for attached degradation, but also shortens the processing time of triphenylmenthane substance in existing waste water, has Good market prospects.
As optimization, the mass volume ratio of the composite adsorbing material and waste water is 1.0 g:1000 mL, when dark processing Between be 120 min.Under such treatment conditions, degradation effect is best.
As optimization, the organic dyestuff is crystal violet.The method of the present invention is best to the removal effect of crystal violet, to crystallization Purple degradation efficiency is up to 92.26%.
Compared with prior art, the invention has the following beneficial effects: the method for the present invention to break through class graphite mould in the prior art Carbonitride and graphene, oxide, simple substance element, polymer etc. carry out preparing composite material, BaCO3As industrial circle application Conventional understanding, be based on g-C3N4Layer structure and BaCO3Collaboration compatibility effect, calcining be made with excellent suction The composite adsorbing material of attached performance, the composite adsorbing material is fast to the triphenylmethane mass degradation efficiency in waste water, degradation is imitated Fruit is good, is especially up to 92.26% to the absorption degradation of crystal violet, achieves unexpected degradation treatment effect.And side of the present invention Method preparation process is simple, for operating convenient, short processing time when wastewater treatment, there is good industrialized production and market to answer Use prospect.
Specific embodiment:
Invention is further described in detail combined with specific embodiments below.The implementation case is premised on the technology of the present invention Under implemented, provide detailed embodiment and specific operating process now to illustrate that the present invention is creative, but this hair Bright protection scope embodiment not limited to the following.
Embodiment 1:
A kind of preparation method of composite adsorbing material, includes the following steps:
1) 6.0g BaCO is taken respectively3、12.0g C3H6N6As mixed raw material, mixed raw material is dissolved in 15 mL deionized waters, Then 15 min of ultrasonic disperse is uniformly mixed it, obtains mixed solution.
2) mixed solution for obtaining step 1) is placed in 60 DEG C of baking ovens, dries 1.5 h, more in mixed solution to remove Remaining moisture obtains drying mixing material.
3) step 2 drying mixing material being placed in Muffle furnace and is calcined, temperature is set as 600 DEG C, calcination time 4h, Obtain calcined materials.
4) after the calcined materials that step 3) obtains are cooled to room temperature, with mortar to get the composite adsorption of preparation after finely ground Material.
The present embodiment additionally provides a kind of for handling the adsorbent of triphenylmenthane substance in waste water, and group is divided into this reality Apply composite adsorbing material made from an above method.
The adsorbent material for being used to handle triphenylmenthane substance in waste water is added into the crystal violet solution into 800 mg/L In (waste water of the simulation containing organic dyestuff), the mass volume ratio of the composite adsorbing material and crystal violet solution is 1.0g: 1000 mL carry out 120 min of adsorption treatment to crystal violet solution at 25 DEG C, use such processing method as the result is shown, right The degradation efficiency of crystal violet may be up to 80.78%, achieve degradation effect outstanding.
Embodiment 2:
A kind of preparation method of composite adsorbing material, includes the following steps:
1) 9.0g BaCO is taken respectively3、9.0 g C3H6N6As mixed raw material, mixed raw material is dissolved in 20 mL deionized waters, Then 20 min of ultrasonic disperse is uniformly mixed it, obtains mixed solution.
2) mixed solution for obtaining step 1) is placed in 80 DEG C of baking ovens, dries 2 h, extra in mixed solution to remove Moisture obtains drying mixing material.
3) step 2 drying mixing material being placed in Muffle furnace and is calcined, temperature is set as 600 DEG C, calcination time 4h, Obtain calcined materials.
4) after the calcined materials that step 3) obtains are cooled to room temperature, with the finely ground composite adsorption material to get preparation of mortar Material.
The present embodiment additionally provides a kind of for handling the adsorbent of triphenylmenthane substance in waste water, and group is divided into this reality Apply composite adsorbing material made from an above method.
The composite adsorbing material for being used to handle triphenylmenthane substance in waste water is added into the crystal violet into 800 mg/L In solution (waste water of the simulation containing organic dyestuff), the mass volume ratio of the composite adsorbing material and crystal violet solution is 1.0g:1000 mL carries out absorption degradation to crystal violet solution at 25 DEG C and handles 120 min, uses such place as the result is shown Reason method may be up to 92.26% to the degradation efficiency of crystal violet, achieve degradation effect outstanding.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (6)

1. a kind of preparation method of composite adsorbing material, which comprises the steps of:
1) with BaCO3And C3H6N6For mixed raw material, mixed solution is made by the mixed raw material is soluble in water;Wherein, described BaCO3And C3H6N6Mass ratio be 3:1,2:1,1:1,1:2,1:3;
2) mixed solution that step 1) is prepared is placed in 1 ~ 2 h of drying at 60 ~ 80 DEG C, obtains drying mixing material;
3) the drying mixing material for obtaining step 2 calcines 3 ~ 6 h at 400 ~ 700 DEG C, obtains calcined materials;
4) pulverization process is carried out to the calcined materials that step 3) obtains, obtains the composite adsorbing material.
2. the preparation method of composite adsorbing material according to claim 1, which is characterized in that mixed raw material described in step 1) Gross mass and the water mass volume ratio >=1:10.
3. the preparation method of composite adsorbing material according to claim 1, which is characterized in that in step 1) that the mixing is former Material is placed in water ultrasonic disperse and handles 10 ~ 30 min, is made into mixed solution.
4. the preparation method of composite adsorbing material according to claim 1, which is characterized in that BaCO described in step 1)3With C3H6N6Mass ratio be 1:1.
5. the preparation method of composite adsorbing material according to claim 1, which is characterized in that mixing material will be dried in step 3) Expect to calcine 4 h at 600 DEG C.
6. a kind of for handling the composite adsorbing material of triphenylmenthane substance in waste water, which is characterized in that its component includes power Benefit requires composite adsorbing material made from 1 ~ 5 any the method.
CN201910591164.9A 2019-07-02 2019-07-02 Alkali salt/g-C3N4The application of composite adsorbing material and its absorption degradation triphenylmethane dye waste water Pending CN110280207A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112275306A (en) * 2020-11-20 2021-01-29 华北理工大学 Simple calcination method for preparing BaTiO3/g-C3N4Method for preparing composite photocatalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103301867A (en) * 2013-06-25 2013-09-18 重庆工商大学 Inorganic ion doped carbon nitride photocatalyst and preparation method thereof
CN106378087A (en) * 2016-11-22 2017-02-08 重庆大学 Preparation method of nano composite adsorbing material as well as adsorbent and treatment method used for treating trihydroxy triphenylmethane substance in wastewater
CN106563485A (en) * 2016-11-08 2017-04-19 江苏大学 Carbon nitride/potassium calcium niobate composite material and preparing method and application thereof
CN108993571A (en) * 2018-08-08 2018-12-14 重庆工商大学 g-C3N4Application in/alkali salt composite photocatalyst material and its wastewater by photocatalysis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103301867A (en) * 2013-06-25 2013-09-18 重庆工商大学 Inorganic ion doped carbon nitride photocatalyst and preparation method thereof
CN106563485A (en) * 2016-11-08 2017-04-19 江苏大学 Carbon nitride/potassium calcium niobate composite material and preparing method and application thereof
CN106378087A (en) * 2016-11-22 2017-02-08 重庆大学 Preparation method of nano composite adsorbing material as well as adsorbent and treatment method used for treating trihydroxy triphenylmethane substance in wastewater
CN108993571A (en) * 2018-08-08 2018-12-14 重庆工商大学 g-C3N4Application in/alkali salt composite photocatalyst material and its wastewater by photocatalysis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112275306A (en) * 2020-11-20 2021-01-29 华北理工大学 Simple calcination method for preparing BaTiO3/g-C3N4Method for preparing composite photocatalyst

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Application publication date: 20190927