The sphere active carbon is a kind of new upscale product that receives people’s attention more and more. It has been attached many merits as a new type active carbon with the good sphere activity, the even loading density, the big surface area and the high intensity, ets.Sphere carbonized resin supported nickel and transition metal was prepared by the carbonization and the reduced process by H-2 gas flow. D152 large pore cation exchange resin was the carrier. Nickel was the active constituent. Transition metal was the assistant. The results showed us that the key factors in preparation of sphere carbonized resin supported metal catalyst were metallic ion exchange, carbonization temperature and reduced time of active constituent. Meanwhile, Carbonizing process of resin was analyzed by DSC, obtaining the best carbonization temperature. The production rate of 2-propanol dehydrogenation as a simulation reaction was used to determine reduced time of active constituent. Its experimental result were given as follows:carbonization temperature was 773K, carbonization time was 30min, reduction process by H2 gas flow was 70min.In order to inspect the reaction condition of nickel supported on the resin, this article was used the matlab software programming computation, obtaining the distribution curve of nickel – ammonia compound under different pH, thus further explained that the nickel ion formed the nickel – ammonia compound under different pH, and provided the theory basis for ion exchange.This thesis dealed with the study on the 2-propanol dehydrogenation and soybean oil hydrogenation reaction using nickel or nickel-cerium supported on carbonized resin as the catalyst to evaluate catalyst activity in details.Effects of reaction temperature, pressure, time on the activity of catalyst, different atom ratio supported on the catalyst, catalyst dosage and stability were investigated. The conditions on the 2-propanol dehydrogenation and soybean oil hydrogenation reaction had been determined.（1）The preparation parameters of the 2-propanol dehydrogenation using nickel supported on carbonized resin as a catalyst were obtained as follows: the dosage of 2-propanol was 100mL, the capacity of nickel supported on catalyst was 35.2wt%, the catalyst was 1.5g, the reaction temperature was 773K, and the reaction time was 1h, the yields of acetone could be up to 12.5%, the selectivity of acetone was 100%.（2） The preparation parameters of the soybean oil hydrogenation using nickel supported on carbonized resin as a catalyst were obtained as follows : the dosage of soybean oil was 100g, the capacity of nickel on catalyst was 21wt%, the catalyst was 1.5g, the reaction temperature was 773K, the reaction time was 2h, and the reaction pressure was 1.5MPa, soybean oil’s iodine value was decreased from 130.0 to 81.7.（3） The preparation parameters of soybean oil hydrogenation using nickel-cerium supported on carbonized resin as a catalyst were obtained as follows : the dosage of soybean oil was 100g, the capacity of nickel on catalyst was 21wt%, The atomic ratio of nickel and cerium was 5:1,the catalyst was 0.5g, the reaction temperature was 773K, the reaction time was 1h, and reaction pressure was 1.5MPa, soybean oil iodine value was decreased from 130.0 to 18.8. Different transition metal were used as the catalyst’s assistant and their active influence rule were obtained: Ce >La> Cr> Ag> Cu>Fe> Co>Cd>Zn.
Post about "Catalyst"
Synthesis of organized mesoporous alumina by inorganic aluminum salts and the application as sorbent in the adsorption of Cr3+ have been studied in detail. Organized mesoporous alumina was prepared by aluminum nitrate. The structure was characterized by several measuring technology. The influence of reaction conditions on structure of organized mesoporous alumina has been investigated. Using the organized mesoporous alumina as sorbent, the adsorption abilities of Cr3+ in different conditions were studied. Cu-containing catalyst on synthesized mesoporous alumina has been prepared by different method. Several techniques weres used to detect the structural characterization of catalyst. The performance of Cu-containing catalyst using in the H2O2 catalytic oxidation has been tested.Organized mesoporous alumina was synthesized by precipitation of aluminum nitrate. PEG 1540 was used as template, monoamonium phosphate and carbamide as assistant solvent. Specific surface area reaches 220-300m2/g. Total pore volume is 0.3-0.5cm3/g, pore diameter up to 2.8-5nm. The method overcomes the shortcut of expensive template and alumina source in the synthesis of mesoporous alumina for its simple technology and inexpensive cost. PEG1540 can make the direct-piling and support function in the formation of mesopore. The pH value of reaction terminal and the change of cleaning produce important influence on mesoporous structure.Using the organized mesoporous alumina as sorbent, the adsorption ability of Cr3+ was studied. The value of pH, the concentration of Cr3+ and the temperature can affect the adsorption performance. The perfect adsorption condition were given and the adsorbed process could be described by Freundlich equation.Cu-containing catalysts were synthesis by overloading impregnation, equivalent-volume impregnation method and in-suit method. The catalytic performance was studied through the application in H2O2 catalytic oxidation. The different impregnation method has important influence on the structure, interaction between metal and carrier, catalysis of Cu-containing catalyst supported on mesoporous alumina.
Catalysis of the Metal Substituted Phosphyotungstic Heteropoly Compounds for Oxidative Desulphurization of Fuel Oil
With the development of economy, the demand of liquid fuels is increasing. SOx that generated in combustion of fuels results in acid rain. Moreover it poisons converted catalysts, which cause the environmental pollution. Therefore, in order to enhance the control of environmental pollution, more stringent standard for sulfur content in liquid fuels has been proposed in many countries. Because of high temperature, high hydrogen pressure, highly active catalyst and longer reaction time, the traditional hydrodesulfurization is facing the great challenges. Since the limitation above, it takes a great significance both on theoretical and practical on non-hydrodesulfurization. Above them the non-hydrodesulfurization, oxidative desulfurization is considered one of promising processes for its mild reaction condition, simple equipment design, and highly efficiency. Meanwhile, because of the simple preparation, the high catalytic activity and the environmental protection, heteropoly compound is becoming the hotspot of research and widely used in the area of catalysis.The different metal substituted phosphyotungstic heteropoly compounds were prepared by one-step method with sodium tungstate, disodium hydrogen phosphate, quaternary ammonium salt and then were applied to the experiments of fuel oil oxidative desulfurization by using hydrogen peroxide as oxidant. Copper substituted phosphyotungstic heteropoly compound showed a relatively high catalytic activity. The structures of the compounds were characterized by IR and UV. Reaction conditions on the desulphurization of fuel oil were investigated. The results showed that taking [（C4H9）4N]4H[PW11CuO39] as catalyst, under the conditions of the dosage of catalyst 4.0% （the mass ratio of catalyst to model oil）, the molar ratio of oxidant to oil 2.5 （the molar ratio of effective oxygen in oxidant to the sulfur of oil）, the reaction temperature 60℃and reaction time 2h, the sulfur removal rate of model oil 1（A simulated oil 1 consists of model sulfur compound of thiophene and n-octane as solvent） reached 96.78%, under the conditions of the dosage of catalyst 10%, the molar ratio of oxidant to oil 27.5, the reaction temperature 70℃and reaction time 2.5h, the sulfur removal rate of FCC diesel was 60.85%; taking [(C16H33)N （CH3）3]4H[PW11CuO39] as catalyst, under the conditions of the dosage of catalyst 4.0%, the molar ratio of oxidant to oil 4.5, the reaction temperature 70℃and reaction time 2h, the sulfur removal rate of model oil 2（A simulated oil 2 consists of model sulfur compound of benzothiophene and n-octane as solvent） reached 98.39%, under the conditions of the dosage of catalyst 3.0%, the molar ratio of oxidant to oil 22, the reaction temperature 80℃and reaction time 2.5h, the sulfur removal rate of FCC diesel was 65.24%. The outcome realizes that the metal ions substituted phosphyotungstic heteropoly compounds we synthesized show relatively high catalytic activity.
The kerosene has been used as an important fuel in the engine. In recent years, with the further research on kerosene, the hydrocarbon group of the kerosene is found cracking at a high temperature, and the coke formed will plug the pipeline and affect the normal operation of the engine.Therefore, higher thermal stability of the kerosne is requested in all countries. At this case, the reason for the coke formed below the 640K lies in its internal dissolved oxygen in the fuel, which plays a lead role in the reaction as the free radicals.But if we can decrease the concentration of the dissolved oxygen down to 1 ppm, by which the kerosene will maintain a relatively high thermal stability below 640K.In this article, the way of removing dissolved oxygen in the kerosen is disscused. We take three methods including the chemical, zeolite adsorption and Nitrogen Filling,and compare each other. The results show that Nitrogen Filling method is the most appropriate method nowadays. At the same time, we also discusses the use of chemicals analysis as a new and high-precision method for detecting the dissolved oxygen which can replace the analyzer for dissolving oxygen.kerosene of steam reforming is a strong endothermic reaction. On the one hand, the reaction can decrease the temperature in the system of the engine which reduces the damage to the engine. On the other hand, the reaction can produce high-efficiency, low-pollution hydrogen fuel which can result in higher efficiency, if it is applied in the engine. About the latent heat of kerosene, we discuss its hydrogen production efficiency in this paper. Because of the high thermal efficiency, storage and transportation convenience, it is used as a hydrogen material which has huge potential commercial value. Light hydrocarbon of steam reforming into hydrogen is the most economical, the most important industrial line.In this paper, the catalyst for steaming reforming into hydrogen is developed, supported by La- Ni-K/cordierite as the main body. We discusse the different conditions in the stability of catalyst and the efficiency of hydrogen production. The catalysts obtained under different calcination temperatures and different reaction temperatures are characterized by TG-DTG-SDTA, XRD and SEM techniques, respectively, and are tested in the fixed bed reactor. The experimental results indicate the catalyst, supported the promoter 5wt. %K2O, 25m. %NiO and 10wt. %La2O3, has excellent activity, stability and resistance to carbon deposition under 773 K of reaction temperature, 873 K of calcination temperature, 3 h-1 of space velocity and S/C=3.5.The catalyst has a good prospect in application.
Study on Modification of Co-Mo/γ-Al2O3 Catalysts and Selective Hydrodesulphurization for FCC Gasoline
In this paper, the CoMo/γ-Al2O3 catalysts modified with the transition metal additives such as Zn, Cu, Fe, Mn were prepared. The influence of additive types and the modifying methods on physicochemical properties of the catalyst and selectivity of the desulfurization was studied. The physicochemical properties of catalyst have characterized by XRD, BET, Py-FTIR, H2-TPR, NH3-TPD and HRTEM techniques.Experimental results show that the CoMoZn/γ-Al2O3 catalysts prepared by co-impregnation method have better activity and selectivity for hydrodesulfurization of FCC gasoline. The optimized preparation condition is that the content of CoO plus MoO3 is 12.0 wt%, the atomic ratio of Zn/Mo is 1.0. XRD and HRTEM verify that Zn added in the catalyst promotes the dispersion of active metals on the surface of supports, therefore, the nanoparticle of MoS2 has a smaller size and slab lengh, so that the better HDS selectivity is reached. The passivation of CoMoZn/γ-Al2O3 catalysts with basic nitrogen compound quinoline is investigated to improve the activity and selectivity for hydrodesulfurization of FCC gasoline. It is verified from experimentals that the selective adsorption of quinoline on the surface of the catalyst may modify the ratio of active sites for desulfurization/hydrogenation, so that the selectivity for desulfurization is improved. Experimental results show that the adsorption of quinoline has little impact on activity for desulfurization, however, it inhibits the activity for hydrogenation of olefins. When HDS percentage reaches 82%-90%, hydrogenation percentage of olefin （HDO） is only 17.4%～21%, the octane number loss of the FCC gasoline is 1 to 2.In order to verify the practical activity, selectivity, stability as well as adaptability to different feedstocks and processing conditions of the catalyst for hydrodesulfurization of FCC gasoline furthermore, the CoMoZn/γ-Al2O3 catalysts are tested on a pilot flow hydrogenation reactor with catalyst capacity of 100ml. The results indicate that the catalyst has high activity for desulfurization, HDS percentage could reach over 85% at conditions of 280°C, 1.6MPa, hydrogen-to-oil ratio of 300:1 and LHSV of 4h-1. For HDS of Shengli and Shenghua FCC gasoline, the low sulfur gasoline with 150μg/g S which is accordant to EU III specification is reached. For HDS of Dagang FCC gasoline, the low sulfur gasoline with 50μg/g S which is accordant to EU IV specification is reached.In order to verify the feasibility of TMD process, the Co-Mo-Zn/γ-Al2O3 catalyst was applied to couple with the aromatization catalyst to processing Dalian FCC gasoline with high olefin and low aromatic contents. This work is finished on a pilot flow unit with three 100ml fixed bed reactors located in the Catalyst Factory of Fushun Petrochemical Company. Experiments show that it can reduce the total sulfur in gasoline feedstocks from 195.7μg/g to 72.1μg/g with RON loss 0.4 units. Therefore, the coupling of the selective HDS catalyst with the aromatization catalyst has better performance in processing high olefin gasoline to meet the requirement of removing sulfur and reducing olefin with little RON loss, so that TMD process has a bright prospect for commercialization.
At present, zincum acetate-active carbon catalyst is mostly produced by the technology which was developed between the 1970s and 1980s in domestic vinyl acetate plant.The capacity is 1m3 in batch processing.The active component can’t be distributed uniformly because of high bed; The operating condition is very bad because of the positive pressure in fluidized bed;The waste water is large because of wet type dust collector.The product quality is fluctuation because of little local control and low automatic level.So the old technology can’t meet the requirements of technology advancement and increasing production scale. Thus it is urgent to investigate a preparation technology and equipment for zincum acetate-active carbon catalyst production, and develop a catalyst preparation technology of stable quality, good environment, and high automatic level in order to meet the large scale ethylene apparatus’s needs and provide technological reserve for PolyVinyl Alcohol (PVA) industry.This research is based on the zincum acetate-active carbon catalyst device with batch processing load of 3m3 active carbon of 50kt/a PVA and auxiliary project. By digestion and technical innovation, a technical route has been proposed which includes optimal zincum acetate solution preparation, solution conveying by pipe and applying auto-cleaning technology, spraying, absorption and drying integration by fluidized bed and tail gas purification. A well-structured fluidized bed of spray, absorption and drying integration is designed with batch processing load of 3m3 active carbon,which is simulated by using Fluent software. The simulating results show that the design of air distribution plate and arrangement of internals parts are both satisfying.Through investigation and analysis, the process parameters and the technological equipment structure are optimized, zincum acetate-active carbon catalyst process technology and equipment package is developed and designed. The quality of catalyst can meet the customer’s needs.The development and application of this packaged technology has built a technical platform for its promotion, larger scale catalyst preparation and development in PVA plant.
As a kind of polynuclear inorganic macromolecule compound containing oxo bridge,heterpoly acid were the oxygenic polyatomic acid that coordinated with center atom（P、Si、As、Ge etc.） and coordinating atom（Mo、V、W etc.）.There are five species such as Keggin、Dawson、Anderson、Waugh、Silverton in heterpoly acid assorting by structure of anions.The heterpoly acids have such unique cage structures that are similar with liquid phase.So catalysis can carry from not only the teeth outwards but also in the body and heterpoly acid have good catalyzed activity and selectivity.The heterpoly acid can catalyst as acid catalysis and oxidization.Furthermore heterpoly acid are provided with photoelectricity catalysis and polymerization retardor.It is one kind of ideal catalyst therefore.The three kind of phosphotungstate were prepared by different of diphenylamine,ammonium oxalate and 8-hydroxyquinoline with phosphotungstic acid（HPA）via double reaction.IR and UV analysis indicated that the compounds kept entire Keggin structure,then the coordination of N-H have strengthened the M-Ob-M bond and M-Oc-M bond;TG analysis indicated that the introduction of N element have improved the stability of water of hydration;XRD analysis indicated that the conclusion is corrected.It is the esterification of acetic acid and n-octanol as probe reaction to test the catalysis of phosphotungstate-diphenylamine and ammonium oxalate-phosphotungstate.The result indicated that the hosphotungstate had the best catalysis when the reaction temperature is 110℃,the molar ratio of octanol to acetic acid is 1:1.4,reaction time is 3.5 hours,the amount of catalyst is 0.4g,the yield of octyl acetate is over 90%.the catalyst may reuse and did not cause second pollution to the environment.It has studied electrochemistry behavior of[（C6H5）2NH2]3[PW12O40] 4H2/PVA laminated film by cyclic voltammetric measurernents（CV）.The result indicated that the constitutive property is stable,it has the good oxidized reducibility and the obvious electrocatalysis to ClO4-.We evaluate photocatalysis activity by using the ammonium oxalate- phosphotungstate to degradation Rodamine B.The result show:the phosphotungstate have good photocatalysis activity and degrade Rodamine B obviously.The catalyst can use repetitively after simple treatment.So the catalyst may use widely in practice.It is the esterification of acetic acid and n-butanol as probe reaction to test the catalysis of phosphotungstate-8-hydroxyquinoline.The result indicated that the phosphotungstate had the best catalysis when the reaction temperature is 98℃,the molar ratio of butanol to acetic acid is 1:1.4,reaction time is 3.5 hours,the amount of catalyst is 0.4g,the yield of butanol acetate is 90.6%.the phosphotungstate may use repetitive and have no pollution to environment.That’s good for industrialization.
Methyl methacrylate (MMA) is an important monomer in the preparation of acrylic resins. At present, MMA is mainly produced by the method of acetone-cyanohydrins(ACH). The raw material are acetone and hydrocyanic acid which is seriously poisonous substance, in the reaction process, high corrosive sulphuric acid is also used, and the by-product of the ammonium hydrogen sulfate is difficult to deal with. The atom utilization of the route is only 47%. The selective oxidation of isobutylene to methacrolein (MAL) is a critical step for clean production of methyl methacrylate (MMA) from isobutylene instead of highly toxic hydrocyanic acid.The main contents and results of this work were as follows:(1) The catalysts were prepared by the method of the co-precipitation. The influence of the preparation conditions such as:,,addition sequence of solutions,the rate of whipped, calcination temperature, component and the ratio of the elements in catalysts on catalytic performance for selective oxidation of isobutylene to methacrolein were studied. The physico-chemical properties of the catalysts were characterized by XRD、SEM、IR and so on. The optimum preparation conditions for catalysts with the component of Mo12Bi1.6Fe1Co8Ce0.4Cs0.4K0.2Sb0.48Ni0.12Ox were that: solution B was added into solution A , the rate of whipped is 80 rev/min, calcination temperature=500℃.(2) Some important reaction parameters for selective oxidation of isobutylene to MAL, such as concentration of isobutylene, reaction temperature, space velocity and the vapor were systematically investigated. The based kinetics equation was obtained. Reaction optimized conditions were optimized. At 380℃, 4500h-1 and volume concentration of isobutylene 6%, conversion of isobutylene was 97.31%,and selectivity to MAL was 92.34%.
With economic development and the fast process of urbanization, the total of municipal solid waste(MSW) rapidly increasing which pose a great threat to the environment. It is proved that the pyrolysis technology is one of the most important MSW disposal ethnics with little secondary pollution, quite innocuity and high reusability. At the same time refuse contains large numbers of hydrogen resources which makes the possibility of hydrogen production. In order to enhance production of the gas and gaseous hydrogen production rate, my dissertation is on the basis of using catalysts to further reform the pyrolysis product to realize the purpose of reusing the resources & economic cycle.To simulate the pyrolysis characteristics of industrial facility, an externally heated catalytic pyrosis furnace was built. Experiments were carried out using MSW as the testing materials. Mainly do the study on the dolomite, nickel-based, rare earth these three types of catalyst to study the gas properties & hydrogen production. Under each catalyst condition, the influences of main parameters such as pyrolysis temperature (750℃～900℃), the feed speed of spiral feeder (25 r/min to～40 r/min), the proportion of catalyst powder mixed materials (0～10%) were experimentally investigated.The results showed that adding the catalyst can significantly increase the gas production and gaseous hydrogen production rate, the best parameters for hydrogen production of each catalyst are also given: Dolomite as a catalyst, the best parameters for hydrogen production are: Pyrolysis temperature is 900℃, Speed is 30r/min, Dolomite powder by 10% proportion of materials, H2 production rate is 40.9% and the gas production is 0.89L/g under that condition; Nano-NiO /γ-Al2O3 as a catalyst, the best parameters for hydrogen production are: Pyrolysis temperature is 900℃, Speed is 30r/min, Nano- NiO powder by 5% proportion of materials, H2 production rate is 56.8% and the gas production is 1.25L/g under that condition;Nano- NiO / red mud as a catalyst, the best parameters for hydrogen production are: Pyrolysis temperature is 900℃, Speed is 30r/min,Nano- NiO powder by 5% proportion of materials, H2 production rate is 44.6% and the gas production is 1.12L/g under that condition;Rare-earth as a catalyst, the best parameters for hydrogen production are: Pyrolysis temperature is 750℃, Speed is 30r/min, catalyst powder by 5% proportion of materials, H2 production rate is 31.4% and the gas production is 0.85L/g under that condition.In 800℃,rare-earth catalyst had signs of inactivation. For other catalysts, under the same experimental conditions, relative to the non-use of catalyst, the rank of increasing for gas production and hydrogen production rate is: Nano NiO /γ-Al2O3> Nano NiO / red mud> dolomite.under the experimental conditions, the catalyst for all kinds of tar removal followed by: nano-NiO /γ-Al2O3> rare-earth > nano-NiO / red mud> dolomite, the catalyst for all kinds of catalytic cracking effects for semi-coke followed by: nano-NiO /γ-Al2O3> nano-NiO / red mud> rare-earth > dolomite.
The technology of the hydrocracking is one of the main way to process heavy oil to light oil.It is the only way of producing cleanness fuel for automobile and high quality chemical raw material while hydrocracking the feeds.It is the most efficient way to utilize crude oil.It has extensive adaptability to many feeds,it can produce many products with high quality,and the yield of liquid is high, so this technology is becoming of one link between the refinery and the chemical plant.The refineries and the research institutes pay more attention on it. Hydrocracking catalyst is the core of the technology,one of the most important way is to research out a kind of catalyst with high active and selectivity to Middle Distillate.It is important to set up a balance between the selectivity of middle distillate and the activity. It is a good catalyst which has high selectivity to Middle Distillate,and has high activity at the same time. Now Hydrocracking catalyst is developing quickly by treating the molecular sieve,optimizing the produsing technology of the catalyst , improving the disperse of the hydrogenation and using many kinds of new catalysis materials.Novel hydrocracking catalyst was developed for producing more middle distillate with two reactors in series process. Evaluation of catalytic performance of the hydrocracking catalyst was carried on a 200mL fixed-bed hydrogenation unit, the results showed that under the 75% conversion of >350℃feedstock distillate, C5+ liquid yield of the hydrocracking product can reach more than 98.2m%, 138～370℃diesel oil yield of hydrocracking product was 67.84m%, selectivity of middle distillate was 80.2%, the catalyst can meet the need of producing more middle distillate in the industrial unit, catalytic performance of the catalyst was better than reference catalyst.