Yellow Phosphoric Tail Transform The System Of Methanol Synthesis Gas Pilot And A New Catalyst Research

Yellow phosphorus is the most important product. The off-gas containing CO of high concentraion, produced in the process of yellow phosphorus, is a potential material gas for C1 chemical industry. The yellow phosphorus off-gas has not been utilized enough, because absence of purificating technologies for impurities such as phosphorus, sulphide, arsenide and fluoride. This result made serious waste of resources and environmental pollution.Recently, the purificating technologies were broken through evidently. It is possible to produce Cl chemical products using purificated yellow phosphorus off-gas as material. Based on the developed purificating technologies for yellow phosphorus off-gas, shift for high concentration CO would be developed to directly produce methanol syngas with appropriate ratio of H2/CO. The shift of low concentration CO is mature technic, but it's just the opposite, shift of high concentration CO is not.In order to prepare the synthesis gas for methanol from purified yellow phosphorus off-gas by water-gas shift reaction, the thermodynamics, hydrostatic, dynamic parameters was calculated, and the teactor was design. By pilot-scale research, the effect of using type B112 shift catalyst in synthesis gas for methanol by partial shift of purified yellow phosphorus off-gas was reviewed. The PILCs and LDHs using for shift of high concentration CO were prefabricated. The basal characters were studied by XRD, BET, EA, SEM and TG-DTA. The activity, selectivity, mithridatism, and best using condition were studied by CO water-gas shift reaction. The intrinsic kinetics and macrokinetics equations were studied by intrinsic kinetics and macrokinetics experiment. The mechanism of reaction was studied by TPD and TPR.The main original conclusions of this work are as follows:(1) Pilot-scale research:The preparation of synthesis gas for methanol by the partial shift of purified yellow phosphorus off-gas was successfully performed on a pilot-scale moderate shift installation. The calculated results showed that the superfluous reaction heat can be removed by adopting of the circular mode of gas-feeding and consequentially the temperature can be kept at the active temperature of shift catalyst. The experimental experiment indicated the choice indirect heat transfer and the direct heat transfer unified the way was feasible. The preparation of synthesis gas for methanol by the partial shift of purified yellow phosphorus off-gas was successfully performed on a pilot-scale moderate temperature shift installation. It was proved that the circular heating method by using burning gas of purified yellow phosphorus off gas was feasible for the heating and deoxidizing of the shift catalyst. The catalyst should be filled to two rather than three layers. The synthesis gas can meet the demand of the ratio of H2/CO for methanol synthesis under the technical conditions. The average temperature of catalyst bed would rise with increasing of inlet temperature of catalyst bed, steam flow and material gas flow. The B112-shift catalyst for the synthesis gas for methanol by partial shift of purified yellow phosphorus off-gas could not be prolonged presence to maintain a stable rate of transformation; bed temperature could not be maintained in the issue, so we must develop new for the comprehensive utilization yellow phosphorus exhaust bears the highly concentrated transformation catalyst.(2) Self-made Catalyst:Got catalytic performance and conditions of using inorganic pillared montmorillonite for high concentration CO shift. Montmorillonite pillared by mixing Fe, Fe-Cr, Al-Fe and Cu-Al complexes was investigated for their catalytic activities for water gas shift reaction (WGSR) and was characterized by XRD, BET, TG/DTA, SEM and elemental analysis. The Fe-PILC, the Fe-Al-PILC the Fe-Cr-PILC and Cu-Al-PILC all can be used for water gas shift catalysts. Using Fe-PILC, the Fe-Al-PILC and the Fe-Cr-PILC, it was found that the most suitable temperature was 330℃-400℃, 330℃-400℃,330℃-450℃and 230℃-380℃, respectively. When the ratio of water and gas was 1-6, shift for high concentration CO would be carried. Compared with the traditional shift catalyst, in the same shift condition, we can use the PILC catalysts to substitute. Using PILCs catalysts can accurately control the constitution of synthesis gas over changing shift rate. The selectivity of Fe-PILCs was very good. They could not be overly deocidized when the time was 400min. Fe-PILCs could not be poisoning, when the concentration of H2S was low of 400mg/m3, and PH3 was low of 200mg/m3.(3) Mechanism research:①Got intrinsic kinetics and macrokinetics experiments of using inorganic pillared montmorillonite for high concentration CO shift. The sequential estimation showed that the PILCs accord with simplified power exponent model. The intrinsic kinetics equations were studied by intrinsic kinetics. Scope of application was:1 atm total pressure,653K-693K (Cu-PILC 573K-613K),CO>85%. The macrokinetics equations were studied by macrokinetics experiment. Scope of application was:1 atm total pressure,653K-693K (Cu-PILC 573K-613K),CO>85%. Results from parameter estimation showed high confidence level of the two kinds of kinetic equations, In same condition, reaction rates of intrinsic and macroscopic were equivalent. This showed that the reaction was controlled by chemistry reaction.②Got shift reaction mechanism of using inorganic pillared montmorillonite for high concentration CO shift.The active material for the Fe-PILCs was inter-Fe, and the active material for the Cu-PILC was inter-Cu. In the design temperature range of deoxidized process, catalysts occurred deoxidized. The active component turned into Fe3O4 and Cu2O. Catalysts had higher dispersion. Additional Cr was conducive to have a porous structure of catalysts; in Fe-PILCs catalyst Fe was not entirely content with the increased activity. As a result of the special structure of PILCs, the catalysts had a higher dispersion of catalytic active sites. After TPR the removal of interlayer water, the active center to form a uniform oxide dispersed in the catalyst layer, the layer spacing in between 1.5-2.0 nm. Fe-PILCs and Cu-PILC were in line with the carboxyl mechanism.