CN113413870A - Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof - Google Patents

Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof Download PDF

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CN113413870A
CN113413870A CN202110536334.0A CN202110536334A CN113413870A CN 113413870 A CN113413870 A CN 113413870A CN 202110536334 A CN202110536334 A CN 202110536334A CN 113413870 A CN113413870 A CN 113413870A
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composite material
metal sulfide
magnesium oxide
biomass charcoal
temperature
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CN113413870B (en
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文静
肖学英
常成功
董金美
郑卫新
郑小刚
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/02—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
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/39—
    • 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
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention provides a magnesium oxide-metal sulfide-biomass carbon composite material which comprises univalent metal sulfide, magnesium oxide and S and N co-doped amorphous carbon. The preparation method of the composite material comprises the following steps: dissolving crop straw, bischofite, monovalent metal salt and nitrogen source organic matter in solvent under stirring, and heating to evaporate solventObtaining a mixed material; grinding and stirring the mixed material and potassium hydroxide, placing the mixture in a reaction furnace, and reacting in a reaction furnace in a reaction condition of H2S and N2The mixed gas is roasted at constant temperature and then cooled to room temperature, and the composite material is obtained. The invention adopts crop straws and bischofite which is a byproduct of a potassium extraction process as raw materials for preparation, realizes resource utilization of the bischofite, and is beneficial to solving the problems of resource waste and environmental pollution. In addition, the composite material has double functions of adsorption and photocatalysis, can adsorb and photocatalytically degrade pollutant molecules in wastewater, and can be applied to treatment of water body pollution.

Description

Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environmental materials, and particularly relates to a magnesium oxide-metal sulfide-biomass charcoal composite material as well as a preparation method and application thereof.
Background
Crop straws are main byproducts of agricultural production, but the current comprehensive utilization technology of straws is still in the states of small resource industrial scale, poor economy and high cost, so that the condition of excessive straws is caused, and the phenomenon of burning a large amount of straws is caused. Because the crop straws contain nitrogen, phosphorus, potassium, hydrocarbon elements, organic sulfur and the like, a large amount of nitrogen oxides, sulfur dioxide, hydrocarbon compounds, smoke dust can be generated through incomplete combustion, secondary pollutants, ozone and the like can be generated under the action of sunlight, and the straws burnt in the field destroy the balance of a biological system, change the physical and chemical properties of soil, aggravate soil hardening and influence the growth of crops. Therefore, the research on the resource utilization of the crop straws is accelerated, so that the resource utilization of the crop straws is promoted, the environmental pollution caused by burning the crop straws can be remarkably reduced, and the comprehensive utilization and the sustainable development of the crop straws can be promoted.
The byproduct old brine in the production of potash fertilizer in salt lake in west China accumulates a large amount of bischofite (MgCl)2·6H2O), which causes increasingly serious damage to salt lake resources and environmental pollution. The old brine discharged to the lake zone flows for the most part during storage, except for a part of the precipitated crystals (formation of bischofite)And the raw brine returns to the salt lake again in a leakage manner, so that the more the bischofite leaks, the chemical composition of the raw brine in the salt lake is disordered, the further development of salt lake resources is seriously damaged, and the ecological environment of the salt lake is seriously damaged.
Because a large amount of industrial wastewater and domestic sewage are discharged without reaching the standard, and agricultural chemicals such as chemical fertilizers, pesticides and the like are used in a large amount in vast rural areas, the ground water is polluted to different degrees. The water pollution is mainly organic matter pollution, and the organic pollutants have great harm to human bodies, which directly or indirectly cause diseases of human bodies, such as secretion system disorder, immune system imbalance, gene mutation and the like.
The process of removing organic matters in water by adsorption mainly refers to the process of removing or reducing the organic matters in water by enriching the organic matters into the adsorbent by utilizing the physical and chemical adsorption properties of the solid adsorbent. The photocatalytic degradation technology for organic pollutants refers to the technology that when a semiconductor catalyst exists in organic wastewater, organic matters can be degraded after being irradiated by light with certain intensity, and then the purpose of treating the organic matters is achieved.
Therefore, the development of the adsorption-photocatalysis composite material has become a current research hotspot, and is more urgent need for treating complex environment systems. At present, the application of crop straws and bischofite, a byproduct of a potassium extraction process, in the development of an adsorption-photocatalysis dual-functional composite material for solving the problem of wastewater pollutants is not involved.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a magnesium oxide-metal sulfide-biomass charcoal composite material, a preparation method and application thereof, and aims to solve the problems of resource utilization and water pollution treatment of the existing crop straws and the byproduct bischofite in the salt lake potassium extraction process.
In order to achieve the above objects, the present invention provides a magnesium oxide-metal sulfide-biomass charcoal composite material, comprising a metal sulfide, magnesium oxide and biomass charcoal, wherein the biomass charcoal is S and N co-doped amorphous charcoal, and the metal sulfide is a monovalent metal sulfide.
Preferably, in the magnesium oxide-metal sulfide-biomass charcoal composite material, the component content of the biomass charcoal is 70-90 parts, the component content of the magnesium oxide is 5-25 parts, and the component content of the metal sulfide is 1-5 parts.
Another aspect of the present invention provides a method for preparing the magnesium oxide-metal sulfide-biomass charcoal composite material as described above, which comprises:
step S10, dissolving the biomass waste, bischofite, monovalent metal salt and nitrogen source organic matter in a solvent, stirring and mixing, heating to evaporate the solvent and obtain a mixed material;
step S20, grinding and stirring the mixed material and potassium hydroxide, placing the mixture into a reaction furnace, and reacting in a reaction furnace in a reaction condition of H2S and N2The mixed gas is roasted to obtain a roasted product;
step S30, the roasted product is put in H2S and N2Cooling in the mixed gas atmosphere to prepare the composite material.
Preferably, in step S10, the biomass waste is crop straws, the bischofite mainly comprises magnesium chloride hexahydrate, the monovalent metal salt is silver nitrate, silver chloride, silver sulfate, cuprous chloride or cuprous sulfate, and the nitrogen source organic matter is melamine, urea or polyvinylpyrrolidone.
Further preferably, the biomass waste is 40-80 parts by weight, the bischofite is 5-30 parts by weight, the monovalent metal salt is 2-10 parts by weight, and the nitrogen source organic matter is 5-20 parts by weight.
Further preferably, the step S10 specifically includes:
putting biomass waste, bischofite, monovalent metal salt and nitrogen source organic matter into a mixing tank containing a solvent according to a predetermined mass part ratio, and stirring and dissolving to obtain a mixed suspension;
and heating the mixed suspension in the dosing tank to increase the temperature, and continuously stirring to completely evaporate the solvent to obtain the mixed material.
Preferably, the step S20 specifically includes: grinding and stirring the mixed material and potassium hydroxide, placing the mixture in a high-temperature converter, and introducing H into the high-temperature converter2S and N2In the said H2S and N2Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
Further preferably, the potassium hydroxide is 5-30 parts by weight.
Further preferably, the temperature rise speed of the high-temperature converter is 5-20 ℃/min, the roasting temperature is 500-800 ℃, and the roasting time is 3-6 h.
Preferably, the step S30 specifically includes:
subjecting the calcined product to reaction in H2S and N2Cooling to room temperature in the mixed gas atmosphere;
and washing and drying the cooled roasting product at constant temperature to obtain the composite material.
Further preferably, in the step S30, the temperature reduction rate of the roasted product is 5 ℃/min to 20 ℃/min, and the temperature of the constant-temperature drying is 50 ℃ to 80 ℃.
Preferably, said H2S and N2In the mixed gas of (2), H2The volume percentage of S is 5-40%; in the step S20, the H2S and N2The flow rate of the mixed gas is 50mL/min to 100 mL/min; in the step S30, the H2S and N2The flow rate of the mixed gas is 20mL/min to 50 mL/min.
The invention also provides application of the magnesium oxide-metal sulfide-biomass charcoal composite material in water body pollution treatment.
The magnesium oxide-metal sulfide-biomass charcoal composite material provided by the embodiment of the invention comprises monovalent metal sulfide, magnesium oxide and biomass charcoal, wherein the biomass charcoal is S and N co-doped amorphous charcoal. The biomass carbon has good surface characteristics, rich pore structures, excellent adsorption effect and extremely strong decomposition resistance, can adsorb and treat organic pollutants in water, has good mechanical and physical properties such as large specific surface area, low thermal expansion coefficient, high temperature resistance and the like, is an ideal composite material reinforcing phase, is used as a material with the highest specific strength and specific rigidity in a metal-based composite material, has excellent damping property, heat creep resistance, dimensional stability and good cold processing performance, and can ensure that the prepared composite material has excellent physical and chemical properties by combining the characteristics of the two materials. In addition, the non-metal doped amorphous carbon has abundant surface active sites and electron capture capacity, and is beneficial to promoting the adsorption of pollutant molecules and expanding the visible light absorption range of the composite material; the monovalent metal sulfide and the S and N co-doped amorphous carbon form a heterojunction surface, more active sites can be provided for adsorption and photon absorption of pollutant molecules, and the utilization rate of sunlight is enhanced, so that the adsorption and photocatalytic degradation effects of the composite material on wastewater pollutants can be improved, and the composite material can efficiently adsorb and photocatalytically degrade the pollutant molecules in wastewater.
According to the preparation method of the magnesium oxide-metal sulfide-biomass charcoal composite material provided by the embodiment of the invention, the crop straws and the byproduct bischofite of the potassium extraction process are used as raw materials for preparation, so that the resource utilization of the crop straws and the byproduct of the potassium extraction process is realized, and the problems of resource waste and environmental pollution caused by the crop straws and the byproduct of the potassium extraction process are solved.
The embodiment of the invention provides application of a magnesium oxide-metal sulfide-biomass charcoal composite material, wherein the composite material has dual functions of adsorption and photocatalysis, can adsorb and photocatalytically degrade pollutant molecules in wastewater, and is favorable for treating water body pollution.
Drawings
Fig. 1 is a process flow diagram of a method for preparing a magnesium oxide-metal sulfide-biomass charcoal composite in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a magnesium oxide-metal sulfide-biomass charcoal composite material, which comprises metal sulfide, magnesium oxide and biomass charcoal, wherein the biomass charcoal is S and N co-doped amorphous charcoal, and the metal sulfide is monovalent metal sulfide.
Preferably, in the magnesium oxide-metal sulfide-biomass charcoal composite material, the component content of the biomass charcoal is 70-90 parts, the component content of the magnesium oxide is 5-25 parts, and the component content of the metal sulfide is 1-5 parts.
The biomass carbon has good surface characteristics, abundant pore structures, excellent adsorption effect and strong decomposition resistance, and can adsorb and treat organic pollutants in water. The magnesium composite material is used as a material with the highest specific strength and specific rigidity in the metal matrix composite material, and has excellent damping property, heat creep resistance, dimensional stability and good cold processing performance. Therefore, the composite material prepared by combining the characteristics of the two materials has excellent physical and chemical properties.
When a semiconductor catalyst is present in organic wastewater, under light irradiation, when the energy of an incident photon is higher than or equal to the band gap energy (Eg), an electron in the Valence Band (VB) of the photocatalyst absorbs the photon energy and is excited to transition to the Conduction Band (CB), and a photo-generated electron-hole pair is generated. Because the photoproduction electrons have strong reducibility and the holes have strong oxidability, the photoproduction electron-hole pairs can rapidly migrate to the surface of the material after being generated and are adsorbed on the H on the surface2O、O2、OH-Oxidation-reduction reaction to generate O2-、H2O2OH, etc. These highly chemically active materials react with most of the organic contaminants adsorbed on the surface of the catalyst to degrade the organic contaminants into H2O、CO2And the like, thereby achieving the purpose of degradation.
The non-metal doped amorphous carbon obtained by modifying the biomass carbon has abundant surface active sites and electron capture capacity, and is beneficial to promoting the adsorption of pollutant molecules and expanding the visible light absorption range of the composite material; the monovalent metal sulfide and the S and N co-doped amorphous carbon form a heterojunction surface, more active sites can be provided for adsorption and photon absorption of pollutant molecules, and the utilization rate of sunlight is enhanced, so that the adsorption and photocatalytic degradation effects of the composite material on wastewater pollutants can be improved, and the composite material can efficiently adsorb and photocatalytically degrade the pollutant molecules in wastewater.
The embodiment of the invention also provides a preparation method of the magnesium oxide-metal sulfide-biomass charcoal composite material, and referring to fig. 1, the preparation method comprises the following steps:
and step S10, dissolving the biomass waste, bischofite, monovalent metal salt and nitrogen source organic matter in a solvent, stirring and mixing, and heating to evaporate the solvent to obtain the mixed material.
Preferably, the biomass waste is crop straws, and the main component of the crop straws is biomass carbon which needs to be crushed firstly; the bischofite is a byproduct of a potassium extraction process, and the main component of the bischofite is magnesium chloride hexahydrate; the monovalent metal salt is silver nitrate, silver chloride, silver sulfate, cuprous chloride or cuprous sulfate; the nitrogen source organic matter is melamine, urea or polyvinylpyrrolidone.
Further preferably, the biomass waste is 40-80 parts by weight, the bischofite is 5-30 parts by weight, the monovalent metal salt is 2-10 parts by weight, and the nitrogen source organic matter is 5-20 parts by weight.
Preferably, the step S10 specifically includes:
step S101, placing biomass waste, bischofite, monovalent metal salt and nitrogen-containing organic matters into a mixing tank containing a solvent according to a preset mass part ratio, and stirring and dissolving to obtain a mixed suspension; the solvent can be deionized water, the dosage of the solvent is 300-800 mL, and the stirring speed of the batching tank is 200-500 r/min.
S102, heating the mixed suspension in the batching tank, and continuously stirring to completely evaporate a solvent to obtain the mixed material; wherein the heating temperature of the mixed suspension is 50-80 ℃.
The magnesium oxide-metal sulfide-biomass charcoal composite material is prepared by adopting the crop straws and the byproduct bischofite of the potassium extraction process as raw materials, so that the resource utilization of the crop straws and the byproduct of the potassium extraction process is realized, the comprehensive utilization and the sustainable development of the crop straws are promoted, and the problems of serious damage to the ecological environment of a salt lake and resource waste caused by the accumulation of a large amount of bischofite in a beach field are solved.
Step S20, grinding and stirring the mixed material and potassium hydroxide, placing the mixture into a reaction furnace, and reacting in a reaction furnace in a reaction condition of H2S and N2The mixed gas atmosphere of (2) is roasted to obtain a roasted product.
Specifically, the mixed material and potassium hydroxide are ground, stirred and placed in a high-temperature converter, and H is introduced into the high-temperature converter2S and N2In the said H2S and N2Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
Preferably, the mass part of the potassium hydroxide is 5-30 parts.
Preferably, the rotating speed of the high-temperature converter is 5 r/min-30 r/min, the heating speed of the high-temperature converter is 5 ℃/min-20 ℃/min, the roasting temperature is 500-800 ℃, and the roasting time is 3-6 h.
Further preferably, said H2S and N2In the mixed gas of (2), H2S accounts for 5 to 40 percent by volume, and H2S and N2The flow rate of the mixed gas is 50mL/min to 100 mL/min.
Preferably, the waste gas generated in the reaction process of step S20 is countercurrent absorbed by lime water, the absorbed waste gas is evacuated after reaching the standard through detection, the solid waste obtained by evaporating the waste liquid is sent to a third party company for treatment, and the obtained calcium salt mixture is filtered, dried and stacked after reaching the standard.
Further preferably, the concentration of the lime water is 0.3-3.0 g/L, the flow rate of the lime water is 5-10L/min, and the flow rate of the waste gas absorbed by the lime water is 130-150 mL/min.
Step S30, the roasted product is put in H2S and N2Cooling in the mixed gas atmosphere to prepare the composite material.
Preferably, the step S30 specifically includes:
step S301, the roasted product is put in H2S and N2Cooling to room temperature in the mixed gas atmosphere; wherein the cooling rate of the roasted product is 5-20 ℃/min; said H2S and N2In the mixed gas of (2), H2S accounts for 5 to 40 percent by volume, and H2S and N2The flow rate of the mixed gas is 20mL/min to 50 mL/min.
And S302, washing the cooled roasting product and drying at constant temperature to obtain the composite material.
Specifically, the cooled roasted product is transferred to a washing tank, washed by deionized water and absolute ethyl alcohol in sequence and dried at constant temperature.
Preferably, the dosage of the deionized water is 50 mL-150 mL, the dosage of the absolute ethyl alcohol is 50 mL-150 mL, and the constant temperature drying temperature is 50-80 ℃.
And washing and separating the roasted product to obtain the magnesium oxide-metal sulfide-biomass charcoal composite slurry and a potassium hydroxide solution. Drying the magnesium oxide-metal sulfide-biomass charcoal composite slurry to obtain the magnesium oxide-metal sulfide-biomass charcoal composite material; and evaporating and concentrating the potassium hydroxide solution to recycle the potassium hydroxide.
According to the preparation method of the magnesium oxide-metal sulfide-biomass charcoal composite material provided by the embodiment of the invention, the crop straws and the byproduct bischofite of the potassium extraction process are used as preparation raw materials, so that the resource utilization of the crop straws and the byproduct of the potassium extraction process is realized, the sustainable development of the comprehensive utilization of the crop straws is promoted, and the problems of serious damage to the ecological environment of a salt lake and resource waste caused by the accumulation of a large amount of bischofite in a beach field are solved. And moreover, waste gas generated in the reaction process is subjected to countercurrent absorption by using lime water, the absorbed waste gas is emptied after reaching the standard through detection, solid waste obtained by evaporating waste liquid is delivered to a third-party company for treatment, and the obtained calcium salt mixture is filtered, dried and stacked after reaching the standard, so that the damage of three-waste discharge to the ecological environment is reduced.
The embodiment of the invention also provides an application of the magnesium oxide-metal sulfide-biomass charcoal composite material. The magnesium oxide-metal sulfide-biomass charcoal composite material is a composite material with double functions of adsorption and photocatalysis, can effectively adsorb and photocatalytically degrade pollutant molecules in wastewater, and is favorable for solving the problem of water body pollution treatment.
The above-described magnesia-metal sulfide-biomass charcoal composite material, the preparation method and the application thereof will be described below with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the above-described magnesia-metal sulfide-biomass charcoal composite material, the preparation method and the application thereof of the present invention, and are not intended to limit the entirety thereof.
Example 1
Step one, 75g of crushed straw, 15g of potassium extraction byproduct bischofite, 2g of silver nitrate and 8g of melamine are weighed into a mixing tank containing 600mL of deionized water, and stirred at the room temperature at the rotating speed of 300 r/min for 0.5 h. And (3) heating the mixed suspension in the dosing tank to 60 ℃, and stirring at constant temperature until the deionized water is completely evaporated to obtain the mixed material.
Step two, adding 20g of potassium hydroxide into the mixed material, stirring uniformly, putting into a high-temperature converter with the rotating speed of 10 r/min, and introducing H2H with S volume fraction of 25% and gas flow rate of 80mL/min2S/N2Exhausting the air in the furnace by the mixed gas, raising the temperature to 600 ℃ at a speed of 10 ℃/min under the atmosphere, and roasting for 3 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by using lime water of 5L/min, the absorbed waste gas is directly emptied after reaching the standard through detection, and solid waste obtained by filtering and drying waste liquid reaches the standard and is stacked.
Step three, putting the roasted product in H2H with S volume fraction of 25% and gas flow rate of 40mL/min2S/N2Cooling to room temperature at a rate of 10 ℃/min in a mixed atmosphere, transferring the mixed atmosphere to a washing tank, washing with 100mL of deionized water and 100mL of absolute ethyl alcohol in sequence, heating the slurry in the washing tank to 60 ℃, and drying at constant temperature to obtain MgO-Ag2The S-S and N co-doped amorphous carbon composite material comprises the following components in percentage by weight: 87% of S, N codoped amorphous carbon, 12% of MgO and 1% of Ag2S。
The composite material is used for removing pollutant molecules in wastewater, and can adsorb 32.6% of antibiotic tetracycline hydrochloride (200mg/L) and degrade 65.9% of the antibiotic tetracycline hydrochloride under the specific conditions of adsorption for 1h and visible light degradation for 1 h;
29.7 percent of ciprofloxacin hydrochloride (300mg/L) capable of adsorbing and 65.9 percent of degradation; rhodamine B (200mg/L) which can absorb 38.2 percent and degrade 60.3 percent; methylene blue (500 mg/L) capable of adsorbing 39.3% and degrading 58.9%.
Example 2
Step one, weighing 70g of crushed wheat straws, 13g of potassium extraction by-product bischofite, 2g of cuprous chloride and 15g of urea, putting the wheat straws, the bischofite and the cuprous chloride into a mixing tank containing 550mL of deionized water, and stirring the mixture at room temperature at the rotating speed of 250 r/min for 0.5 h. And (3) heating the mixed suspension in the dosing tank to 65 ℃, and stirring at constant temperature until the deionized water is completely evaporated to obtain the mixed material.
Step two, toAdding 15g of potassium hydroxide into the mixed material, stirring uniformly, putting the mixed material into a high-temperature converter at the rotating speed of 10 r/min, and introducing H2H with S volume fraction of 30% and gas flow rate of 70mL/min2S/N2Exhausting the air in the furnace by the mixed gas, raising the temperature to 650 ℃ at 15 ℃/min under the atmosphere, and roasting at constant temperature for 2.5h to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by lime water of 7L/min, the absorbed waste gas is directly emptied after reaching the standard through detection, and solid waste obtained by filtering and drying waste liquid reaches the standard and is stacked.
Step three, putting the roasted product in H2H with S volume fraction of 30% and gas flow rate of 35mL/min2S/N2Cooling to room temperature at a rate of 15 ℃/min in a mixed atmosphere, transferring the mixed atmosphere to a washing tank, washing with 120mL of deionized water and 120mL of absolute ethyl alcohol in sequence, heating the slurry in the washing tank to 65 ℃ and drying at constant temperature to obtain MgO-Cu2The S-S and N co-doped amorphous carbon composite material comprises the following components in percentage by weight: 86% of S, N codoped amorphous carbon, 12% of MgO and 2% of Cu2S。
The composite material is used for removing pollutant molecules in wastewater, and can adsorb 36.4% and degrade 62.2% of antibiotic tetracycline hydrochloride (200mg/L) under the specific conditions of adsorption for 1h and visible light degradation for 1 h;
ciprofloxacin hydrochloride (300mg/L) which can absorb 31.3% and degrade 67.5%; rhodamine B (200mg/L) which can adsorb 36.9 percent and degrade 61.6 percent; methylene blue (500 mg/L) which can absorb 38.8 percent and degrade 59.9 percent can be absorbed.
Example 3
Weighing 80g of crushed corn straws, 12g of potassium extraction by-product bischofite, 2g of silver nitrate and 6g of PVP, putting the crushed corn straws, the potassium extraction by-product bischofite, the silver nitrate and the PVP into a mixing tank containing 750mL of deionized water, and stirring at the rotating speed of 400 r/min for 0.5h at room temperature. And (3) heating the mixed suspension in the dosing tank to 70 ℃, and stirring at constant temperature until the deionized water is completely evaporated to obtain the mixed material.
Step two, adding 25g of potassium hydroxide into the mixed material, stirring uniformly, and then placing at a high temperature with a rotating speed of 15r/minIn the converter, H is introduced2H with S volume fraction of 35% and gas flow rate of 60mL/min2S/N2Exhausting the air in the furnace by the mixed gas, raising the temperature to 600 ℃ at a speed of 10 ℃/min under the atmosphere, and roasting for 4 hours at constant temperature to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by lime water of 6L/min, the absorbed waste gas is directly emptied after reaching the standard through detection, and solid waste obtained by filtering and drying waste liquid reaches the standard and is stacked.
Step three, putting the roasted product in H2H with S volume fraction of 35% and gas flow rate of 30mL/min2S/N2Cooling to room temperature at a rate of 10 ℃/min in a mixed atmosphere, transferring the mixed atmosphere to a washing tank, washing with 120mL of deionized water and 120mL of absolute ethyl alcohol in sequence, heating the slurry in the washing tank to 70 ℃, and drying at constant temperature to obtain MgO-Ag2The S-S and N co-doped amorphous carbon composite material comprises the following components in percentage by weight: 90% of S, N codoped amorphous carbon, 9% of MgO and 1% of Ag2S。
The composite material is used for removing pollutant molecules in wastewater, and can adsorb 34.3% of antibiotic tetracycline hydrochloride (200mg/L) and degrade 64.1% of the antibiotic tetracycline hydrochloride under the specific conditions of adsorption for 1h and visible light degradation for 1 h;
ciprofloxacin hydrochloride (300mg/L) capable of adsorbing 32.3% and degrading 66.1%; rhodamine B (200mg/L) which can adsorb 37.1 percent and degrade 61.6 percent; methylene blue (500 mg/L) which can adsorb 37.6% and degrade 61.2%.
Example 4
Step one, weighing 75g of crushed wheat straw, 12g of potassium extraction by-product bischofite, 3g of cuprous chloride and 10g of melamine, putting the wheat straw, the bischofite and the melamine into a mixing tank containing 700mL of deionized water, and stirring the mixture at room temperature at the rotating speed of 350r/min for 0.5 h. And (3) heating the mixed suspension in the dosing tank to 70 ℃, and stirring at constant temperature until the deionized water is completely evaporated to obtain the mixed material.
Step two, adding 20g of potassium hydroxide into the mixed material, stirring uniformly, putting into a high-temperature converter at the rotating speed of 15r/min, and introducing H2The volume fraction of S is 40 percent and the gas flow rate is 50mL/mH of in2S/N2Exhausting the air in the furnace by the mixed gas, raising the temperature to 700 ℃ at the speed of 20 ℃/min under the atmosphere, and roasting at the constant temperature for 3h to obtain a roasted product.
Waste gas generated in the reaction process is subjected to countercurrent absorption by lime water of 6L/min, the absorbed waste gas is directly emptied after reaching the standard through detection, and solid waste obtained by filtering and drying waste liquid reaches the standard and is stacked.
Step three, putting the roasted product in H2H with S volume fraction of 40% and gas flow rate of 25mL/min2S/N2Cooling to room temperature at a rate of 20 ℃/min in a mixed atmosphere, transferring the mixed atmosphere to a washing tank, washing with 150mL of deionized water and 150mL of absolute ethyl alcohol in sequence, heating the slurry in the washing tank to 70 ℃, and drying at constant temperature to obtain MgO-Cu2The S-S and N co-doped amorphous carbon composite material comprises the following components in percentage by weight: 88% of S, N codoped amorphous carbon, 10% of MgO and 2% of Cu2S。
The composite material is used for removing pollutant molecules in wastewater, and can adsorb 35.7% and degrade 62.9% of antibiotic tetracycline hydrochloride (200mg/L) under the specific conditions of adsorption for 1h and visible light degradation for 1 h;
ciprofloxacin hydrochloride (300mg/L) which can absorb 30.4% and degrade 67.8%; rhodamine B (200mg/L) which can adsorb 39.2 percent and degrade 59.4 percent; methylene blue (500 mg/L) which can absorb 38.6% and degrade 60.1%.
The magnesium oxide-metal sulfide-biomass charcoal composite material provided by the embodiment of the invention comprises monovalent metal sulfide, magnesium oxide and biomass charcoal, wherein the biomass charcoal is S and N co-doped amorphous charcoal. The magnesium-based composite material is used as a material with the highest specific strength and specific stiffness in the metal-based composite material, and has excellent damping property, heat creep resistance, dimensional stability and good cold processing performance; in addition, the S and N co-doped amorphous carbon has good mechanical and physical properties such as large specific surface area, low thermal expansion coefficient, high temperature resistance and the like, and abundant surface active sites and electron capture capacity, is beneficial to promoting the adsorption of pollutant molecules and expanding the visible light absorption range of the composite material, and can improve the adsorption and photocatalytic degradation effects of the composite material on wastewater pollutants; the monovalent metal sulfide and the S and N co-doped amorphous carbon form a heterojunction surface, more active sites can be provided for adsorption and photon absorption of pollutant molecules, and the utilization rate of sunlight is enhanced. Therefore, the composite material prepared by combining the characteristics of the materials not only has the adsorption-photocatalysis dual functions, but also has excellent physical and chemical properties, and can efficiently adsorb and photocatalytically degrade pollutant molecules in wastewater. In addition, the magnesium oxide-metal sulfide-biomass charcoal composite material is prepared by using the crop straws and the byproduct bischofite of the potassium extraction process as raw materials, so that the resource utilization of the crop straws and the byproduct of the potassium extraction process is realized, and the problems of resource waste and environmental pollution caused by the crop straws and the byproduct of the potassium extraction process are solved.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.

Claims (10)

1. The magnesium oxide-metal sulfide-biomass charcoal composite material is characterized by comprising a metal sulfide, magnesium oxide and biomass charcoal, wherein the biomass charcoal is S and N co-doped amorphous charcoal, and the metal sulfide is a monovalent metal sulfide.
2. The magnesium oxide-metal sulfide-biomass charcoal composite material according to claim 1, wherein the composite material comprises, in parts by mass, 70 to 90 parts of biomass charcoal, 5 to 25 parts of magnesium oxide and 1 to 5 parts of metal sulfide.
3. A method for preparing the magnesium oxide-metal sulfide-biomass charcoal composite material according to claim 1 or 2, comprising:
step S10, dissolving the biomass waste, bischofite, monovalent metal salt and nitrogen source organic matter in a solvent, stirring and mixing, heating to evaporate the solvent and obtain a mixed material;
step S20, grinding and stirring the mixed material and potassium hydroxide, placing the mixture into a reaction furnace, and reacting in a reaction furnace in a reaction condition of H2S and N2The mixed gas is roasted to obtain a roasted product;
step S30, the roasted product is put in H2S and N2Cooling in the mixed gas atmosphere to prepare the composite material.
4. The magnesium oxide-metal sulfide-biomass charcoal composite material according to claim 3, wherein in the step S10, the biomass waste is crop straw, the bischofite comprises magnesium chloride hexahydrate as a main component, the monovalent metal salt is silver nitrate, silver chloride, silver sulfate, cuprous chloride or cuprous sulfate, and the nitrogen source organic matter is melamine, urea or polyvinylpyrrolidone;
the biomass waste is 40-80 parts by weight, the bischofite is 5-30 parts by weight, the monovalent metal salt is 2-10 parts by weight, and the nitrogen source organic matter is 5-20 parts by weight.
5. The method for preparing the magnesium oxide-metal sulfide-biomass charcoal composite material according to any one of claims 3 to 4, wherein the step S10 specifically includes:
putting biomass waste, bischofite, monovalent metal salt and nitrogen source organic matter into a mixing tank containing a solvent according to a predetermined mass part ratio, and stirring and dissolving to obtain a mixed suspension;
and heating the mixed suspension in the dosing tank to increase the temperature, and continuously stirring to completely evaporate the solvent to obtain the mixed material.
6. The method for preparing a magnesium oxide-metal sulfide-biomass charcoal composite material according to claim 3, wherein the step S20 specifically includes: grinding and stirring the mixed material and potassium hydroxide, placing the mixture in a high-temperature converter, and introducing H into the high-temperature converter2S and N2In the said H2S and N2Heating the mixture to a preset roasting temperature in the atmosphere of the mixed gas, and then roasting the mixture at a constant temperature to obtain a roasted product.
7. The preparation method of the magnesium oxide-metal sulfide-biomass charcoal composite material according to claim 6, wherein the potassium hydroxide is 5 to 30 parts by mass; the temperature rise speed of the high-temperature converter is 5-20 ℃/min, the roasting temperature is 500-800 ℃, and the roasting time is 3-6 h.
8. The method for preparing the magnesium oxide-metal sulfide-biomass charcoal composite material according to claim 3, wherein the step S30 specifically comprises:
subjecting the calcined product to reaction in H2S and N2Cooling to room temperature in the mixed gas atmosphere;
washing and drying the cooled roasting product at constant temperature to obtain the composite material;
wherein the cooling rate of the roasted product is 5-20 ℃/min, and the constant-temperature drying temperature is 50-80 ℃.
9. The method for preparing a magnesium oxide-metal sulfide-biomass charcoal composite material according to any one of claims 6 to 8, wherein the H is2S and N2In the mixed gas of (2), H2The volume percentage of S is 5-40%; in the step S20, the H2S and N2The flow rate of the mixed gas is 50mL/min to 100 mL/min; in the step S30, the H2S and N2The flow rate of the mixed gas is 20mL/min to 50 mL/min.
10. Use of the magnesium oxide-metal sulfide-biochar composite of claim 1 or 2 in water pollution treatment.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103143377A (en) * 2013-02-19 2013-06-12 中国科学院理化技术研究所 Application of heteroatoms doped aqueous carbon quantum dot in photocatalyst
CN103861632A (en) * 2014-04-07 2014-06-18 吉林大学 Preparation method for multi-hole carbon nitride photocatalytic material doped with sulphur
CN104409706A (en) * 2014-12-22 2015-03-11 湖南大学 Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof
CN105271319A (en) * 2015-10-28 2016-01-27 内江师范学院 Method for preparing nanometer MgO
CN106179408A (en) * 2016-07-14 2016-12-07 扬州天辰精细化工有限公司 A kind of Argentous sulfide. load Radix Raphani derives the preparation method of carbon aerogel material
KR20170006773A (en) * 2015-07-09 2017-01-18 한국과학기술원 Metal/semiconductor hybrid nanoparticle and method for manufacturing the same
CN106744937A (en) * 2016-12-07 2017-05-31 中国科学院新疆理化技术研究所 The preparation method and purposes of a kind of graphitization grading-hole Carbon Materials of N doping
CN109364951A (en) * 2018-12-21 2019-02-22 苏州科技大学 A kind of visible light catalytic composite material and preparation method and application
CN110075869A (en) * 2019-05-31 2019-08-02 华南理工大学 A kind of method that the oil-tea camellia husks of heavy metal polluted waste water processing prepare photochemical catalyst
CN110280296A (en) * 2019-07-19 2019-09-27 华东理工大学 A kind of method of azotized carbon nano on piece growth in situ defect cuprous sulfide nano particle
WO2019229255A1 (en) * 2018-05-31 2019-12-05 Cambridge Enterprise Limited Photocatalyst and photocatalytic methods for producing hydrogen
CN110935280A (en) * 2019-12-06 2020-03-31 四川大学 Nitrogen-doped mesoporous bamboo-based biochar and application thereof
CN111530487A (en) * 2020-04-29 2020-08-14 清华大学深圳国际研究生院 Preparation method of bismuth tungstate nitrogen sulfur co-modified biochar

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103143377A (en) * 2013-02-19 2013-06-12 中国科学院理化技术研究所 Application of heteroatoms doped aqueous carbon quantum dot in photocatalyst
CN103861632A (en) * 2014-04-07 2014-06-18 吉林大学 Preparation method for multi-hole carbon nitride photocatalytic material doped with sulphur
CN104409706A (en) * 2014-12-22 2015-03-11 湖南大学 Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof
KR20170006773A (en) * 2015-07-09 2017-01-18 한국과학기술원 Metal/semiconductor hybrid nanoparticle and method for manufacturing the same
CN105271319A (en) * 2015-10-28 2016-01-27 内江师范学院 Method for preparing nanometer MgO
CN106179408A (en) * 2016-07-14 2016-12-07 扬州天辰精细化工有限公司 A kind of Argentous sulfide. load Radix Raphani derives the preparation method of carbon aerogel material
CN106744937A (en) * 2016-12-07 2017-05-31 中国科学院新疆理化技术研究所 The preparation method and purposes of a kind of graphitization grading-hole Carbon Materials of N doping
WO2019229255A1 (en) * 2018-05-31 2019-12-05 Cambridge Enterprise Limited Photocatalyst and photocatalytic methods for producing hydrogen
CN109364951A (en) * 2018-12-21 2019-02-22 苏州科技大学 A kind of visible light catalytic composite material and preparation method and application
CN110075869A (en) * 2019-05-31 2019-08-02 华南理工大学 A kind of method that the oil-tea camellia husks of heavy metal polluted waste water processing prepare photochemical catalyst
CN110280296A (en) * 2019-07-19 2019-09-27 华东理工大学 A kind of method of azotized carbon nano on piece growth in situ defect cuprous sulfide nano particle
CN110935280A (en) * 2019-12-06 2020-03-31 四川大学 Nitrogen-doped mesoporous bamboo-based biochar and application thereof
CN111530487A (en) * 2020-04-29 2020-08-14 清华大学深圳国际研究生院 Preparation method of bismuth tungstate nitrogen sulfur co-modified biochar

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
HAI-BO HUANG等: "Lotus-Leaf-Derived Activated-Carbon-Supported Nano-CdS as Energy-Efficient Photocatalysts under Visible Irradiation", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 *
MAO, W等: "Facile assembled N, S-codoped corn straw biochar loaded Bi2WO6 with the enhanced electron-rich feature for the efficient photocatalytic removal of ciprofloxacin and Cr(VI)", 《CHEMOSPHERE》 *
XIAOGANG ZHENG等: "Enhanced adsorption capacity of MgO/N-doped active carbon derived from sugarcane bagasse", 《BIORESOURCE TECHNOLOGY》 *
郑小刚等: "Ag掺杂方式对g-C3N4降解亚甲基蓝光催化行为的影响", 《化工新型材料》 *
陆俊炜: "MxS(M=Ag,Cu,Zn)/CA复合材料的可控制备及其可见光催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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