Propylene, from methanol

The conditions that lead to the formation of the first C-C bond during MTO, the mechanism for making ethylene and propylene from methanol, the critical catalyst parameters that are responsible for the wide variation in light alkene selectivities observed among different framework types and between fresh versus aged catalysts are some of the most intriguing questions of the catalysis field today [100-105]. 

The catalyst is based on high levels of a ZSM-5 type zeolite which has been doped with a combination of phosphorus, magnesium and calcium. This type of formulation has been used to produce ethylene and propylene from methanol and is known to promote olefin formation from a wide variety of feeds. ... 

Because the market for olefins currently greatly exceeds that for methanol production, olefin production could become an important new outlet for the potentially vast quantities of low-cost methanol. Methanol conversion produces a mixture of ethylene and propylene of various ratios or primarily propylene depending on the process. Currently, there are two processes for the production of propylene from methanol the first process is methanol to olefin (MTO) process, developed by UOP and Hydro,... 

Application The UOP/HYDRO Methanol-to-Olefins (MTO) Process produces ethylene and propylene from methanol derived from raw materials such as natural gas, coal, petroleum coke or biomass. 

This section reviews the Lurgi MTF technology for production of propylene from methanol on a proprietary ZSM-5 type catalyst MTPROP supplied from Slid Chemie [12,13]. Lurgi started the development of methanol to propylene (MTP ) in 1993. The proprietary zeolite-based MTP catalyst is exclusively supplied by Slid Chemie [47]. The process begins with a vapor phase dehydration of methanol to DME to produce an equilibrium mixture of DME, methanol, and steam. This mixture is then converted to propylene in a fixed-bed MTP reactor at 400-500°C in the presence of steam and recycled C -C olefins. By-products of the Lurgi MTP process are gasoline, LPG, and fuel gas. The ethylene could be recycled back or used as a copolymer. 

Hack M, Koss U, Kijnig P, Rothaemel M, Holtmann HD. Method for producing propylene from methanol,... 

By far the preponderance of the 3400 kt of current worldwide phenolic resin production is in the form of phenol-formaldehyde (PF) reaction products. Phenol and formaldehyde are currently two of the most available monomers on earth. About 6000 kt of phenol and 10,000 kt of formaldehyde (100% basis) were produced in 1998 [55,56]. The organic raw materials for synthesis of phenol and formaldehyde are cumene (derived from benzene and propylene) and methanol, respectively. These materials are, in turn, obtained from petroleum and natural gas at relatively low cost ([57], pp. 10-26 [58], pp. 1-30). Cost is one of the most important advantages of phenolics in most applications. It is critical to the acceptance of phenolics for wood panel manufacture. With the exception of urea-formaldehyde resins, PF resins are the lowest cost thermosetting resins available. In addition to its synthesis from low cost monomers, phenolic resin costs are often further reduced by extension with fillers such as clays, chalk, rags, wood flours, nutshell flours, grain flours, starches, lignins, tannins, and various other low eost materials. Often these fillers and extenders improve the performance of the phenolic for a particular use while reducing cost. 

Freshly distilled propanal (4.4 g, 0.075 mol) was added at room temperature over a period of 20 min to a stirred mixture of benzyl carbamate (7.55 g, 0.05 mol), phenyldichlorophosphine (8.95 g, 0.05 mol), and glacial acetic acid (10 ml). The mixture was refluxed for 40 min, treated with 4 N hydrochloric acid (50 ml), and then refluxed again for 30 min. After cooling, the organic layer was removed, and the aqueous layer was boiled with charcoal (2 g) and evaporated to dryness in vacuum. The residue was dissolved in methanol (40 ml) and treated with propylene oxide until a pH of 6 to 7 was attained. The resultant precipitate was filtered, washed with acetone, and crystallized from methanol/water to give pure (l-aminopropyl)phenylphos-phinic acid (4.08 g, 41%) of mp 256-258°C. 

Petrochemicals and fossil fuels entail chemicals produced from hydrocarbon feedstocks, such as crude oil products and natural gas. They include such chemicals as hydrocarbons and industrial chemicals (e.g., alcohols, acrylates, acetates), aromatics (e.g., benzene, toluene, xylenes), and olefins (e.g., ethylene, propylene, butadiene, methanol). 

Methyl acrylate and methyl methacrylate, which are critical to the production of polyesters, plastics, latexes, and synthetic lubricants, can also be produced. For example, methyl methacrylate can be produced from propylene and methanol ... 

Tian J-S, Miao C-X, Wang J-Q et al (2007) Efficient synthesis of dimethyl carbonate from methanol, propylene oxide and C02 catalyzed by recyclable inorganic base/phosphonium halide-functionalized polyethylene glycol. Green Chem 9(6) 566—571... 

Li Y, X-q Zhao, Y-j Wang (2005) Synthesis of dimethyl carbonate from methanol, propylene oxide and carbon dioxide over KOH/4A molecular sieve catalyst. Appl Catal A-Gen 279(1-2) 205-208... 

The solution was cooled to — 20 °C., and 50 mmoles of AlEtCl2 were added dropwise to prepare the AN-AlEtCL complex. The solution of complex was warmed to the desired temperature and 50 grams of propylene which had been passed through columns containing KOH pellets and molecular sieves were passed into the reaction mixture in 30 min. The reaction is so rapid that reaction times longer than 5-6 min. make no difference in this polymer yield. The reaction solution was then poured into a large amount of methanol to precipitate the polymer, which was filtered, washed with fresh methanol, and dried to constant weight. If necessary, the polymer was dissolved in acetone and reprecipitated from methanol. 

Fig. 4.21. Stability constants of the (2.2.1) cryptates in propylene carbonate, methanol and water at 298 K. From data reported by J.-C.G. Biinzli, in Handbook on the Physics and Chemistry of Rare Earths, eds K.A. Gschneidner Jr., L. Eyring, Vol. 9, Ch. 60, North Holland, Amsterdam, 1987.

Application To produce propylene from natural gas via methanol. This route delivers dedicated propylene from nonpetroleum sources, i.e., independently from steam crackers and FCCs. 

Applications To primarily produce propylene from C4 to C8 olefins supplied by steam crackers, refineries and/or methanol-to-olefins (MTO) plants via olefin cracking. 

Design a reaction system to maximize the selectivity of p-xylene from methanol and toluene over a HZSM-8 zeolite catalyst. [2nd Ed. 1 9-17] Oxidation of propylene to acrolein (Chem. Eng. Sci. 51,2189 (1996)). 

Small quantities of methanol and ethanol are sometimes added to the C3S in pipelines to protect against freezing because of hydrate formation. Although the beta zeolite catalyst is tolerant of these alcohols, removing them from the feed by a water wash may still be desirable to achieve the lowest possible levels of EB or cymene in the cumene product. Cymene is formed by the alkylation of toluene with propylene. The toluene may already be present as an impurity in the benzene feed, or it may be formed in the alkylation reactor from methanol and benzene. Ethylbenzene is primarily formed from ethylene impurities in the propylene feed. However, similar to cymene, EB can also be formed from ethanol. 

Utilization of methanol or DME for petrochemical applications has a much better chance of succeeding, as there is a much higher value added in going from methanol to light olefins. Even when the markets are soft, ethylene and propylene command prices of at least about 400 per tonne, and usually substantially more. Even on a pure fuel value basis, 400 per tonne for ethylene would be equivalent to about 8.00 per giga-Joule, or a very significant value-added markup. 

Current technologies for the conversion of methane into gasoline, middle distillate and petrochemicals require initial formation of intermediate feedstocks such as synthesis gas, methanol and lower olefins which in turn must be converted to the desired products. Whilst adding an extra stage such an approach may add flexibility to the overall conversion of methane. For example, the production of lower olefins such as ethylene and propylene from methane has the potential to satisfy needs in the fuels, commodity and speciality chemicals a reas. 

In contrast to lower olefins from diminishing resources like naphtha or associated gas, the lower olefins from methanol or dimethyl ether produced from abundant coal or natural gas are attracting attention. Of particular interest is the synthesis of ethylene and propylene from dimethyl ether because of their growing demand as raw materials for polyethylene and polypropylene. The usage of these polymers in everyday life is diverse (e.g., molded plastic items, plastic packaging films, etc.). Increasing demand for isobutene is inevitable since isobutene is used as the raw material for MTBE, MMA (methyl... 

The synthesis of olefins from methanol using aluminophosphate molecular sieve catalysts was studied [76], Process studies were conducted in a fluid-ized-bed bench-scale pilot plant unit utilizing small-pore silicaluminophosph-ate catalyst synthesized at Union Carbide. These catalysts are particularly effective in the catalytic conversion of methanol to olefins, when compared to the performance of conventional aluminosilicate zeolites. The process exhibited excellent selectivities toward ethylene and propylene, which could be varied considerably. Over 50 wt% of ethylene and 50 wt% propylene were synthesized on the same catalyst, using different combinations of temperatures and pressures. These selectivities were obtained at 100% conversion of methanol. Targeting light olefins in general, a selectivity of over 95% C2-C4 olefins was obtained. The catalyst exhibited steady performance and unaltered... 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

Methyl terf-butyl ether (MTBE) is an important industrial product used as oxygenate additive in reformulated gasoline. Environmental concern makes its future uncertain, however. Although mainly manufactured by reaction of isobutylene with methanol, it is also produced commercially from methanol and fcrr-butyl alcohol, a by-product of propylene oxide manufacture. Numerous observations from the use of heteropoly acids have been reported. These compounds were used either as neat acids [74], or supported on oxides [75], silica or K-10 montmorillonite [76]. They were also used in silica-included form [77] and as acidic cesium salts [74,77]. Other catalysts studied were sulfated ZrOj [76], Amberlyst 15 ion-exchange resin [76], HZSM-5 [76], HF-treated montmorillonite, and commercial mineral acid-activated clays [75]. Hydrogen fluoride-treatment of montmorillonite has been shown to furnish particularly active and stable acid sites thereby ensuring high MTBE selectivity (up to 94% at 413 K) [75]. 

Needles from methanol, mp 151-152°, Practically insol in water. Slightly sol in alcohol, glycertil, propylene glycol. therap cat Anxiolytic muscle relaxant (skeletal). 

Crystals from methanol- mp 53% Sol in acetone, cyclohexanone. ethyl acetate, toluene, xylene, ethylene glycol -propylene glycol, some oils Practically insol in water. LDm in male, female rats 400, 330 mg/kg orally 790, 1250... 

Crystals from methanol, practically tasteless, mp 105 106. Very sparingly sol in hot water (0.05%), somewhat more (l to 2%) in 95% ale, in glycerol, in propylene glycol. therap cat Antidepressant. 

Preparation and Utilization of CaF2-Zr02 as a Novel Solid base for the Synthesis of Dimethyl Carbonate from Methanol and Propylene Carbonate... 

The Wacker process, the oxidation of ethylene to acetaldehyde, lost its original importance over the past 30 years. While at the beginning more than 40 factories with a total capacity of more than 2 million tons of acetaldehyde per year were installed, acetaldehyde as an industrial intermediate was replaced successively by other processes. For example, compounds such as butyraldehyde/butanol are produced by the oxo process from propylene, and acetic acid by the Monsanto process from methanol and CO or by direct oxidation of ethane. The way via acetaldehyde to these products is dependent on the price of ethylene. Petrochemical ethylene from cracking processes became considerably more expensive during these years. Thus, only few factories would be necessary to meet the demand for other derivatives of acetaldehyde such as alkyl amines, pyridines, glyoxal, and pentaerythritol. 

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