Thermal Treatment for Decreasing the Acidity of Crude Oil

Highly acidic crude oil is thermally soaked to investigate how the temperature and time involved affect the removal of organic acid in feedstock. Experimental results indicate that thermal treatment is an effective approach to decreasing acidity and the acid removal rate reaches 80%. Temperature is one of the main factors that determine the acid removal reaction. When the temperature ranges from 420oC to 440oC, the acid removal rate increases with the rise of the reaction temperature, but the increase slows down gradually. At the reaction temperature below 440oC, the long reaction time favors the acid removal. The cracking and polymerization of hydrocarbon molecules take place so that the properties of the crude oil change at the same time when the highly acidic crude is thermally treated.

Kinetic Implication from Temperature Effect on Hydrogen Evolution Reaction at Ag Electrode

Hydrogen evolution reaction （HER） at polycrystalline silver electrode in 0.1 mol/L HClO4 solution is investigated by cyclic voltammetry in the temperature range of 278-333 K. We found that at electrode potential φa,app decreases with φ, while pre-exponential factor A remains nearly unchanged,which conforms well the prediction from Butler-Volmer equation. In contrast, with φ nega-tive shifts from the onset potential for HER to the potential of zero charge （PZC≈-0.4 V）, both Ea,app and A for HER increase （e.g., Ea,app increases from 24 kJ/mol to 32 kJ/mol）. The increase in Ea,app and A with negative shift in φ from -0.25 V to PZC is explained by the increases of both internal energy change and entropy change from reactants to the transition states, which is correlated with the change in the hydrogen bond network during HER. The positive entropy effects overcompensate the adverse effect from the increase in the activation energy, which leads to a net increase in HER current with the activation energy negative shift from the onset potential of HER to PZC. It is pointed out that entropy change may contribute greatly to the kinetics for electrode reaction which involves the transfer of electron and proton, such as HER.

Preparation of boric acid from low-grade ascharite and recovery of magnesium sulfate

Boric acid and kieserite were prepared from low-grade ascharite by sulfuric acid method.This method results in the recovery of 71.06%and 45.03%for boric acid and kieserite,respectively.Meanwhile,the boric acid was precipitated from the filtrate at low temperature and the solution was recycled without discharging waste liquid in the whole process.The influence of amount of sulfuric acid,mass fraction of sulfuric acid,reaction temperature and reaction time on the leaching rate of boric acid were studied. The results show that the leaching rate of boric acid reaches 93.80%under the following conditions:the amount of sulfuric acid is 85%of theoretical dosage;the mass fraction of sulfuric acid is 25%;reaction temperature is 95℃;and the reaction time is 100 min. Meanwhile,the effects of mass fraction of magnesium sulfate,crystallization temperature and crystallization time on the crystallization of kieserite were investigated and the optimal crystallization conditions are obtained:the mass fraction of magnesium sulfate is 28%;the crystallization temperature is 180℃and the crystallization time is 4h.

Application of Choline Chloride·xZnCl2 Ionic Liquids for Preparation of Biodiesel

The inexpensive and moisture-stable Lewis-acidic ionic liquids were prepared and applied for transesterification of soybean oil to biodiesel.The influences of molar ratio of methanol to soybean oil,reaction temperature and amount of ionic liquids were investigated.The transesterification of soybean oil to biodiesel catalyzed by choline chloride·xZnCl2 ionic liquids showed many advantages such as mild conditions and lower cost.On the other hand,the non-ideal yield and complicated separation between biodiesel and soybean oil were also investigated and analyzed.The improvement on the systems of choline chloride·xZnCl2 was proposed for further investigation.

Synthesis of Biodiesel Using ZrO_2 Polycrystalline Ceramic Foam Catalyst in a Tubular Reactor

With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.

The effect of operating conditions on acylation of 2-methylnaphthalene in a microchannel reactor

Acylation of 2-methylnaphthalene(2-MN) is a very important reaction in organic synthesis,and the effiency of the continuous reactor is more than one of the batch reactor.Considering that the Friedel–Crafts acylation is a rapid exothermic reaction,in this study,we perform the acylation of 2-MN in a stainless steel microchannel flow reactor,which is characterized by high mass and heat transfer rates.The effect of reactant ratio,mixing temperature,reaction temperature,and reaction time on product yield and selectivity were investigated.Under the optimal conditions,2-methyl-6-propionylnaphthalene(2,6-MPN) was obtained in 85.8% yield with 87.5% selectivity.Compared with the conventional batch system,the continuous flow microchannel reactor provides a more efficient method for the synthesis of 2,6-MPN.

The Shandong Shidao Bay 200 MW_e High-Temperature Gas-Cooled Reactor Pebble-Bed Module(HTR-PM) Demonstration Power Plant: An Engineering and Technological Innovation

In 2005, the US passed the Energy Policy Act of 2005 mandating the construction and operation of a high-temperature gas reactor （HTGR） by 2021. This law was passed after a multiyear study by national experts on what future nuclear technologies should be developed. As a result of the Act, the US Congress chose to develop the so-called Next-Generation Nuclear Plant, which was to be an HTGR designed to produce process heat for hydrogen production. Despite high hopes and expectations, the current status is that high temperature reactors have been relegated to completing research programs on advanced fuels, graphite and materials with no plans to build a demonstration plant as required by the US Con- gress in 2005. There are many reasons behind this diminution of HTGR development, including but not limited to insufficient government funding requirements for research, unrealistically high temperature requirements for the reactor, the delay in the need for a ＂hydrogen＂ economy, competition from light water small modular light water reactors, little utility interest in new technologies, very low natural gas prices in the US, and a challenging licensing process in the US for non-water reactors.

Investigation of Nitration Processes of iso-Octanol with Mixed Acid in a Microreactor

In this paper, the nitration characteristic of alcohols with mixed acid for the synthesis of energetic mate-rials in a stainless steel microreactor was investigated experimentally. The nitration of iso-octanol with HNO3-H2SO4 mixed acid was chosen as a typical model reaction which involved fast and strong exothermic liquid-liquid heterogeneous reaction process. The influences of mixed acid composition, flow rate, organic/aqueous flow ratio and reaction temperature have been investigated. The results indicated that the reaction could be con-ducted safely and stably in the microreactor at 25-40°C, which are enhanced compared to 15°C or below for safe operating conditions in the conventional reactors. Moreover, the 98.2% conversion of iso-octanol could be obtained and no by-products were detected in all cases.

Synthesis of Novel Ionic Liquid ([C_4 CNmim]^+ PF_6^-) and Application to Preparation of Polyketone

N-valeronitrile-N'-methylimidazolium hexafluorophosphate ([C 4 CNmim]+ PF 6),as a novel ionic liquid with polar nitrile functional group,was prepared.The structure of the ionic liquid was characterized by using IR and 1 H NMR.As a medium,the ionic liquid plays an important role in copolymerization of carbon monoxide (CO) with styrene (St).Some synthetic conditions were determined,including the usage of ionic liquid,palladium composite catalyst and methanol,CO pressure,reaction time and reaction temperature.The influence of these factors on catalytic activity was analyzed.The results show that the catalytic activity has reached 1 724.1 gStCO/(gPd·h) and the catalyst could be reused 5 times under the optimal condition:composite catalyst 0.015 mmol,ionic liquid 3 mL,methanol 0.75 mL,CO pressure 2MPa,reaction time 2 h and reaction temperature 70℃.This CO/St copolymerization within [C 4 CNmim]+ PF 6 system could facilitate ionic liquids with efficient and economical applications to polymeric materials.

Dissolution kinetics of aluminum and iron from coal mining waste by hydrochloric acid

The extrartion of aluminum from coal mining waste(CMW) is an important industrial process.The two major problems in applications are low aluminum dissolution efficiency and high iron content in the raw material,which affect the quantity and quality of products.To improve the aluminum recovery process,the leaching kinetics of CMW with hydrochloric acid was studied.A shrinking core model was used to investigate aluminum and iron dissolution kinetics.Based on the kinetic characteristics,a process for recovering aluminum was proposed and tested experimentally.It is found that the aluminum leaching reaction is controlled by surface reaction at low temperatures(40-80℃) and by diffusion process at higher temperatures(90-106℃).The iron dissolution process is dominated by surface reaction at 40-100℃.The results show that iron could be dissolved or separated by concentrated hydrochloric acid.Fine grinding will improve aluminum dissolution significantly.

Temperature Effect on Hydrogen Evolution Reaction at Au Electrode

The temperature dependence of hydrogen evolution reaction （HER） at a quasi-single crystalline gold electrode in both 0.1 mol/L HCl04 and 0.1 mol/L KOH solutions was investigated by cyclic voltammetry. HER current displays a clear increase with reaction overpotential （η） and temperature from 278-333 K. In 0.1 mol/L HClO4 the Tafel slopes are found to increases slightly with temperature from 118 mV/dec to 146 mV/dec, while in 0.1 mol/L KOH it is ca. 153±15 mV/dec without clear temperature-dependent trend. The apparent activation energy （Ea） for HER at equilibrium potential is ca. 48 and 34 kJ/mol in 0.1 mol/L HC104 and 0.1 mol/L KOH, respectively. In acid solution, Ea decreases with increase in η, from Ea-37 kJ/mol （η=0.2 V） to 30 kJ/mol （η=0.35 V）. In contrast, in 0.1 mol/L KOH, Ea does not show obvious change with U. The pre-exponential factor （A） in 0.1 mol/L HC104 is ca. 1 order higher than that in 0.1 mol/L KOH. Toward more negative potential, in 0.1 mol/L HC104 A changes little with potential, while in 0.1 mol/L KOH it displays a monotonic increase with U. The change trends of the potential-dependent kinetic parameters for HER at Au electrode in 0.1 mol/L HClO4 and that in 0.1 mol/L KOH are discussed.

Syngas Production from Crude Glycerol Using Pyrolysis

Glycerol pyrolysis is carried out in a fixed bed reactor filled with alumina oxide. The packing material diameter was examined according to each one, but in general it was varied between 0.1-5.0 mm. The reaction temperature was varied in the range of 700-900 ℃, the reaction time from 10 to 50 min and flow rate of carrier gas from 0 to 60 mL/min. The process parameters listed above （factors） were used to evaluate the syngas production yield （response）. Also, syngas properties such as composition and heat value were evaluated. The experiments were carried out according to a 23 factorial design plus three central points. At last, a technical-economical analysis is carried out to examine the feasibility of syngas production from glycerol pyrolysis considering not only feedstock, catalyst and energy required costs but also conventional procedures used nowadays to produce syngas such as water electrolysis and natural gas catalytic reform.

Et_3NHCl-AlCl_3 Ionic Liquids as Catalyst for Alkylation of Toluene with 2-Chloro-2-methylpropane

Alkylation of toluene With 2-chloro-2-methylpropane （t-Bu-C1） to synthesize para-tert-butyltoluene （PTBT） was carded out in the presence of triethylamine hydrochloride-aluminum chloride ionic liquids used as the catalyst. The ionic liquids were prepared with different molar ratios of Et3NHC1 to A1CI3, and the effect of the molar ratio between A1C13 and Et3NHC1, the reaction time, the reaction temperature, the ionic liquid dosage, as well as the molar ratio of toluene to chloro- 2-methylpropane on the alkylation reaction of toluene with chloro-2-methyl-propane was investigated. The test results showed that the acidic ionic liquids prepared with Et3NHC1 and A1C13 had good activity and selectivity for the alkylation reaction of toluene with alkyl chloride to produce PTBT. The optimal reaction conditions were specified at an A1C13 to Et3N- HCI ratio of 1.6, a reaction temperature of 20 ℃, a mass fraction of toluene to ionic liquid of 10%, and a chloro-2-methyl- propane to toluene molar ratio of 0.5. Under the suitable reaction conditions, a 98% conversion of chloro-2-methylpropane and an 82.5% selectivity of PTBT were obtained. Ionic liquids could be reused 5 times with its catalytic activity unchanged, and the regenerated ionic liquids can be recycled.

Research on Ethylene and Propylene Formation during Catalytic Pyrolysis of Methylcyclohexane

The influence of operating parameters and type of zeolite catalysts on formation of ethylene and propylene during catalytic pyrolysis of methylcyclohexane (MCH) was studied in a laboratory fixed fluidized bed reactor. The results indicated that higher reaction temperature and lower WHSV tended to produce more ethylene and propylene, among which the reaction temperature was an important factor influencing the ethylene formation. Compared with the FAU and BEA type zeolites, the MFI structured zeolite catalyst, thanks to more acid sites and smaller pore diameter of the catalyst, was conducive to the formation of ethylene and propylene. The protonation occurred on different C—C bonds and C—H bonds in the carbon chain of MCH led to different product slates, and the protonation on C—C bonds located at naphthenic ring was favorable to the formation of ethylene and propylene.

Promotional Effect of CoO(OH) on Selective Hydrogenation of Maleic Anhydride to γ-Butyrolactone over Supported Ruthenium Catalyst

A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, TGDTG and N2 adsorption techniques. The characterization tests revealed that the catalyst carrier was composed of monoclinic zirconia(m-ZrO2) and hydroxyl cobalt oxide(CoO(OH)). The hydrogenation results showed that the content of CoO(OH), the reaction temperature, the hydrogen pressure and the reaction time significantly affected the catalytic selectivity to GBL. The promotional effect of CoO(OH) was remarkable, which led to an obvious increase in GBL selectivity. An 100% MA conversion and 92.0% selectivity to GBL were achieved over the Ru/ZrO2-CoO(OH)(35%) catalyst in water solvent under the conditions involving a reaction temperature of 180 ℃, a hydrogen pressure of 3.0 MPa, and a reaction time of 6 h.

The extraction of potassium from K-feldspar ore by low temperature molten salt method

The low temperature molten salt method was used to extract potassium from K-feldspar ore, and some related factors including mass ratio between NaNO_3, NaOH, H_2O and K-feldspar ore, particle size of K-feldspar ore,reaction temperature and time were investigated, respectively. In addition, the optimum condition for this method was determined by a series of condition experiments. What was more, the K-feldspar ore and the leach residue after reaction based on the above optimum condition were analyzed by XRD, SEM and EDS,separately. The results of which indicated that the mechanism of extraction of potassium for this method was according to the ion exchange reaction between sodium ion and potassium ion, and the extraction ratio of potassium had an obvious improvement than that of traditional methods, which could reach up to 96.25%.Therefore, this method can be a feasible solution to extract potassium from K-feldspar ore for its low energy consumption and high efficiency.

Commercial Application of CPP for Producing Ethylene and Propylene from Heavy Oil Feed

A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene andpropylene from heavy oil feedstock has been developed. The catalyst CEP was specially designedfor this process, which has bi-functional catalytic activities for both carbonium ion reaction andfree radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trialshowed that the yield of ethylene and propylene was 20.37% and 18.23% respectively inmaximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylenewas 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene andpropylene.

Reduction smelting on bismuth oxide residue in FeO-SiO2-CaO ternary slag system

Reduction smelting of the bismuth oxide residue from pressure leaching of bismuth sulfide was investigated in the FeO-SiO_2-CaO ternary slag system.The results show that all the recovery ratios of Bi,Ag,Cu and Pb increase with the increase of reductive coal proportion,reaction temperature and time,while too much reductive coal would help Fe enter metal phase;CaO/SiO_2and Fe O/SiO_2 of the chosen slag system should be 0.5-0.75 and 1.25-1.75,respectively,for the reason that the slag system has the optimum mobility and is beneficial for the recovery of metals.The corresponding optimum conditions are determined as follows:the added coal proportion is 7%of the leaching residue,CaO/SiO_2 mass ratio in the chosen slag system is 0.5 and FeO-SiO_2 is 1.5,the reaction temperature is 1300°C and the reaction time is 40 min.Under the above conditions,the recovery ratios of Bi,Ag,Cu and Pb are 99.6%,99.8%,97.0%and 97.3%,respectively.

Investigation of Propene Oligomerization Catalyzed by Phosphotungstic Acid Catalysts

In this paper, the propene oligomerization reaction catalyzed by phosphotungstic acid supported on two kinds of silica gel was studied, it had been found out that the conversion of propene catalyzed by the type A silica gel-phosphotung- stic acid catalyst was 3.38 m%, while the conversion of propene catalyzed by the type B silica gel-phosphotungstic acid catalyst was 90.1 m% with a nonene selectivity of 42.33 m%, and a dodecene selectivity of 31.79 m%. The influence of reaction temperature, pressure and liquid hourly space velocity （LHSV） on the reaction catalyzed by the type B silica gel- phosphotungstic acid catalyst was investigated. It had been verified that when the reaction temperature increased from 170 ~C to 190 ~C, the conversion of propene increased while the selectivity of nonene and dodecene decreased; when the re- action pressure increased from 3.5 MPa to 4.5 MPa, the conversion of propene increased also, and the selectivity of nonene and dodecene changed very little. The conversion of propene at a space velocity of between 0.5 h-1 and 1.0 h-~ was higher than that achieved at 2.0 h-~, but the selectivity of nonene and dodecene did not show regular fluctuations. An optimum conversion of propene （91.05 m%） and an optimum selectivity of nonene and dodecene （89.51 m%） could be achieved at a reaction temperature of 170 ~C, a reaction pressure of 4.5MPa, and a LHSV of 1.0 fit. The experiments on catalyst life showed that the activity of the type B silica gel-phosphotungstic acid catalyst could be only maintained in 25 hours, and the reason was explained also.