Tertiary recycling of commingled polymer waste over commercial FCC equilibrium catalysts for producing hydrocarbons

A mixture of post-consumer polymer waste (PE/PP/PS) was pyrolysed over cracking catalysts using a fluidising reaction system similar to the FCC process operating isothermally at ambient pressure. Greater product selectivity was observed with a commercial FCC equilibrium catalyst (FCC-E1) with about 53 wt% olefin products in the C₃-C₆ range. Experiments carried out with various catalysts gave good yields of valuable hydrocarbons with differing selectivity in the final products dependent on reaction conditions. A kinetic model based on a lumping reaction scheme for the observed products and catalyst coking behaviours has been investigated. The model gave a good representation of experiment results. This model provides the benefits of lumping product selectivity, in each reaction step, in relation to the performance of the catalyst used and particle size selected as well as the effect of operation conditions, such as rate of fluidising gas and reaction temperature. It is demonstrated that under appropriate reaction temperatures and suitable catalysts can have the ability to control both the product yield and product distribution from polymer degradation, and can potentially lead to a cheaper process with more valuable products.     

Chemical catalysed recycling of polypropylene over a spent FCC catalyst and various commercial cracking catalysts using TGA

Thermogravimetric analysis (TGA) has been used as a tool to characterise the activity, regenerability and deactivation behaviour of spent FCC commercial catalyst (FCC-s1) in the degradation of polypropylene. The FCC-s1 catalysts and amorphous silica–alumina (SAHA) significantly reduced the activation energy as compared with thermal process, and zeolites (ZSM-5 and HUSY) further reduced the activation energy. However, silicalite catalysts gave very minimal effect on PP degradation at a temperature similar to that of thermal cracking. Analysis of the TGA results allowed a relationship between catalyst activity and coke content to be derived. The activity of FCC-s1 catalysts was found to fall exponentially with coke content, and it could be recover most its initial value. The results represent an interesting alternative to have significant impact on the economics of a catalytic polymer degradation process employing post-use FCC commercial catalysts of zero market value.     

The WCl6-e-Al-CH2Cl2 catalyzed polypentenamer formation via ring-opening metathesis polymerization (ROMP)

The synthesis of polypentenamer by an electrochemically generated metathesis polymerization catalyst from methylene chloride solution of WCl₆ was investigated. The active species formed by electroreduction of this salt under controlled potential of +900 mV at a platinum cathode with an aluminum anode were found to catalyze the ring-opening metathesis polymerization (ROMP) of cyclopentene, monocyclic olefin of relatively low strain, in high yield (89%) and at short period (32 min) under mild conditions. The effect of reaction parameters, e.g., olefin/catalyst ratio, reaction time, electrolysis time, catalyst aging, on the polymerization yield have been studied. The resulting polymer has been characterized by ¹H and ¹³C NMR, IR and gel permeation chromatography (GPC) techniques. Analysis of the polypentenamer microstructure by means of ¹³C NMR spectroscopy indicates that the polymer contains a mainly trans stereoconfiguration of the double bonds (σ_c = 0.31) and a slightly blocky distribution (r_tr_c > 1) of cis and trans double bond dyads (r_tr_c = 1.44). However, this electrochemical system is reluctant to facilitate the competing vinyl type addition polymerization reactions.     

The hydrogenation of olefins using a polymer supported ruthenium complex

RuCl₂(PPH₃)3 has been attached to a phosphinated polymer support (phosphinated polystyrene crosslinked with 2% divinylbenzene) and the reagent converted to the polymer supported analogue of RuClH(PPH₃)₃ in the presence of base. The polymer supported catalyst efficiently hydrogenates terminal olefins under ambient conditions. Hydrogenation of 1-hexene has revealed that the reaction rate is proportional to [Ru], [H₂] and [olefin]/(1 + [olefin]). The polymer support environment allows for selectivity in olefin hydrogenation and under suitable reaction conditions short chain terminal olefins are hydrogenated more rapidly than long chain terminal olefins. The extent of metal loading on the polymer and the reaction solvent composition also influence the reaction selectivity and these effects are discussed.     

Enantioselective glyoxylate-ene reactions catalysed by (salen)chromium(III) complexes

An enantioselective carbonyl-ene reaction of alkyl glyoxylates with various 1,1-disubstituted olefins, catalysed by chiral (salen)Cr(III)BF₄ complexes, has been studied. We found that a chromium complex bearing adamantyl substituents at the 3,3′-positions of the salicylidene moiety catalysed the reaction with much greater selectively than the classic Jacobsen-type catalyst. The reaction proceeded effectively under undemanding conditions in the presence of 2 mol % of the catalyst in an acceptable yield and with 59-92% ee.     

Recycling of osmium catalyst in oxidative olefin cleavage: a chemoentrapment approach

A new chemoentrapment strategy for recycling osmium in the catalytic olefin cleavage reaction is reported. The new strategy utilizes KOH/i-PrOH to generate water-soluble Os(VI) species as a recyclable metal catalyst after the oxidative cleavage reaction. For the recycling of the catalyst, NaIO₄-NaClO₂ was found to be the best combination of secondary oxidants and acetonitrile-water was chosen as an optimal solvent for the best recycling results. The new method allows for an efficient recycling of osmium in the reactions involving mono- and di-substituted olefins with 1 mol % of OsO₄ without any significant side reactions and loss of yield.     

Substitution effects on the catalytic activity of Mn(III)-porphyrins in epoxidation of alkenes with iodosylbenzene: A comparison between the electron-rich and electron-deficient porphyrins

Oxidation of different olefins with iodosylbenzene in the presence of Mn(III) complexes of meso-tetra(para-tolyl)porphyrin, meso-tetra(ortho-tolyl)porphyrin, meso-tetra(thien-2-yl)porphyrin and β-hexaboromo-meso-tetra(thien-2-yl)porphyrin as catalyst has been studied. Oxidation of cis- and trans-stilbene in a competitive reaction strongly suggests the involvement of a high valent (porphyrin)MnO as the active oxidant intermediate, in the case of each catalyst. Clear observation of the band relevant to a (porphyrin)Mn(IV)O species in the presence of excess amounts of styrene shows the stability of this moiety towards reaction with olefins. Although, the stability of metalloporphyrins towards oxidative degradation decreases in the order MnT(o-tolyl)P(OAc) > MnT(thien-2-yl)PBr₆(OAc) > MnT(p-tolyl)P(OAc) ? MnT(thien-2-yl)P(OAc), a complex pattern of catalytic activity and product (epoxide) selectivity has been found for the Mn-porphyrins in oxidation of various alkenes.     

Alkylation of isobutane with C<Subscript>4</Subscript> olefins under conventional and supercritical conditions

The solid acid alkylation of isobutane with butylenes on the ultrastable zeolite Y is studied in the temperature range from 120 to 150°C and in a pressure range of 20–120 atm. The catalyst service life becomes longer on passing from the conventional (liquid- and gas-phase) conditions of alkylation to supercritical conditions. The maximum period of complete butylene conversion at 150°C and 120 atm is 3.5 h. The composition of the reaction products is determined by the phase state of the reaction mixture, the reaction time, and the conversion of the C₄ olefins. When the alkylation is carried out under supercritical conditions, the C₈ hydrocarbon selectivity varies between 30 and 40%. Thermoanalytical data suggest that the surface of the spent catalyst contains carbon deposits indicating the formation of oligomeric and cyclic structures.     

Catalytic degradation of high density polyethylene over nanocrystalline HZSM-5 zeolite

High density polyethylene (HDPE) was catalytically degraded using a laboratory fluidised bed reactor in order to obtain high yield of gas fractions at mild temperatures, between 350 and 550 °C. The catalyst used was nanocrystalline HZSM-5 zeolite. High yields of butenes (25%) were found in the gas fractions, which were composed mainly of olefins. Waxes were wholly composed of linear and branched paraffins, with components between C₁₀ and C₂₀. The effects of both temperature and polymer to catalyst ratio on the product yield were studied. Gas conversion was dramatically decreased when the operation temperature was low (below 450 °C) or when the polymer to catalyst ratio was greatly increased (9.2). Gas and wax compositions significantly altered over 500 °C, showing that a part of the HDPE was degraded thermally, increasing the olefin concentration in the waxes. The same variation was observed in the experiments carried out at high polymer to catalyst ratios, obtaining a 50% olefinic concentration in the waxes. The differences observed in product distributions can be attributed to both thermal and catalytic degradations.     

Vinyl polymerization of norbornene catalyzed by a series of bis(β-ketoiminato)nickel (II) complexes in the presence of methylaluminoxane

A series of nickel complexes with β-ketoiminato ligands based on pyrazolone derivative were synthesized and characterized, which are highly active catalyst precursors for norbornene polymerization under mild reaction conditions through a vinyl-type polymerization mechanism. The catalytic activity could be up to 3.38 × 10⁷ g polymer/mol Ni h. The molecular weight distributions of the polynorbornenes (M_w/M_n = 2.05-2.56) indicate the presence of a single active species in the polymerization process.     

Addition reaction of 2-phenylbenzoic acid onto unactivated olefins catalyzed by Ru(II)-xantphos catalysis

Ru(II)-xantphos catalysis is found to be effective for the addition reaction of 2-phenylbenzoic acid onto unactivated olefins. Thus, the reactions of 2-phenylbenzoic acid and unactivated olefins are carried out in the presence of 5 mol % of Ru(II)-xantphos catalysis in refluxing CHCl₃ for 48 h to afford the corresponding esters in 40-95% yield. The control experiments indicate that the influence of TfOH for Brønsted acid catalyst was vanishingly small in our new catalytic system.     

Direct hydroxylation of substituted benzenes to phenols with air and CO using molybdovanadophosphates as a key catalyst

A direct synthetic method of cresols from toluene by hydroxylation with air using CO as a reducing agent was developed. The reaction of toluene with air (15 atm) and CO (5 atm) in the presence of catalytic amounts of H₄PMo₁₁VO₄₀·31H₂O and Pd/C in aqueous acetic acid at 120 °C for 2 h afforded a mixture of o-, m-, and p-cresols in 9.9% yield at 83% selectivity. Cresols were obtained in 19% yield by recharging air and CO under these conditions. A variety of substituted benzenes were hydroxylated by this method to give the corresponding phenol derivatives in higher selectivity.     

Catalytic Transformation of Bio-oil to Olefins with Molecular Sieve Catalysts

Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM_-5, MCM_-41, SAPO_-34 and Y_-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order:HZSM_-5>SAPO_-34>MCM_-41>Y_-zeolite. The highest olefins yield from bio-oil using HZSM_-5 catalyst reached 0.22 kg/kg_bio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.     

Conjugate addition of aromatic amines to ethenetricarboxylates

The conjugate addition of amines is considered to be a useful reaction in synthetic organic chemistry. The reaction of reactive electrophilic olefins, ethenetricarboxylates, and aromatic amines with and without catalytic Lewis acids such as ZnCl₂ and ZnBr₂ at room temperature gave amine adducts in high yields. The products were converted to α-amino acid, dl-aspartic acid derivatives. Using Lewis acids such as Sc(OTf)₃ and Zn(OTf)₂ at higher temperature (40-80 °C), the reaction of ethenetricarboxylates and N-methylaniline gave an aromatic substitution product. A catalytic enantioselective conjugate addition using a chiral Lewis acid was also investigated. For example, the reaction of 1,1-diethyl 2-tert-butyl ethenetricarboxylate with N-methylaniline in the presence of chiral bisoxazoline-Cu(II) complex in THF at −20 °C for 17 h gave an amine adduct in 91% yield and 78% ee. On the other hand, the reaction with aniline and primary aniline derivatives gave adducts with almost no ee%.     

Ir-catalyzed asymmetric allylic alkylation using chiral diaminophosphine oxides: DIAPHOXs. Formal enantioselective synthesis of (−)-paroxetine

An Ir-catalyzed asymmetric allylic alkylation using chiral diaminophosphine oxide is described. Asymmetric allylic alkylation of terminal allylic carbonates proceeded using 5 mol % of Ir catalyst, 5 mol % of DIAPHOX 1i, 10 mol % of NaPF₆, 10 mol % of LiOAc, and N,O-bis(trimethylsilyl)acetamide (BSA), affording the corresponding branched products in excellent yield and in up to 95% ee. The developed catalytic asymmetric reaction was successfully applied to a formal enantioselective synthesis of (−)-paroxetine.     

Gallium(III) triflate-catalyzed one-pot selective synthesis of 2,3-dihydroquinazolin-4(1H)-ones and quinazolin-4(3H)-ones

A series of 2,3-dihydroquinazolin-4(1H)-ones and quinazolin-4(3H)-ones have been synthesized in good to excellent yields and high selectivity by one-pot reaction using isatoic anhydride, ammonium acetate (or amines), and aldehydes in ethanol or in DMSO under mild conditions, respectively. The reaction was efficiently promoted by 1 mol % Ga(OTf)₃ and the catalyst could be recovered easily after the reactions and reused without evident loss of reactivity.     

Platinum-catalyzed double silylations of alkynes with bis(dichlorosilyl)methanes

Bis(dichlorosilyl)methanes 1 undergo the two kind reactions of a double hydrosilylation and a dehydrogenative double silylation with alkynes 2 such as acetylene and activated phenyl-substituted acetylenes in the presence of Speier’s catalyst to give 1,1,3,3-tetrachloro-1,3-disilacyclopentanes 3 and 1,1,3,3-tetrachloro-1,3-disilacyclopent-4-enes 4 as cyclic products, respectively, depending upon the molecular structures of both bis(dichlorosilyl)methanes (1) and alkynes (2). Simple bis(dichlorosilyl)methane (1a) reacted with alkynes [R¹-CC-R²: R¹ = H, R² = H (2a), Ph (2b); R¹ = R² = Ph (2c)] at 80 °C to afford 1,1,3,3-tetrachloro-1,3-disilacyclopentanes 3 as the double hydrosilylation products in fair to good yields (33-84%). Among these reactions, the reaction with 2c gave a trans-4,5-diphenyl-1,1,3,3-tetrachloro-1,3-disilacyclopentane 3ac in the highest yield (84%). When a variety of bis(dichlorosilyl)(silyl)methanes [(Me_nCl_3 − nSi)CH(SiHCl₂)₂: n = 0 (1b), 1 (1c), 2 (1d), 3 (1e)] were applied in the reaction with alkyne (2c) under the same reaction conditions. The double hydrosilylation products, 2-silyl-1,1,3,3-tetrachloro-1,3-disilacyclopentanes (3), were obtained in fair to excellent yields (38-98%). The yields of compound 3 deceased as follows: n = 1 > 2 > 3 > 0. The reaction of alkynes (2a-c) with 1c under the same conditions gave one of two type products of 1,1,3,3-tetrachloro-1,3-disilacyclopentanes 3 and 1,1,3,3-tetrachloro-1,3-disilacyclopent-4-enes (4): simple alkyne 2a and terminal 2b gave the latter products 4ca and 4cb in 91% and 57% yields, respectively, while internal alkyne 2c afforded the former cyclic products 3cc with trans form between two phenyl groups at the 3- and 4-carbon atoms in 98% yield, respectively. Among platinum compounds such as Speier’s catalyst, PtCl₂(PEt₃)₂, Pt(PPh₃)₂(C₂H₄), Pt(PPh₃)₄, Pt[ViMeSiO]₄, and Pt/C, Speier’s catalyst was the best catalyst for such silylation reactions.     

Thermal degradation behaviors of polybenzoxazine and silicon-containing polyimide blends

Thermal behaviors of polymer blends between common-type polybenzoxazine (PBA-a) and polysiloxane-block-polyimide (SPI) were studied using Dynamic Mechanical Analysis (DMA) and Thermogravimetric Analysis (TGA). The polymer blends showed only one glass-transition temperature (T_g) that increased as the content of SPI increased. Synergistic behavior in the char formation of the alloys was clearly observed. The DTG curves showed three stages and two stages of decomposition reaction in neat PBA-a and SPI, respectively. For the blending systems with 25 wt%, 50 wt%, and 75 wt% of SPI, the DTG thermograms of the blends exhibited four stages of thermal decomposition reaction. The apparent activation energies (E_a) of each step were determined using Kissinger method, Flynn-Wall-Ozawa method and Coats-Redfern method. The type of solid state mechanism was determined by Criado method. From the calculation, the solid state thermal degradation mechanism is proposed to be F1 (random nucleation with one nucleus on the individual particle) type for PBA-a, SPI, and their blends.     

Highly efficient deprotection of phenolic tetrahydropyranyl and methoxymethyl ethers and sequel cyclization to indanones using Sn(IV)Cl4 catalyst

Sn(IV)Cl₄ catalyst provided a rapid and efficient deprotection method for the phenolic THP and MOM ethers and sequel intramolecular Friedel–Crafts alkylation reaction of THP and MOM protected chalcone epoxides under mild conditions. The reaction took 2–3 min to give the products in excellent yield (90–98%) at 0 °C without affecting the other functional groups.     

Effect of Fe-loading and reaction temperature on the production of olefins from ethanol by Fe/H-ZSM-5 zeolite catalysts

Lower loading of Fe (1 wt%) and higher reaction temperature (450 °C) led to higher and stable selectivity of C₃₊ olefins by ethanol conversion using Fe/H-ZSM-5 catalysts. Carbon deposition and framework collapse of zeolite support, which may be the cause of change in selectivity of products, was suppressed in some degree.