Using CO as the probe molecule, infrared diffuse reflectance spectroscopy was used to study the adsorption of Pd⁃Ag/Al2O3 catalysts prepared by impregnation method and the carbon monoxide adsorption on the support and a series of changes in the surface species of the catalyst. The results showed that in the Pd⁃Ag/Al2O3 catalytic system, due to the different order of silver addition, the active center of the catalyst was affected by the electronic effect and the geometric effect, which caused the surface species adsorption morphology of the catalyst after CO adsorption. It was found that there was no bridge adsorption of CO on Pd⁃Ag/Al2O3⁃LM⁃2 catalyst when CO was adsorbed and desorbed before and after heating. The characteristic peak intensity of HCO〖_3^-〗 was found decreased with the increase of CO adsorption and desorption temperature. At the same time, the adsorption characteristic peak of HCOO- was relatively enhanced, and the consistent growth and decline relationship between the two indicated that HCO〖_3^-〗 was converted to HCOO- during the heating process.

The Hβ zeolite was modified with different concentrations of citric acid. The textures of the modified Hβ zeolites were characterized by XRD and Ar adsorption, and the acid properties were characterized by NH3⁃TPD and Py⁃FTIR. In addition, the interaction between the pyridine molecules and the active constituent units of the Hβ zeolite was also analyzed by Py⁃FTIR. The results showed that several active sites, such as the Brønsted acid sites associated with the bridging hydroxyl groups (SiOHAl), the weak Lewis acid sites associated with EFAL hydroxyl groups and the strong Lewis acid sites associated with the three⁃coordinated Al hydroxyl species and AlO+ cations were existed in the Hβ zeolite. The synergistic effect between the EFAL and the adjacent bridging hydroxyl groups was found on the adsorption of pyridine. The pyridine molecule which adsorbed in the Lewis acid site and bonded with the adjacent B acid sites was less likely to desorb at high temperature. Pyridine molecules were preferentially adsorbed on the strong acidic bridging hydroxyls and defect sites associated with the three⁃coordinated Al hydroxyl species. It was only weakly interacted with EFAL hydroxyl groups. After citric acid treatment, EFAL hydroxyl groups were selectively removed while the framework aluminum was not severe damaged. The strong Lewis acid sites were preserved in the modified Hβ zeolite after citric acid treatment, and the strong Lewis acid sites may be related to AlO+ and the three⁃coordinated Al species of defect sites.

The supported SnCl4 catalyst was prepared using activated carbon as the carrier. Different contents of BiCl3 and CuCl2 were added into SnCl4 catalyst as assistant in order to study the effect of assistant on the catalytic performance of acetylene hydrochlorination. The results showed that when the ratio of BiCl3⁃CuCl2⁃SnCl4 was 5%,10%,10%.The catalyst showed the highest activity for acetylene hydrochlorination. The conversion of acetylene can reach 94% under the conditions of hydrogen chloride/acetylene ratio 1∶1.1, reaction temperature 170 ℃ and GHSV(C2H2) of 60 h-1. The characterization results showed that the introduction of additives inhibited the loss of Sn during the reaction and thus improved the stability of the catalyst. Finally, the activity of Sn based catalyst was effectively improved.

Brønsted acid in Y zeolite plays a key role in the processes of catalyst,and the structure reflects the strength of B acid.The stable structures of Brønsted acid sites of HY,[AlO]+/HY,and [Al(OH)]2+/HY were simulated by periotic models.The relationship between the structures of Brønsted acid sites and its environments was identified by combination of dynamic simulation with DFT calculation.By analyzing the structure and electronic permanent,together with the statistical results of molecular dynamics,it can be found that the strength of Brønsted acid can connected with the number of H atoms in the 12 membered ring that the small number.The weaker the binding ability of H atoms to O atoms in B acid center is,and the more electrons H atoms lose,the stronger the B acid acidity is.The addition of extra⁃framework aluminum can enhance the acidity of B acid,and [Al(OH)]2+ has more obvious effect on B acid properties.These results can lead the synthetic and modification of B acid site in a theoretical support.

The C3N4/AC catalyst was prepared by using the same nitrogen content of cyanamide,thiourea,urea as precursor and activated carbon as the carrier. The reaction performance of C3N4/AC catalyst for the catalytic pyrolysis of 1,2⁃dichloroethane was evaluated by using fixed bed reactor,and the properties of catalyst structure were characterized by SEM,XRD,BET,XPS and TGA. The results showed that the initial activity and selectivity of the catalyst prepared from 0.110 mol precursor were close to 100%,but the stability of the catalyst was different obviously. The catalyst synthesized with urea as precursor had the highest catalyst stability compared with the other two precursors. However,the catalysts synthesized by using low loading of precursors showed differences on the catalytic performance. The structure and morphology of the catalysts with low loading of precursor were investigated. The results showed that when the load was reduced to 0.057 mol,the C3N4/AC catalyst prepared with urea had the highest catalytic activity for dehydrochlorination of 1,2⁃dichloroethane and the best stability.The different morphologies of carbon nitride was synthesized by different precursors. The carbon nitride productivity of thiourea and cyanamide is higher than urea but is more easily to form bulk carbon nitride which will result in poor stability. After all,urea is the optimal precursor for the C3N4/AC catalyst for dehydrochlorination of 1,2⁃dichloroethane.

Hβ zeolites were modified by hydrochloric acid. The crystal structure, textual properties and total acid content of the Hβ zeolites were characterized by XRD, N ₂ adsorption and NH ₃­TPD. Using thiophene as the probe molecule, the mass transfer behavior of Hβ zeolites modified by hydrochloric acid was studied by Frequency Response. The results showed that hydrochloric acid washed away the non skeleton aluminum which blocked the pore of zeolites, enhanced the permeability of molecular sieve pore and improved the mass transfer performance of the molecular sieve. In the frequency response spectrum, the response intensity of thiophene in the modified Hβ zeolites was obviously greater than that in the unmodified zeolite. The mass transfer performance of modified Hβ zeolites was improved, and the ability to adsorb thiophene was also enhanced obviously, which was significant for catalyzing thiophene reaction and optimizing industrial desulfurization.

CeY, NdY and HoY zeolites were prepared by liquid phase ion exchange method, and the Ni contamination was carried out by Mitchell impregnation method. The acid properties of the catalysts were characterized by ammonia temperature programmed desorption （NH ₃-TPD） and in situ pyridine infrared spectroscopy. The results indicate that REY zeolite has a better ability to inhibit the destruction of the Brnsted （B） acid sites with the decrease of the radius of rare earth ions. Further acidity and activity were associated, it was found that the catalytic cracking activity of REY zeolite was increased with the decrease of the radius of RE. And the content of gasoline in the reaction liquid phase increased with the decrease of the radius of RE ions in Ni/REY zeolite catalyst. So the smaller the RE ionic radius, the better the nickel tolerance of REY zeolite.

In order to improve the safety of air flooding and quality of heavy oil, static oxidation experiments were conducted to research the effect of oil displacement agent on the catalytic low temperature oxidation (CLTO) of heavy oil. The results showed that the oil displacement agent could accelerate the oxygen consumption rate, and especially the effect of NaOH and PAM on oxygen consumption rate were obvious. Saturates, aromatics, resins and asphaltenes (SARA) analysis and experiments using oil displacement agent were preformed to study the effect of oil displacement agent on the crude oil components. Saturates and aromatics were converted to resins and asphaltenes during low temperature oxidation (LTO), and the addition of Fe3O4 nanoparticles could reverse this change. This study can provide guidelines to select of oil displacement agent, improve the safety and increase the application of air flooding technology.

CuOZnOZrO2 catalyst was modified by combustion method, using Al2O3, CeO2, NiO metal oxides as promoters. The effects of Al2O3, CeO2, NiO on phase composition and catalyst structure were illuminated by using Xraydiffraction (XRD), temperatureprogrammed reduction ofhydrogen(H2TPR), temperatureprogrammed desorption of hydrogen (H2TPD) and carbon dioxide (CO2TPD) techniques. And the effects of the three chosen promoters on catalytic performance for CO2 hydrogenation to methanol were studied in a fixedbed plug flow reactor. The results indicated that the three promotes of Al2O3, CeO2, NiO all contributed to improving theactivity of catalysts and CeO2modified catalyst had best catalytic performance. Moreover, the three promotes all could inhibit CuO crystal grain growth and improve the dispersion of CuO, which could benefit the reduction of catalysts and H2 adsorptiondissociation. Besides that, the three metal oxides could modulate the intensity amount of basic sites on the catalyst surface in different degrees. Comparing with NiOmodified catalyst, CeO2modified catalyst and Al2O3 modified catalyst both possessed higher basic intensity and more basia sites, which led to CO2 adsorptionactivation easily.

Using active carbon as carrier, SnCl4 based non mercury catalysts, including Sn@AC, Sn - Bi@AC, Sn - Bi - Co@AC, were synthesized by adding different content of BiCl3 and CoCl3. The catalysts were evaluated in acetylene hydrochlorination atmospheric fixed bed reactor. The results showed that the catalytic properties of synthetic three component catalysts were optimal on the proportion of 10%SnCl4, 5%BiCl3 and 10%CoCl3. Acetylene's conversion rate was more than 90% and the selectivity of vinyl chloride was a round 95% within the reaction time of 100 h. Through the XRD and physical adsorption instrument, catalyst microstructures were characterized. Coconut shell activated carbon's specific surface area and pore size was significant increased after nitric acid t reatment; adding component BiCl3 and CoCl3 could make the coke phenomenon on catalytic surface weakened.

Adsorption and diffusion behavior of benzene in NaY zeolite are studied by using the frequency response method. The TG/DTG curves and Py FTIR technique are used to analyze the adsorption and diffusion mechanism of benzene on NaY. The results indicate that NaY zeolite contains two kinds of acidic centers, namely, the weak B acid and weak L acid sites. And L acid sites are in a dominant position. There are two adsorption interactions on NaY zeolite at 333 K and 423 K, the adsorption of low frequency through the π electronic interactions and high frequency of adsorption belong to pore filling. Adsorption is still the controlling stepat 573 K. However, diffusion is the controlling step on NaY at 623 K, indicating that weak adsorption results in easier desorption and easier diffusion of aromatic molecules on NaY, there by improving the performance of the hydro cracking reaction.

The density functional theory has been employed to study the influence rule of the catalytic cleavage activity of C—H bond in hydrocarbons affected by adjacent groups under the copper acetate catalyst. The computed results suggested that the order of catalytic cleavage activity of C—H bond of methyl and methyne linking with different adjacent groups was: phenyl>nhexyl > cyclohexyl, while the order of catalytic cleavage activity of C—H bond of methylene was: phenyl>cyclohexyl>nhexyl. It was found that the effect of adjacent groups on catalytic cleavage activity of C—H bondwas related with charge value and space steric hindrance of adjacent groups before and after the adsorption on catalyst.

The physical and chemical properties of NaY and HY zeolites were characterized by N2 adsorption. The adsorption and diffusion behavior of benzene on NaY and HY zeolites were studied by using Frequency Response (FR) and Intelligent Gravimetric Analysers (IGA ) technique. These results indicate that the interaction of benzene on NaY zeolite with the Na+ in the framework is greater than the interaction of benzene on HY zeolite with the B acid.In addition, the higher temperature is conducive to the spread of benzene in the zeolite. Different mass transfer processes and the strength of the force of the molecules in the microporous of these zeolites can be validly identified by FR technique. It is an effective way to study the dynamics of microporous materials.

Air injection low temperature oxidation reaction of heavy oil has been simulated in the highpressure reactor to study the oxidative mechanism of the reaction without or with catalyst. The before and after oxidation changes of oxygen content in tail gas and products of heavy oil were detected using TY3160type oxygen analyzer and NDJ4Atype potentiometric titrator, respectively. The results show that the using of transition metal salt as primary catalyst not only accelerates the oxidizing reaction, but also affects the selectivity of oxidation products. The addition of transition metal salt is helpful for the production of carboxylic acid, aldehyde and ketone, but reduces the production of alcohol. This research can provide the favorable theoretical basis for improving mining technology of air injection low temperature of heavy oil and further optimizing the design of catalyst.

Adsorption and diffusion behavior of aromatic hydrocarbons (benzene, pxylene and cumene) on Fluid Catalytic Cracking (FCC) catalysts and multisites of components REUSY zeolite have been systematically investigated by N2 adsorption, Intelligent Gravimetric Analyser (IGA) and Temperature Programmed Desorption (TPD) technology. Only one adsorption model for aromatic hydrocarbons in FCC catalysts and REUSY zeolite was observed in TG/DTG profiles, speculating that the adsorption mode was π electron interactions between aromatic and adsorbent. The controlling steps for the overall mass transfer process in the FCC catalyst particles are the diffusion process in the length scale of macropore of the matrix or/and the mass transfer at the zeolitematrix interface rather than the intracrystalline diffusion one in the micropores of the zeolite crystals.

Surface acidities of the Y zeolites(NaY, HY, LCeY and HRSY3) were characterized by temperatureprogrammed desorption of ammonia(NH3TPD) and in situ fourier transform Infrared Spectroscopy using pyridine as probe molecule (PyFTIR). The adsorption and catalytic transformation behaviors of sulfides on Y zeolites modified by rare ions were studied by in situ fourier transform Infrared Spectroscopy (in situ FTIR) technology using thiophene andthiophane as the probe molecules, respectively. The results indicated that thiophene molecules protonated upon the strong Brnsted acid sites of the zeolites at room temperature, then protonated products could further oligomerize. The synergy between L acid sites (included Ce species andnonframework aluminum species) and Brnsted (B) acid sites was favorable to oligomerization reaction of Thiophene, however, there were no reactions of thiophane over NaY, HY and REY. 

The physical and chemical properties of NaY zeolites and liquid phase cerium ion exchanged Y zeolites (LCeY) were characterized by XRD, N ₂ adsorption, NH3TPD, and insitu PyFTIR. The adsorption behavior of thiophene on NaY and LCeY zeolites was studied by using frequency response (FR) technique and intelligent gravimetric analyzer (IGA), and the different adsorption models of thiophene on Y zeolites modified by rare earth metal were investigated simultaneously. The results indicate that different mass transfer processes in the micropores of these zeolites can be validly identified by FR technique. The adsorption behavior of thiophene on NaY zeolites is relatively simple. Two mass transfer processes can be measured, containing channel adsorption and π electron interaction. While, the adsorption behavior of thiophene on LCeY zeolites is relatively complex. Except for two adsorption processes of adsorption in micropores and "SM" adsorption, complex catalytic reaction processes is also detected in LCeY zeolites under the condition of high temperature.

The ZSM5/KL composite zeolite, using ZSM5 as base material, was synthesized by twostep crystallization. The morphology of shell was controlled by regulating the series, temperature and time of crystallization. These samples were characterized by XRD, Nitrogen adsorptiondesorption and SEM, respectively, and evaluated by the npentane aromatization. The results show that different ways of crystallization has great effect on composite zeolite morphology. Compared with singlestep crystallization method, the twostep crystallization can effectively control the grain growth of shell phase L nanocrystals on the ZSM5 surface, and promote the formation of coreshell structure composite zeolite. Reaction experiment shows that the coreshell composite zeolite has better performance of aromatization than epitaxial crystal type composite zeolite.

TiO ₂MCM41mesoporous molecular sieve（n(Si)/n(Ti)=5）was synthesized by heating reflux method, using titanium tetrabutoxide as the Ti source,MCM41 as the carrier. The samples were investigated by means of XRD,FTIR and N ₂ adsorption/desorption. The static and dynamic desulfurization experiment was carried out using fluid catalytic cracking (FCC) fuel oils. Properties of selective adsorptive desulfurization of FCC gasoline on the adsorbents have been investigated in this paper by a fixedbed adsorption experiment and a GCSCD technique. It was indicated thatthe titania homodisperses in the modified MCM41,titania connected with the pendant OH groups of MCM41 via Si—O—Ti bonds. After the load of TiO ₂,the properties of adsorptive desulfurization on the adsorbents weresignificantly improved. The removal selectivities of the sulfur compounds in the gasoline changed slightly before and after the load of TiO ₂,while the poor removal selectivities of benzothiophene, 2/3methylthiophene, 2,3dimethylthiophene,2,4dimethylthiophene and 2, 5dimethylthiophene on MCM41 and TiO ₂MCM41 were the same.

Acidity and accessibility of LNiY were characterized by in situ FTIR spectroscopy with pyridine (Py), 2,6dimethylpyridine (DTPy) and 2,6ditertbutylpyridine (DTBPy) as the probing molecules, and the texture properties were characterized by N2 adsorption method. The textual property results indicate thatmesoporous defect positions exist in the prepared LNiY zeolites.The in situ FTIR results imply that hydroxyl are strong Brnsted acid in supercages of the LNiY zeolites. The accessibility of the Brnstedacid sites is different, and the ones in the defect positions show the more excellent accessibility. 

Surface acidities of the Y zeolites(NaY、HY、LCeY) were characterized by insitu PyFTIR and NH3TPD methods. The adsorption and catalytic transformation behaviors of thiophene on Y zeolites were studied by insitu FTIR technique. The results indicate that Brnsted (B) acid sites of Y zeolites play an important role in the progress of protonation and oligomerization. The order of catalytic properties of Y zeolites is LCeY > HY, which can be attributed to the concentration and strength of the surface acidities and the synergy between rareearth ions species and Brnsted (B) acid sites.

HY/MCM41 mesomicroporous composite materials composed of a core of HY zeolite and a thin layer of MCM41 have been synthesized by the overgrown crystallization. The samples were characterized by means of Xray diffraction (XRD), N2 adsorptiondesorption, scanning electron microscope (SEM), transmission electron microscope (TEM), Pyridine in situ infrared (PyIR) and Intelligent Gravimetric Analyzer (IGA) instruments. It was found that the composite material exhibited both properties of mesoporous MCM41 and microporous HYzeolite sieves. Adsorptive desulfurization performances of Ce ion supported over the synthesized composites as a sulfur adsorbent were evaluated. It was found that when the adsorbent was prepared by a solidstate grinding method with sulfur capacity of 1.81 mg/g can be obtained. While for the liquid ion exchange method, only 1.32 mg/g sulfur capacity can be reached. Through the batch methods it is found that for the former modified adsorbents the desulfurization degree can be reached to 90.6% while the latter only 81.2%. It also can be found that the Brnsted (B) acid of the adsorbent inhibited the adsorption desulfurization whereas the Lewis (L) acid, especially weak L acid, had a positive effecton adsorption desulfurization.

The CuHY zeolites adsorbents with different Cu loadings were prepared via impregnation method. The crystal structure of the adsorbent was characterized by XRD, and the surface acidity was measured by PyFTIR technique. The adsorption desulfurization performance was evaluated using fixed bed method with a WK2D micro coulometer analyzer. The results show that the adsorbents have the best adsorption desulfurization ability when the copper loading is 4%. The adsorption desulfurization performance becomes better with the decrease of the ratio of B acid amount and L acid amount. However, the adsorption desulfurization ability reduces severely, when copper loading is too large which results the surface copper oxide species, even though there is no B acidic sites existing on the surface of the adsorbent.

CeY zeolites were prepared by liquid phase ion exchange (LPIE) and solid state ion exchange (SSIE). The adsorbents were characterized by means of XRD,N ₂ physisorption,ICP and the total surface acidity of the adsorbents was monitored by NH ₃TPD and in situ FTIR spectroscopy using pyridine as a probe. Properties of selective adsorptive desulfurization of HDS gasolines on the adsorbents have been investigated in this paper by using a fixedbed adsorber and a GCSCD technique. The adsorption capacity was found to follow the order of SCeY＞LCeY＞NaY＞HY. After LPIE and SSIE, and CeY zeolites had different surface acidity from NaY and HY, which greatly affected the adsorption desulfurization process. Additionally, Brnsted (B) acid sites was thought toresult in catalytic reaction of thiophene.

Sample of CuY/Beta was prepared by modifying a NaY/Beta composite zeolite with a liquid ionexchange method and characterized by means of Xray diffraction(XRD), N ₂ adsorption and pyridine infrared spectroscopy(PyFTIR). Desulfurization performance of CuY/Beta for fluid catalytic cracking (FCC) and hydrodesulfurization gasoline were evaluated by a fixedbed and the intermittent static methods. The results show that the surface Lewis (L) acidity quantity of CuY/Beta adsorbent increased greatly，but its strength decreased, with respect to CuY adsorbents witch was prepared by liquid ion exchange method by our lab. CuY/Beta adsorbents for two kinds of fuel oils show greater performance of desulfurization than NaY/Beta and CuY adsorbents.

The adsorptiondesorption isotherms of thiophene and benzene in the NiY and NiY/Beta zeolites, prepared by liquid phase ion exchange, have been investigated by an intelligent gravimetric analyzer (IGA) and the diffusion coefficients were also calculated. Properties of selective adsorptive desulfurization of FCC gasoline on the zeolites were evaluated by a fixedbed adsorption experiment. The results show that the NiY/Beta zeolites remain the microporous structure. The saturated adsorption amount of thiophene is larger than that of benzene and so it is to the diffusion coefficients. The better diffusivity of thiophene inhibits the adsorption of benzene, resulting in the absorption desulfurization capability of the NiY/Beta zeolites improved.