Preparation Of Magnetic Nickel Solid Acid Catalyst And Its Catalytic Conversion To Kerosene Co-Hydrogenation

The coal-oil co-refining technology is developed on the basis of the direct coal liquefaction technology.It has the characteristics of two processes of coal liquefaction and heavy oil upgrading.It is an important means for the efficient utilization of coal and low-quality residue.Coal-oil hydroprocessing can be realized because coal direct liquefaction technology and heavy oil hydrocracking technology have very similar conditions.On this basis,coal-oil coprocessing can improve or even eliminate the defects in coal direct liquefaction technology.It has the advantages of synergistic effect between coal and heavy oil,high conversion rate of raw materials,high production efficiency,high product quality and low production cost.Therefore,coal-oil co-refining is one of the effective ways to solve the rational utilization of coal and deep processing of heavy oil.The research and preparation of catalysts are the key to coal-oil co-refining technology.In this study,firstly prepared magnetic nano-Fe₃O₄ spheres（MFONPs）,g-Al₂O₃ was wrapped on MFONPs to form core-shell structures（MPMCs）,and then MPMCs were immersed in trifluoromethanesulfonic acid（TFMSA）to obtain magnetic solid super acid catalyst（MSSA）,and finally Ni（CO）₄ was thermally decomposed on MSSA by in-situ decomposition method to prepare nickel-based solid super acid catalyst（Ni-MSSA）.The Ni15%-MSSAwas subsequently characterized,and the results showed that Ni was successfully loaded on MSSA with a uniform and low amount,and TFMSA was also successfully loaded on MPMCs.Ni15%-MSSA has a large specific surface area and strong acidity.The loaded Ni reacts with TFMSA andg-Al₂O₃,and a strong interaction occurs between them.The biphenyl ether（ODB）was selected as the related model compounds（CRMCs）of coal to explore the catalytic hydrogenation ability and mechanism of Ni15%-MSSA.It is preliminarily speculated that Ni15%-MSSAcan release free H⁺,and can activate H₂ to generate H···H and then split to form free H⁺and（39）^-adsorbed on Ni15%-MSSA.The cycle time proved that Ni_15%-MSSA has good stability and recyclability.The synergistic effect between different coal types and catalytic cracking oil slurry（FCCO）was studied.The extraction residue of Longquan lignite(LL_ER)and the extraction residue of Yanchang Weiqiang bituminous coal(WBC_ER)were reacted with FCCO,and it was discovered that there is a good synergistic effect between the co-hydrotreating of LL_ER and FCCO,and the best ddition amount of FCCO is 10%;There is no synergistic effect between WBC_ER and FCCO co-hydroprocessing,and it will even hinder the liquefaction of WBC_ER.Through further exploration,the most suitable solvent for dissolving FCCO is n-hexane-anhydrous ethanol（v/v,1:1）.The catalyst Ni_15%-MSSA was used to conduct catalytic co-hydrogenation experiments on LL_ER and FCCO,and the effects of FCCO addition amount,atmosphere,pressure,temperature,and time on the reaction system were explored.In addition,the soluble component of LL_ER non-catalytic hydrogenation(SP_NCHC-LL),the soluble component of LL_ER and FCCO non-catalytic hydrogenation(SP_NCHC-LL+FCCO),the soluble component of LL_ER and FCCO catalytic hydrogenation(SP_CHC-LL+FCCO)was qualitatively and quantitatively analyzed by GC/MS.Based on this,the catalytic effect of Ni_15%-MSSA on the hydrocracking of the LLER and FCCO co-processing system was investigated.The results show that through the co-treatment of LLER and FCCO,the conversion rate of catalytic addition of CHC and the yield of liquid products are increased by 12.34%and 10.51%,respectively,than those of non-catalytic hydrocracking NCHC coal.SPNCHC-LL,SPNCHC-LL+FCCO and SPCHC-LL+FCCO mainly include linear alkanes,branched alkanes,alkenes,alkynes,cycloalkanes,alkyl substituted benzene,alkenyl substituted benzene,methoxybenzene,ethyl Derivatives of oxybenzene,naphthalene,phenanthrene,indene and anthracene,alcohols,phenols,ketones,aldehydes,esters,acids,furans,nitrogen-containing compounds,sulfur-containing compounds and chlorine-containing compounds.In addition,it was found that there are a large number of nitrogen-containing,sulfur-containing and benzophenone compounds in SP_NCHC-LL.After adding FCCO,the types and quantities of paraffin and alcohol compounds in SP_NCHC-LL+FCCO have been greatly improved.After adding the catalyst,the relative content of branched alkanes and nitrogen-containing sulfur-containing heteroatom compounds in SP_CHC-LL+FCCO decreased,and the relative content of phenols and cycloalkanes increased,indicating that FCCO and the catalyst interacted during the hydrogenation process.And Ni_15%-MSSA can promote the cleavage of the macromolecule C_ar-C_alk and part of the C-O bonds in coal.At the same time,FCCO is used as a hydrogen supply solvent to provide part of the activated hydrogen and Ni_15%-MSSA converts the hydrogen dissolved in the liquid into active hydrogen together to promote hydrogenation of aromatic rings.And through the reaction of LL_ER with FCCO’s non-catalytic hydrogenation（NCHC）and catalytic hydrogenation（CHC）,it was found that under NCHC conditions,the coal conversion rate of the reaction under hydrogen atmosphere and nitrogen atmosphere is similar,indicating that the active hydrogen comes from the FCCO circulating solvent.This proves that under non-catalytic conditions,the main source of active hydrogen is the hydrogen supply solvent;Under CHC conditions,the conversion rate of coal in hydrogen atmosphere is higher than that under nitrogen atmosphere,indicating that part of the active hydrogen comes from the FCCO circulating solvent and part of it comes from hydrogen,which proves that under the catalytic conditions,the active hydrogen comes from hydrogen and hydrogen supply solvent.There are 37 figures,36 tables and 123 references in this thesis.