High Efficieney Synthesis of Isotaetie Polypropylene and Linear Polyethylene Using a New C_2-symmetric Carbon-bridged Zirconocene Catalyst

Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.

i-PP/EPR REACTOR ALLOY PREPARED THROUGH ETHYLENE/PROPYLENE SLURRY COPOLYMERIZATION CATALYZED BY METALLOCENE SUPPORTED iPP PARTICLES

i-PP/m-EPR reactor alloy were prepared through ethylene/propylene slurry copolymerization catalyzed by metallocene(rac-Et(Ind)_2ZrCl_2)supported on porous iPP particles.Polar monomer(dihydromyrcene alcohol)treated with triethyaluminum was added in the preparation of porous iPP particles to introduce hydroxyl groups and thus enhance the ability for chemically supporting the metallocene catalyst.The effects of MAO/Zr ratio and monomer composition in feed on the reaction activity and property of polymer were i...

Synthesis of 2-methylpyrazine from cyclocondensation of ethylene diamine and propylene glycol over promoted copper catalyst

The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.

RANDOM COPOLYMER OF PROPYLENE OXIDE AND ETHYLENE OXIDE PREPARED BY DOUBLE METAL CYANIDE COMPLEX CATALYST

Copolymerization of propylene oxide (PO) and ethylene oxide (EO) using double metal cyanide (DMC) complex as the catalyst was carried out. The structure of random copolymers was confirmed by C-13-NMR and IR spectra. H-1-NMR analysis shows that the EO content in the copolymer is the same as that in the initial monomer feed. Moderate molecular weight copolymers with various EO content were obtained and their values of molecular weight distribution (MWD) fell in the range of 1.21-1.55. It was found that the molecular weight of copolymers is controlled by the mass ratio of EO+PO to initiator moles used, The reaction rate as well as polymer yield decrease with increasing EO content in the feed composition.

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.

COPOLYMERIZATION OF ETHYLENE AND PROPYLENE WITH (CpCH_2CH_2CH=CH_2)_2MCl_2(M=Zr,Hf)AND Cp_2ZrCl_2 CATALYSTS

(CpCH_2CH_2CH = CH_2)_2MCl_2(M=Zr, Hf)/MAO and Cp_2ZrCl_2/MAO (Cp=cyclopentadienyl; MAO=methylaluminoxane) catalyst systems have been compared for ethylene copolymerization to investigate the influence of theligand and transition metal on the polymerization activity and copolymer properties. For both CH_2CH_2CH=CH_2 substitutedcatalysts the catalytic activity decreased with increasing propene concentration in the feed. The activity of the hafnocenecatalyst was 6～8 times lower than that of the analogous zirconocene catalyst, ^(13)C NMR analysis showed that the copolymerobtained using the unsubstituted catalyst Cp_2ZrCl_2 has greater incorporatien of propene than those produced byCH_2CH_2CH=CH_2 substituted Zr and Hf catalysts. The melting point, crystallinity and the viscosity-average molecularweight of the copolymer decreased with an increase of propenc concentration in the feed. Both CH_2CH_2CH= CH_2 substitutedZr and Hf catalysts exhibit little or no difference in the melting point and crystallinity of the produced copolymers. However,there are significant differences between the two zirconocene catalysts. The copolymer produced by Cp_2ZrCl_2 catalyst havemuch lower T_m and X_c than those obtained with the (CpCH_2CH_2CH=CH_2)_2ZrCl_2 catalyst. The density and molecular weightof the copolymer decreased in the order: (CpCH_2CH_2CH=CH_2)_2HfCl_2>(CpCH_2CH_2CH=CH_2)_2ZrCl_2>Cp_2ZrCl_2. The kineticbehavior of copolymerizaton with Hf catalyst was found to be different from that with Zr catalyst.

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.

Electromechanical Properties of Ethylene Propylene Diene Elastomers: Effect of Ethylene Norbornene Content

Ethylene propylene diene elastomers (EPDM) of various side chains and molecular weights were prepared as thin discs and the effects of electric field strength and temperature on the electromechanical properties were investigated. The electrical conductivity, the dielectric constant, the storage and loss moduli (G' and G'), the storage modulus response (ΔG’1000 V/mm), and the storage modulus sensitivity (ΔG’1000 V/mm/G’0) of the elastomers of different ethylene norbornene (ENB) contents and molecular weights were measured under electric field strengths varying from 0 V/mm to 1000 V/mm and at temperatures between 300 K and 380 K. The storage modulus response and sensitivity increase with increasing molecular weight and dielectric constant, consistent with the existing theory. However, for the case of EPDMs with different ENB contents, the storage modulus response and sensitivity vary inversely with the dielectric constant. EDPM is potentially a new type of electroactive materials.

A dual-bed catalyst for producing ethylene and propylene from syngas

Ethylene and propylene(C_(2)^(–)3=)are the two most demanded olefin products,which are mainly produced by thermal and catalytic cracking of petroleum-derived hydrocarbons now[1].With the depletion of petroleum resources,the use of non-petroleum resources such as natural gas,coal,biomass,even CO_(2)etc.

^(13)C NMR Study of Ethylene/propylene/octene-1 Terpolymers Synthesized with TiCl_4/MgCl_2/ i -Bu_3Al as the Catalyst

The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.

Copolymerization Kinetics of Ethylene Oxide and Propylene Oxide

The copolymerization kinetics of ethylene oxide and propylene oxide in an atomizing-circulation reactorunder semi-continuous operation is studied which is of great importance for molecular designation. The kineticparameters are obtained by numerical optimization of the kinetic model.

Effect of Water Vapour on the Acidity of ZSM-5 Zeolite Used for Catalytic Cracking of Naphtha to Manufacture Ethylene and Propylene

The change in acidity of the ZSM-5 zeolite was investigated after it was treated with water vapour, and its capability on ammonia adsorption was also studied after having adsorbed water vapour. The effect of water vapour on products distribution was studied during catalytic cracking of naphtha, the changes in the adsorption ability and catalytic performance of the ZSM-5 zeolite was investigated after the catalyst was loaded with phosphorus species. These results all indicated that water vapour could reduce the acid strength and acid density of ZSM-5 zeolite and affect the capability of ZSM-5 on adsorption of gases, therefore the activated energy contributed by the ZSM-5 zeolite to the catalytic cracking reaction would be low to prevent the feedstock from deepened catalytic cracking and coke formation.

Effects of Hydrophobicity of Ethylene Oxide-Propylene Oxide Copolymers on Phase Diagrams of Aqueous Two-Phase Systems and Partition Behaviors of Cephalexin and 7-Aminodeacetoxicephalos-poranic Acid

A series of ethylene oxide (EO)-propylene oxide (PO) randomco-polymers (EOPO) were used to form aqueous two-phase systems (ATPS)with ammonium sulfate. Effects of EOPO's properties on the phaseseparation behaviors and on the partition of cephalexin and7-aminodesacetoxicephalosporanic acid (7-ADCA) in ATPS wereinvestigated. Both the molar mass and molar ratio of EO to PO of EOPOcould greatly influence partition behaviors of cephalexin and 7-ADCAas well as the binodal curve of ATPS.

CRYSTALLIZATION KINETICS OF ETHYLENE-PROPYLENE COPOLYMERS PREPARED BY LIVING COORDINATION POLYMERIZATION

In this paper,crystallization kinetics of a series of ethylene-propylene copolymers prepared by living polymerization coordination catalyzed by a fluorinated bis(phenoxyimine)Ti catalyst(FI-EP copolymers)was studied,and was compared with that of ethylene-propylene copolymers prepared by a conventional Ziegler-Natta catalyst(ZN-EP copolymers).It is found that,the Avrami exponent and the crystallization rate constant of the FI-EP and ZN-EP copolymer show similar dependence on crystallization temperature,but t...

Metathesis of Butylene-2 and Ethylene to Propylene over 3.0Mo/(Hβ+γ-Al_(2)O_(3))Catalysts with Differentγ-Al_(2)O_(3)Contents

A series of 3.0Mo/(Hβ+γ-Al_(2)O_(3))samples withγ-Al_(2)O_(3)contents in the range of 0_100%(mass fraction)was studied by means of XRD,NH_(3)-TPD,TPR and BET determinations for characterizing their structures.The Hβzeolite structure in the 3.0Mo/Hβsample can be effectively stabilized by adding someγ-Al_(2)O_(3)to Hβzeolite.γ-Al_(2)O_(3)mainly favors the formation of polymolybdate or multilayered Mo oxide,while Hβmainly forms the Al_(2)(MoO_(4))_(3)species,as evaluated by the TPR technique.When used as the catalyst for the metathesis of butylene-2 and ethylene to propylene,there exists a close correlation between the specific surface area and stability of the catalyst.The specific surface area of the catalyst shows the maximum when{(Hβ+}γ-Al_(2)O_(3))contains 30%γ-Al_(2)O_(3),which is in agreement with that of the time needed for the reaction stablization.In the case of maximum surface area,the rate of coke deposition is the minimum.

On the Vickers Microhardness and Wide-Angle X-Ray Line Width for Characterization of the Oxidative Stability of Poly(ethylene-co-propylene) Pipes

The purpose of the current study is to evaluate the ageing of poly(ethylene-co-propylene) fittings produced by several manufacturers. The fittings were aged for varying times as follows: 0, 2, 13, 23, 45, 106, 225 and 391 days at 100°C. In a previous paper, the oxidation induction time (OItime) and oxidation induction temperature (OItemp) were evaluated with respect to every single step of the ageing process [1]. Here, the Vickers microhardness and wide-angle X-ray line width were used for characterization of the oxidative stability of poly(ethylene-co-propylene) pipes. Both the Vickers microhardness and wide-angle X-ray line width as evaluated from a certain reflex of the diffractogram generally increase with ageing for most samples. The higher microhardness is most likely related to higher fragility of the pipes. The increase of the X-ray line width with ageing indirectly proves that reducing the crystallite size as well as increase of the crystallite defectiveness take place.

Synthesis of Polynorbornene-Poly(ethylene-co-propylene)Diblock Copolymer

Transformation of living ring-opening metathesis polymerization into coordination polymerization by converting the titanacyclobutane group attached to a polynorbornene chain into titanocene alkoxide has been used for the synthesis of polynorbornene-poly(ethylene-co-propylene) block copolymer. Preliminary characterizations of the copolymerization products by solvent extraction and C-13 NMR spectrum are reported.

A Hybrid Algorithm Based on Differential Evolution and Group Search Optimization and Its Application on Ethylene Cracking Furnace

To find the optimal operational condition when the properties of feedstock changes in the cracking furnace online,a hybrid algorithm named differential evolution group search optimization(DEGSO) is proposed,which is based on the differential evolution(DE) and the group search optimization(GSO).The DEGSO combines the advantages of the two algorithms:the high computing speed of DE and the good performance of the GSO for preventing the best particle from converging to local optimum.A cooperative method is also proposed for switching between these two algorithms.If the fitness value of one algorithm keeps invariant in several generations and less than the preset threshold,it is considered to fall into the local optimization and the other algorithm is chosen.Experiments on benchmark functions show that the hybrid algorithm outperforms GSO in accuracy,global searching ability and efficiency.The optimization of ethylene and propylene yields is illustrated as a case by DEGSO.After optimization,the yield of ethylene and propylene is increased remarkably,which provides the proper operational condition of the ethylene cracking furnace.

Advances in DCC Process and Catalyst for Propylene Production from Heavy Oils

Deep Catalytic Cracking （DCC） developed by RIPP （Research Institute of Petroleum Processing）, SINOPEC is a catalytic conversion process derived from the FCC process using heavy feedstocks for producing raw materials used in the petrochemical industry, such as ethylene and propylene. It was firstly demonstrated in 1990 and has been commercialized since 1994. Up to now, seven units have been put into production inside and outside China, and many other DCC units are under construction and in the phase of design now. Products ofpropylene and ethylene from DCCU have been used as feedstock for manufacturing high quality polypropylene, polyethylene and acrylonitrile. Many innovations on technological process, and preparation of catalytic materials used in the DCC process will be presented in this paper.

Optimization of the separation unit of methanol to propylene(MTP)process and its application

Based on a typical gas composition from a methanol-to-propylene (MTP) reactor, and guided by a requirement to recover both propylene and ethylene, three separation strategies are studied and simulated by using PROI1 package. These strategies are sequential separation, front-end dethanization, and front-end depropanization. The process does not involve an ethylene refrigeration system, using the separated stream as absorbent, and absorbing further the medium-pressure demethanization, and a proprietary technology by combining intercooling oil absorption and throttle expansio n. In fluences of different process streams as absorbent are studied on energy consumptions, propylene and ethylene recovery percentages, and other key-performance indicators of the separation strategies. Based on a commercial MTP plant with a methanol capacity of 1700 kt·a^-1, the simulated results show that the front-end dethanization using the C4 mixture as absorbent is the optimal separation strategy, in which the standard fuel oil consumption (a key-performance in dicator of energy con sumption) is 18.97 kt·h^-1, the total power consumption of two compressors is 22.4 MW, the propylene recovery percentage is 99.70%, and the ethylene recovery percentage is 99.70%. For a further improvement, the pre-dethanization and thermal coupling methods are applied. By using front-end pre-dethanization (partial cutting) with debutanizeroverhead, i.e. the C4 mixture, as absorbent, the power consumption of the compressors decreases to 19.9 MW, an 11% reduction compared with the clear-cutting method. The energy consumption for the dual compressors for crude gaseous product mixture and main product propylene refrigeration is 16.69 MW, 16.55% lower than that of the present MTP industrial plant with the same scale, and a total energy consumption of 20 MW for the triple compressors including product gas mixture compression, and ethylene and propylene refrigeration.