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CN-122010160-A - Method for synthesizing calcium sulfate nanorod by morphology regulation and control of waste gypsum, calcium sulfate nanorod and application thereof, supported aromatic nitro hydrogenation catalyst and preparation method thereof

CN122010160ACN 122010160 ACN122010160 ACN 122010160ACN-122010160-A

Abstract

The invention relates to a method for synthesizing a calcium sulfate nano rod by morphology regulation and control of waste gypsum, the calcium sulfate nano rod, application thereof and a supported aromatic nitro hydrogenation catalyst and a preparation method thereof, belonging to the technical field of high-added-value resource utilization of solid waste and the field of heterogeneous hydrogenation catalysis. The method comprises the steps of mixing waste gypsum with a solution containing an inducing agent and a modifying agent, stirring for reaction, washing and drying a solid to obtain a calcium sulfate nanorod, wherein the inducing agent is soluble sulfate and/or soluble persulfate, and the modifying agent is at least one selected from a surfactant, an organic acid sodium salt, an organic acid potassium salt, an alkali metal chloride, an alkaline earth metal chloride and a soluble polymer. The invention innovatively adopts the waste gypsum as the raw material, synthesizes the calcium sulfate nanorods from the waste gypsum by using the inducing reagent and the modifying reagent, and further prepares the calcium sulfate nanorods into the high-added-value hydrogenation catalyst, thereby solving the problems of cost, environmental pollution and the like of the traditional recycling waste gypsum.

Inventors

  • Ren zhenxing
  • XU XIANG
  • LIAN LIZHEN
  • LIU YOUNIAN

Assignees

  • 中南大学

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1. A method for synthesizing a calcium sulfate nano rod by morphology regulation of waste gypsum is characterized by comprising the following steps: Mixing waste gypsum with a solution containing an induction reagent and a modification reagent, stirring for reaction, and washing and drying a solid substance to obtain a calcium sulfate nano rod; the modifying reagent is at least one selected from a surfactant, an organic acid sodium salt, an organic acid potassium salt, an alkali metal chloride, an alkaline earth metal chloride and a soluble polymer; The surfactant is at least one of Tween-20, tween-40, tween-60 and Tween-80; the organic acid sodium salt is at least one selected from disodium ethylenediamine tetraacetate, sodium malate, sodium tartrate and sodium oxalate; The organic acid potassium salt is at least one selected from potassium malate, potassium tartrate and potassium oxalate; The alkali metal chloride is potassium chloride and/or sodium chloride; the alkaline earth metal chloride is selected from at least one of magnesium chloride, calcium chloride and barium chloride; The soluble polymer is polyethylene glycol and/or polyacrylic acid.
  2. 2. The method for synthesizing the calcium sulfate nanorods by morphology regulation of the waste gypsum according to claim 1, wherein the soluble sulfate is at least one selected from the group consisting of sodium sulfate, potassium sulfate, sodium bisulfate, potassium bisulfate and magnesium sulfate; the soluble persulfates are sodium persulfate and/or potassium persulfate.
  3. 3. The method for synthesizing the calcium sulfate nanorods by morphology regulation of the waste gypsum according to claim 1 or 2, wherein the mass concentration of the inducing agent is 1-50wt% and the concentration of the modifying agent is 0.01-0.4 mol/L in the solution containing the inducing agent and the modifying agent; and/or the mass concentration of the waste gypsum in the solution containing the induction reagent and the modification reagent is 1-50wt%.
  4. 4. The method for synthesizing the calcium sulfate nanorods by morphology regulation of the waste gypsum according to claim 1 or 2, wherein the stirring reaction is carried out at a temperature of 1-120 ℃ for 1-96 h at a stirring rate of 1-1000 r/min; And/or the temperature of the drying treatment is 1-100 ℃ and the time is 1-48 hours, and the drying mode adopts vacuum drying and/or freeze drying.
  5. 5. The method for synthesizing the calcium sulfate nanorods by morphology regulation of the waste gypsum according to claim 1 or 2, wherein the washing reagent adopted by the washing is water and/or ethanol.
  6. 6. A calcium sulfate nanorod prepared by the control method according to any one of claims 1 to 5.
  7. 7. The use of the calcium sulfate nanorod as a carrier for preparing a supported aromatic nitro hydrogenation catalyst.
  8. 8. The supported aromatic nitro hydrogenation catalyst is characterized in that a carrier of the hydrogenation catalyst is a calcium sulfate nanorod, an active ingredient is ruthenium, and the load of the active ingredient is 0.1-2.5wt%; The calcium sulfate nanorods are the calcium sulfate nanorods according to claim 6.
  9. 9. A method for preparing a supported aromatic nitro hydrogenation catalyst according to claim 8, which is characterized in that the method comprises the steps of stirring and mixing a calcium sulfate nano rod with ruthenium-containing solution, and then carrying out reduction calcination to obtain the supported aromatic nitro hydrogenation catalyst.
  10. 10. The preparation method of the supported aromatic nitro hydrogenation catalyst according to claim 9, wherein the stirring and mixing temperature is 90-120 ℃ for 20-36 hours, the reduction and calcination temperature is 250-750 ℃ for 1-4 hours; and/or the reducing gas in the reduction calcination contains 5-15% by volume of hydrogen and 85-95% by volume of inert gas, and the flow rate of the reducing gas is 10-100 mL/min.

Description

Method for synthesizing calcium sulfate nanorod by morphology regulation and control of waste gypsum, calcium sulfate nanorod and application thereof, supported aromatic nitro hydrogenation catalyst and preparation method thereof Technical Field The invention relates to a method for synthesizing a calcium sulfate nano rod by morphology regulation and control of waste gypsum, the calcium sulfate nano rod, application thereof and a supported aromatic nitro hydrogenation catalyst and a preparation method thereof, belonging to the technical field of high-added-value resource utilization of solid waste and the field of heterogeneous hydrogenation catalysis. Background Industrial waste gypsum refers to gypsum-based materials having calcium sulfate dihydrate or calcium sulfate hemihydrate as a main chemical component, which is produced as a by-product or waste in an industrial production process. If a large amount of industrial waste gypsum cannot be effectively treated and utilized, the waste gypsum is only piled in open air, so that serious environmental hazard and social problems are brought. The existing resource utilization of waste gypsum has the following way (1) to prepare calcium sulfate powder. Chinese patent (CN 113603128A) discloses a method for preparing various calcium sulfate powder by industrial byproduct gypsum, which comprises the steps of dissolving industrial byproduct gypsum in an acid solution to obtain a crude calcium sulfate acid solution, filtering to obtain a refined calcium sulfate acid solution, adding concentrated sulfuric acid or concentrated sulfuric acid and an ethanol solution to obtain a first calcium sulfate dihydrate suspension or a calcium sulfate hemihydrate suspension, and carrying out suction filtration to obtain a product by regulating pH. However, the method has complex process, needs strong acid, can emit toxic and harmful gas in the reaction process to harm the environment, and has high corrosion resistance requirement on the reaction vessel. (2) And growing calcium sulfate whiskers from the fluorine gypsum slag. Chinese patent (CN 110528060A) discloses a method for growing calcium sulfate whisker by using fluorine gypsum slag, which comprises the steps of taking the fluorine gypsum slag as a raw material, grinding the fluorine gypsum slag, and mixing the ground fluorine gypsum slag with water to obtain slurry. Adding soluble carbonate into the slurry, stirring for reaction, and filtering to obtain a first filtrate and a first filter residue. Adding acid liquor into the first filter residue, stirring for reaction, and filtering to obtain a second filtrate and a second filter residue. And mixing the first filtrate and the second filtrate to obtain the calcium sulfate colloid solution. Adding a crystal growth promoter into the calcium sulfate colloid solution, performing hydrothermal reaction, standing for reaction, and drying to obtain the calcium sulfate whisker. However, the method has the advantages of complex process, large amount of greenhouse gases released by acid and carbonate, high energy consumption in the reaction, and no contribution to large-scale popularization and application. (3) calcining to produce gypsum powder. The Chinese patent (publication No. CN 101033118A) discloses a novel gypsum calcining process, which aims at the characteristics of industrial byproduct gypsum (complex components, tiny particles and higher water content), adopts a unique calcining process method, namely, a countercurrent and concurrent combination mode, and a rotary tube capable of introducing a heat medium is arranged in a kiln body, so that the novel process of external (indirect) calcining and internal (direct) calcining mixed calcining is achieved, but the environment is polluted due to volatilization of phosphoric acid and fluoride during calcining, equipment is corroded, and the high-temperature calcining energy consumption cost is higher, and the application is greatly limited. meanwhile, because the impurity with the largest content in phosphogypsum is quartz, the calcination process cannot remove the quartz impurity, so that the method cannot produce a high-whiteness and high-purity high-quality gypsum product. (4) preparing a non-fired brick. Document （Jun Zhou, Hui Gao, Zhu Shu, Yanxin Wang, Chunjie Yan.Utilization of waste phosphogypsum to prepare non-fired bricks by a novel Hydration–Recrystallization process[J].Construction and Building Materials,2012,34:114-119.） proposes a new process called "hydration-recrystallization process" for preparing unburned bricks from waste phosphogypsum. In the process, the pressed raw bricks are subjected to thermal drying at 180 ℃ to dehydrate gypsum into hemihydrate gypsum, then soaking water to enable the gypsum to recrystallize in situ, and finally naturally air-drying to obtain the unfired brick products. the technology has the problems of high energy consumption, low natural air drying efficiency and difficult large-s