Ruobing Zhang

The spent caustic with strong alkali first replaced the alkali activator to prepare the geopolymer. The influence of spent caustic to the geopolymer was characterized through compressive strength measurement, XRD, MIP analysis and NMR, and the immobilization efficiency of organic in geopolymer was evaluated through the measurement of total organic carbon (TOC). The results show that the spent caustic can partially replace the alkali activator to prepare the geopolymer, and it shows a better performance than that which was activated with pure NaOH solution when the alkalinity is between 4 mol and 14 mol. The organic matter in the spent alkali can be effectively fixed in the geopolymer, which will hinder the geopolymerization in the initial stage of the polymerization reaction but has little effect on the chemical structure and mechanical properties of the final product. With the degree of alkalinity increasing, the immobilization efficiency is improved, and the maximum can reach 84.5%. The organics in the spent caustic will hinder geopolymerization at the initial stage but has little effect on the chemical structure and mechanical property of the final product. This study proposes a new method for the recycling of spent caustic, which also reduces the preparation cost of geopolymers.

In this work, we propose a rapid and facile method (oxalic acid leaching under microwave-assisted conditions) to study the simultaneous recovery of vanadium (V) and nickel (Ni) from spent fluid catalytic cracking (SFCC) catalysts. The central issue in all of these studies is to test the modeling and experimental results of excellent fitting effects of leaching parameters. In order to maximize the recovery of V and Ni, leaching parameters were investigated. Furthermore, response surface methodology (RSM) was applied to optimize the leaching parameters. The optimum conditions obtained were as follows: oxalic acid concentration of 1.8 mol/L; leaching time of 91 min; microwave-assisted power of 500 W; H₂O₂ concentration of 1.1 mol/L. The maximum leaching rates of V and Ni reached the values of 91.36% and 46.35%, respectively. The results showed that microwave energy was very helpful in improving the efficiency of the leaching process and shortening the leaching time by 75%. According to the shrinking core model, test results showed that a surface chemical reaction was the controlling step of the overall reaction kinetics. The activation energy of V and Ni during the leaching reaction was calculated to be 3.28 and 34.41 kJ/mol, respectively.

The problem of spent fluid catalytic cracking (SFCC) catalyst resource utilization, draws more and more attention to system analysis. SFCC was leached in an oxalic solution for comprehensive utilization. The results showed that for a D50 ≤ 17.34 μm, the catalyst leached for 240 min at 95 °C in the presence of a 2 mol/L oxalic acid solution, and the extent of leaching of V, Ni, Fe, and Al was 73.4%, 32.4%, 48.2%, and 36.8%, respectively. Studies on the occurrence state of the main ions (V, Ni, Fe, and Al) in the leaching solution were presented. Additionally, the separation of the main ions from such a solution by the “solvent extraction-stripping-hydrothermal precipitation-comprehensive recovery of valuable metal” process was studied. The immobilization rates of vanadium and nickel in geopolymers can be obtained using the toxicity characteristic leaching procedure (TCLP) test, and the geopolymers prepared by SFCC leaching residues can be considered a non-hazardous material. A process diagram of the comprehensive utilization of SFCC catalysts is presented.

As a common industrial by-product, the spend fluid catalytic-cracking (SFCC) catalyst was used to prepare phosphate-based geopolymer for the first time. The structure and property of geopolymer with phosphoric acid concentration ranging from 6 to 14 mol/L was characterized by compressive strength measurements, X-ray powder diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and ²⁷Al and ²⁹Si nuclear magnetic resonance (NMR). A stable binder was formed with the compressive strength in the range of 9.8 to 30.2 MPa when the acid concentration was between 6 and 12 mol/L. The higher concentration of acid can promote the dissolution of raw materials and formation of geopolymer gels. The coordination of silicon and aluminum in geopolymer gel synthesized with the SFCC catalyst and metakaolin is similar. Compared with the geopolymer with metakaolin, which forms more Si-O-Al bonds, in the networks of geopolymer with the SFCC catalyst, more Si(Al)-O-P bonds were formed. These results indicate that the SFCC catalyst can be an excellent raw material for the synthesis of phosphate-based geopolymer.