CN113274983A - Method for removing Congo red through adsorption of bean dreg-hydrocalumite composite material - Google Patents

Method for removing Congo red through adsorption of bean dreg-hydrocalumite composite material Download PDF

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CN113274983A
CN113274983A CN202110765172.8A CN202110765172A CN113274983A CN 113274983 A CN113274983 A CN 113274983A CN 202110765172 A CN202110765172 A CN 202110765172A CN 113274983 A CN113274983 A CN 113274983A
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hydrocalumite
congo red
bean dregs
composite material
water
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CN202110765172.8A
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CN113274983B (en
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周喜
唐辈
罗德仪
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Shaoyang University
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Shaoyang University
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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
    • B01J20/04—Solid 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
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • 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
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2101/40—Organic compounds containing sulfur

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (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)

Abstract

A method for removing Congo red through bean dregs-hydrocalumite composite material adsorption is characterized in that the bean dregs-hydrocalumite composite material is used as an adsorbent to adsorb and remove Congo red in water, and the preparation process of the bean dregs-hydrocalumite composite material comprises the following steps: (1) mixing soluble calcium salt and water to obtain salt solution, and adding NaAlO2、NaOH、Na2CO3Mixing with water to prepare an alkali solution; (2) dispersing bean dregs in water, heating to 50-90 ℃, and addingAnd (3) continuously stirring the salt solution and the alkali solution for reaction for 0.5-3 h, stopping stirring, crystallizing for 10-25 h at the temperature of 70-100 ℃, and dehydrating and drying the precipitate obtained by the reaction to obtain the bean dregs-hydrocalumite composite material. The bean dreg-hydrocalumite composite material has higher removal rate and adsorption capacity on Congo red in water, has better adsorption performance than single hydrocalumite or bean dreg, and shows good synergistic effect.

Description

Method for removing Congo red through adsorption of bean dreg-hydrocalumite composite material
Technical Field
The invention belongs to the technical field of functional materials and water treatment, and particularly relates to a method for removing Congo red by adsorbing bean dregs-hydrocalumite composite materials.
Background
The bean dregs are main by-products in the processing process of bean products, and the yield of wet bean dregs in China is more than 2000 million tons every year. The wet bean dregs have high protein content, high water content, easy decay and deterioration and difficult preservation, most of the bean dregs are still directly discarded, and the environmental pollution and the resource waste are caused. Therefore, the high-value utilization of the bean dregs becomes a key technical problem which is urgently needed to be solved by the bean product processing industry.
The bean dregs have larger specific surface area and abundant pore structures, contain active functional groups such as hydroxyl, carboxyl and the like, and have the potential of being used as a biomass adsorbent. In recent years, the literature reports a series of modification treatment methods of the bean dregs and application performance of the bean dregs in the field of adsorption. However, compared with inorganic high-efficiency adsorbing materials such as zeolite, activated carbon and hydrotalcite, the adsorbing capacity of the bean dregs is relatively small, and the large-scale application of the bean dregs as the adsorbing materials is limited.
Therefore, the bean dregs are used as raw materials to develop the composite material with high-efficiency adsorption performance so as to solve the problem that the adsorption capacity of the bean dregs is relatively small, and the composite material has important significance for realizing high-value utilization of the bean dregs.
Disclosure of Invention
The invention aims to provide a method for removing Congo red by adsorbing bean dregs-hydrocalumite composite materials.
The method for removing Congo red by bean dregs-hydrocalumite composite material adsorption provided by the invention takes the bean dregs-hydrocalumite composite material as an adsorbent to remove Congo red in water by adsorption, and is characterized in that the preparation process of the bean dregs-hydrocalumite composite material comprises the following steps:
(1) mixing soluble calcium salt and water to obtain salt solution, and adding NaAlO2、NaOH、Na2CO3Mixing with water to prepare an alkali solution;
(2) dispersing bean dregs in water, heating to 50-90 ℃, adding a salt solution and an alkali solution, continuously stirring for reaction for 0.5-3 h, stopping stirring, crystallizing for 10-25 h at 70-100 ℃, dehydrating and drying precipitates obtained by the reaction, and obtaining the bean dregs-hydrocalumite composite material.
The steps are[ Ca ] of calcium salt in step (1)2+]=1～3 mol/L。
In a further aspect of the present invention,
n(NaAlO2)/n(Ca2+)=0.2～0.5；
n(NaOH)/n(Ca2+)=0.8～1.0；
n(Na2CO3)/n(Ca2+)= 0.4～0.6。
the bean dregs and NaAlO2The mass ratio of (A) to (B) is 0.5-1.5: 1.
the soluble calcium salt is calcium chloride, calcium sulfate or calcium nitrate.
The addition amount of the bean dregs-hydrocalumite composite material is 0.5-3 g/L.
The initial concentration of the Congo red is 10-1000 mg/L.
Compared with the prior art, the technical scheme provided by the invention has the following advantages: (1) the related bean dregs-hydrocalumite composite material has higher removal rate and adsorption capacity to Congo red in water, and the adsorption performance is superior to that of single hydrocalumite or bean dregs, so that good synergistic effect is embodied; (2) the bean dregs-hydrocalumite composite material prepared by taking the bean dregs as the raw material has low production cost; (3) provides a new method for high-value utilization of the bean dregs.
Detailed Description
The following provides a more detailed description of the present invention. The above and other objects, features and advantages of the present invention will be apparent to those skilled in the art from the detailed description of the present invention.
Example 1
Preparation of an adsorbing material: dissolving 0.1 mol of calcium chloride in water to prepare 50 mL of salt solution, wherein [ Ca2+]=2.0 mol/L; 0.025 mol of NaAlO20.09 mol of NaOH and 0.05 mol of Na2CO3Dissolving in water to prepare 50 mL of alkaline solution, wherein n (NaAlO)2)/n(Ca2+)=0.25，n(NaOH)/n(Ca2+)=0.9，n(Na2CO3)/n(Ca2+) = 0.5; dispersing 2.08 g bean dregs in water, and maintaining at constant temperature of 80 deg.CAdding a salt solution and an alkali solution under the condition of continuous stirring, and reacting for 2 hours; stopping stirring, and crystallizing at 80 ℃ for 17 h; filtering, washing, drying and crushing to obtain the bean dregs-hydrocalumite composite material.
Example 2
Preparation of an adsorbing material: 0.1 mol of calcium sulfate was dissolved in water to prepare 100 mL of a salt solution, wherein [ Ca ]2+]=1.0 mol/L; 0.05 mol of NaAlO20.08 mol of NaOH and 0.04 mol of Na2CO3Dissolving in water to prepare 100 mL of alkaline solution, wherein n (NaAlO)2)/n(Ca2+)=0.5，n(NaOH)/n(Ca2+)=0.8，n(Na2CO3)/n(Ca2+) = 0.4; dispersing 5.02 g of bean dregs in water, adding a salt solution and an alkali solution under the conditions of constant temperature of 60 ℃ and continuous stirring, and reacting for 3 hours; stopping stirring, and crystallizing at 100 deg.C for 10 hr; filtering, washing, drying and crushing to obtain the bean dregs-hydrocalumite composite material.
Example 3
Preparation of an adsorbing material: 0.1 mol of calcium nitrate was dissolved in water to prepare 40 mL of a salt solution in which [ Ca ]2+]=2.5 mol/L; 0.02 mol of NaAlO20.1 mol of NaOH and 0.06 mol of Na2CO3Dissolving in water to prepare 40 mL of alkaline solution, wherein n (NaAlO)2)/n(Ca2+)=0.2，n(NaOH)/n(Ca2+)=1.0，n(Na2CO3)/n(Ca2+) = 0.6; dispersing 2.25 g of bean dregs in water, adding a salt solution and an alkali solution under the conditions of constant temperature of 90 ℃ and continuous stirring, and reacting for 0.5 h; stopping stirring, and crystallizing at 70 deg.C for 25 h; filtering, washing, drying and crushing to obtain the bean dregs-hydrocalumite composite material.
Example 4
Adsorption of congo red in water: adding 1.6 g of the bean dregs-hydrocalumite composite material prepared in the example 1 into 1L of an aqueous solution with the Congo red concentration of 800 mg/L, and stirring and adsorbing for 2 h; after centrifugal separation, spectrophotometry is adopted for sampling and detection, the adsorption rate of Congo red in water is 95.5%, and the adsorption capacity is 477.5 mg/g.
Example 5
Adsorption of congo red in water: adding 0.5 g of the bean dregs-hydrocalumite composite material prepared in the example 2 into 1L of an aqueous solution with the Congo red concentration of 200 mg/L, and stirring and adsorbing for 1 h; after centrifugal separation, spectrophotometry is adopted for sampling detection, the adsorption rate of Congo red in water is 99.2%, and the adsorption capacity is 396.8 mg/g.
Example 6
Adsorption of congo red in water: 2.5 g of the bean dregs-hydrocalumite composite material prepared in the example 3 is added into 1L of an aqueous solution with the Congo red concentration of 1000 mg/L, and stirred and adsorbed for 2 hours; after centrifugal separation, the Congo red is sampled and detected by a spectrophotometry method, the adsorption rate of the Congo red in water is 98.5%, and the adsorption capacity is 394 mg/g.
Comparative example 1
Hydrocalumite was prepared in the same manner as in example 1, except that the bean dregs were not added; the prepared hydrocalumite is used for adsorbing and removing Congo red in water, and the adsorption condition and the detection method are the same as those in the embodiment 4; the results show that the adsorption rate of the hydrocalumite on the Congo red in water is 65.9 percent, and the adsorption capacity is 329.5 mg/g.
Comparative example 2
The bean dregs are used for adsorbing and removing Congo red in water, and the adsorption condition and the detection method are the same as those in the embodiment 4; the result shows that the adsorption rate of the bean dregs to the Congo red in the water is 50.6 percent, and the adsorption capacity is 253 mg/g.
According to the results of the examples 4-6 and the comparative examples 1 and 2, the okara-hydrocalumite composite material has high removal rate and adsorption capacity for congo red in water, the adsorption performance of the okara-hydrocalumite composite material is superior to that of single hydrocalumite or okara, and good synergistic effect is shown among the components. The bean dregs-hydrocalumite composite material takes the bean dregs as one of the raw materials, and the production cost is low. Based on the characteristics, the technical scheme provided by the invention provides a new method for high-value utilization of the bean dregs and treatment of wastewater containing Congo red.
It should be understood that although the present invention has been clearly illustrated by the foregoing examples, various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended to cover all such changes and modifications as fall within the scope of the appended claims.

Claims (7)

1. A method for removing Congo red through bean dregs-hydrocalumite composite material adsorption is characterized in that the preparation process of the bean dregs-hydrocalumite composite material comprises the following steps:
(1) mixing soluble calcium salt and water to obtain salt solution, and adding NaAlO2、NaOH、Na2CO3Mixing with water to prepare an alkali solution;
(2) dispersing bean dregs in water, heating to 50-90 ℃, adding a salt solution and an alkali solution, continuously stirring for reaction for 0.5-3 h, stopping stirring, crystallizing for 10-25 h at 70-100 ℃, dehydrating and drying precipitates obtained by the reaction, and obtaining the bean dregs-hydrocalumite composite material.
2. The method for adsorptive removal of congo red according to claim 1, wherein [ Ca ] of the calcium salt in said step (1)2+]=1～3 mol/L。
3. The method for adsorptive removal of congo red according to claim 1,
n(NaAlO2)/n(Ca2+)=0.2～0.5；
n(NaOH)/n(Ca2+)=0.8～1.0；
n(Na2CO3)/n(Ca2+)= 0.4～0.6。
4. the method for adsorptive removal of congo red according to claim 1, wherein said okara is separated from NaAlO2The mass ratio of (A) to (B) is 0.5-1.5: 1.
5. the method for adsorptive removal of congo red according to claim 1, wherein said soluble calcium salt is calcium chloride, calcium sulfate or calcium nitrate.
6. The method for adsorbing and removing congo red according to claim 1, wherein the addition amount of the bean dregs-hydrocalumite composite material is 0.5-3 g/L.
7. The method for adsorbing and removing congo red according to claim 1, wherein the initial concentration of congo red is 10-1000 mg/L.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115246971A (en) * 2021-12-30 2022-10-28 邵阳学院 Preparation method of modified hydrocalumite-bean dregs for PVC (polyvinyl chloride) heat stabilizer

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH09241019A (en) * 1996-03-11 1997-09-16 Denki Kagaku Kogyo Kk Method of synthesis of carbonated hydrocarmite
CN107973362A (en) * 2017-12-22 2018-05-01 中国地质大学（武汉） A kind of method and device for removing removing fluorine in water and arsenate at the same time based on hydrocalumite
CN110697710A (en) * 2019-11-21 2020-01-17 北京工商大学 Bean dreg-based porous carbon material, preparation method and application thereof
CN112062201A (en) * 2020-09-19 2020-12-11 邵阳学院 Method for removing glyphosate in water by adsorption of calcined hydrocalumite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09241019A (en) * 1996-03-11 1997-09-16 Denki Kagaku Kogyo Kk Method of synthesis of carbonated hydrocarmite
CN107973362A (en) * 2017-12-22 2018-05-01 中国地质大学（武汉） A kind of method and device for removing removing fluorine in water and arsenate at the same time based on hydrocalumite
CN110697710A (en) * 2019-11-21 2020-01-17 北京工商大学 Bean dreg-based porous carbon material, preparation method and application thereof
CN112062201A (en) * 2020-09-19 2020-12-11 邵阳学院 Method for removing glyphosate in water by adsorption of calcined hydrocalumite

Non-Patent Citations (1)

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Title
谢梦姣等: "改性水铝钙石的清洁制备及其对PVC的热稳定性能研究", 《邵阳学院学报(自然科学版)》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115246971A (en) * 2021-12-30 2022-10-28 邵阳学院 Preparation method of modified hydrocalumite-bean dregs for PVC (polyvinyl chloride) heat stabilizer
CN115246971B (en) * 2021-12-30 2023-05-16 邵阳学院 Preparation method of modified hydrocalumite-bean dregs for PVC heat stabilizer

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