Process For Converting Oxygenates To Olefins (Shell)

CATEGORY: OXYGENATES TO OLEFINS
Process For Converting Oxygenates To Olefins (Shell)
United States Patent Application 20160257626
SANBORN; Richard Addison ;   et al.   September 8, 2016
Applicant: Shell Oil Company
Abstract
A process for converting oxygenates to olefins comprising: a) providing an oxygenate containing stream to an oxygenate to olefins conversion reactor; b) passing the oxygenate containing stream through a feed introduction system comprising one or more nozzles and one or more corresponding caps; c) contacting the oxygenate containing stream with a molecular sieve catalyst in the oxygenate to olefins conversion reactor to form an olefin containing product stream; and d) removing the product stream from the reactor.
FIELD OF THE INVENTION
[0002] The invention provides a process for converting oxygenates to olefins. The process includes passing the oxygenate containing stream through a feed introduction system comprising one or more nozzles and one or more corresponding caps.
BACKGROUND OF THE INVENTION
[0003] Oxygenate-to-olefin ("OTO") processes are well described in the art. Typically, oxygenate-to-olefin processes are used to produce predominantly ethylene and propylene. An example of such an oxygenate-to-olefin process is described in US Patent Application Publication No. 2011/112344, which is herein incorporated by reference. The publication describes a process for the preparation of an olefin product comprising ethylene and/or propylene, comprising a step of converting an oxygenate feedstock in an oxygenate-to-olefins conversion system, comprising a reaction zone in which an oxygenate feedstock is contacted with an oxygenate conversion catalyst under oxygenate conversion conditions, to obtain a conversion effluent comprising ethylene and/or propylene.
[0004] U.S. Pat. No. 6,737,556 describes a method and system for reducing the formation of metal catalyzed side-reaction byproducts formed in the feed vaporization and introduction system by forming and/or coating one or more of the heating devices, feed lines or feed introduction nozzles with a material that is resistant to the formation of metal catalyzed side reaction byproducts.
[0005] U.S. Pat. No. 7,034,196 describes a method and apparatus for reducing the amount of metal catalyzed side-reaction byproducts formed in the feed vaporization and introduction system of a methanol to olefin reactor system by maintaining a sufficiently low temperature in the feed vaporization and introduction system.
SUMMARY OF THE INVENTION
[0006] The invention provides a process for converting oxygenates to olefins comprising: a) providing an oxygenate containing stream to an oxygenate to olefins conversion reactor; b) passing the oxygenate containing stream through a feed introduction system comprising one or more nozzles and one or more corresponding caps; c) contacting the oxygenate containing stream with a molecular sieve catalyst in the oxygenate to olefins conversion reactor to form an olefin containing product stream; and d) removing the product stream from the reactor.
[0007] The invention further provides a system for converting oxygenates to olefins comprising: a) an oxygenate to olefins conversion reactor; b) one or more catalyst inlets for introducing catalyst into the reactor; c) one or more feed inlet nozzles located at the bottom of the reactor for introducing an oxygenate containing feed into the reactor; and d) one or more protective caps located above each of the feed inlet nozzles.
[0008] The invention also provides a feed introduction system for an oxygenates to olefins conversion system comprising: a) one or more feed inlet nozzles located in the bottom of an oxygenate to olefins conversion reactor; and b) one or more protective caps located above each of the feed inlet nozzles.
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Conversion of organic oxygenates to hydrocarbons (ExxonMobil)

CATEGORY: OXYGENATES
Conversion of organic oxygenates to hydrocarbons (ExxonMobil)
United States Patent Application 20160178132
Harandi; Mohsen N. ;   et al.   June 23, 2016
Assignee: ExxonMobil Research and Engineering Company
Abstract
In a process for the catalytic conversion of organic oxygenates to hydrocarbons, a feed comprising at least one organic oxygenate is contacted with a zeolite catalyst under conditions effective to produce a hydrocarbon product comprising aromatics, olefins and paraffins. At least a fraction of the hydrocarbon product containing C.sub.4+ hydrocarbons, including at least part of the olefins, is then contacted with hydrogen in the presence of a hydrogenation catalyst under conditions effective to saturate at least part of the olefins in the C.sub.4+-containing fraction and produce a hydrogenated effluent containing less than 1 wt % olefins. The hydrogenated effluent is useful as a diluent for heavy crude oils.
FIELD OF THE INVENTION
[0002] This invention relates to a process for converting organic oxygenates to hydrocarbons.
BACKGROUND
[0003] It is well known that organic oxygenates, particularly methanol and dimethyl ether, can be converted to a wide range of hydrocarbons, including aromatics, olefins and paraffins, over a special class of crystalline aluminosilicate zeolite catalysts of which H-ZSM-5 is the most preferred. The process is generally referred to as the MTG process at least partly because the hydrocarbon product has a high octane value and is useful as a gasoline blending stock. The MTG process is described in many patents and publications, including U.S. Pat. Nos. 3,931,349; 3,969,426; 3,899,544; 3,894,104; 3,904,916; and 3,894,102; the disclosures of each of which are incorporated by reference.
[0004] U.S. Pat. No. 4,304,951 describes a process for hydrotreating a 200-400.degree. F.+ bottoms fractions resulting from conversion of methanol to gasoline in order to decrease the durene content of the bottoms fraction and produce distillate.
[0005] There is, however, continuing interest in developing new applications for the hydrocarbon product of the MTG process, particularly at sites which have a plentiful supply of natural gas which can be converted to the methanol and dimethyl ether feedstocks of the MTG process. In addition, there is growing interest in developing processes which allow greater flexibility in the final product slate of the MTG process according to site needs and customer demand.
SUMMARY
[0006] According to the present invention, it has now been found that by hydrotreating a broad fraction of the MTG effluent, containing at least some of the C.sub.4+ component, it can be possible to saturate most or all of the olefins in the effluent, with or without significant saturation of durene and other aromatics, and produce a hydrogenated product of enhanced volume and an olefin content less than 1 wt %. Such a product can be useful as, for example, a pipeline diluent. Thus, as the need to transport heavy crudes oils and bitumen grows, this process can address the increasing need for alternatives to the current diluents, mainly condensate and naphtha, used to lower the viscosity of these crudes and render them subject to transportation by pipeline.
[0007] Moreover, the present process can offer the possibility for a dual operation strategy, in which advantage can be taken of olefin saturation capability to produce diluents for pipelines when gasoline demand may be low, such as during the winter. Alternatively, when operating in normal gasoline mode, the durene content of the C.sub.10 rich fraction can be reduced to produce gasoline meeting durene specifications.
[0008] Thus, in one aspect, the invention can relate to a process for the catalytic conversion of organic oxygenates to hydrocarbons, the process comprising: (a) contacting a feed comprising at least one organic oxygenate with a zeolite catalyst under conditions effective to produce a hydrocarbon product comprising aromatics, paraffins, and olefins; and (b) contacting at least a fraction of the hydrocarbon product containing C.sub.4+ hydrocarbons, including at least part of the olefins, with hydrogen in the presence of a hydrogenation catalyst under conditions effective to decrease the olefin content of the C.sub.4+-containing fraction and to produce a hydrogenated effluent containing less than 1 wt % olefins.
[0009] In a further aspect, the invention can relate to a continuous process for the catalytic conversion of organic oxygenates to hydrocarbons, the process comprising: (a) contacting a feed comprising at least one organic oxygenate with a crystalline aluminosilicate zeolite under conditions effective to produce a hydrocarbon product comprising aromatics, paraffins, and olefins; (b) contacting at least a fraction of the hydrocarbon product with hydrogen in the presence of a hydrogenation metal catalyst under conditions effective to reduce at least part of the durene in the fraction and to produce a hydrogenated effluent, wherein the process can periodically be switched between at least first and second operating modes, wherein, during the first operating mode, the contacting (b) can be conducted on the entire hydrocarbon product or a C.sub.4+-containing fraction thereof, and wherein, during the second operating mode, the contacting (b) can be conducted on a 300-400.degree. F.+ bottoms fraction of the hydrocarbon product.
[0010] In still yet a further aspect, the invention can relate to a pipelineable hydrocarbon composition comprising a mixture of a heavy crude oil, or fraction thereof, having an API gravity of less than 20 degrees and/or a viscosity at 25.degree. C. greater than 400 centipoise and a diluent, wherein the diluent comprises at least part of the effluent obtained by hydrogenation of at least a fraction of the hydrocarbon product produced by the reaction of organic oxygenate with a crystalline aluminosilicate zeolite.
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Apparatus And Process For Producing Gasoline, Olefins And Aromatics From Oxygenates (ExxonMobil)

CATEGORY: OXYGENATES: GASOLINE
Apparatus And Process For Producing Gasoline, Olefins And Aromatics From Oxygenates (ExxonMobil)
United States Patent Application 20160102032
Du; Bing ;   et al.   April 14, 2016
Assignee: ExxonMobil Research and Engineering Company
Abstract
Apparatuses and processes for converting an oxygenate feedstock, such as methanol and/or dimethyl ether, in a fluidized bed containing a catalyst to hydrocarbons, such as gasoline boiling components, olefins and aromatics are provided herein.
FIELD OF THE INVENTION
[0002] The present invention relates to converting an oxygenate feedstock, such as methanol and dimethyl ether, in a fluidized bed containing a catalyst to hydrocarbons, such as gasoline boiling components, olefins and aromatics.
BACKGROUND OF THE INVENTION
[0003] Processes for converting lower oxygenates such as methanol and dimethyl ether (DME) to hydrocarbons are known and have become of great interest because they offer an attractive way of producing liquid hydrocarbon fuels, especially gasoline, from sources which are not petrochemical feeds. In particular, they provide a way by which methanol and DME can be converted to gasoline boiling components, olefins and aromatics. Olefins and aromatics are valuable chemical products and can serve as feeds for the production of numerous important chemicals and polymers. Because of the limited supply of competitive petroleum feeds, the opportunities to produce low cost olefins from petroleum feeds are limited. However, methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes. As an alternative, the methanol may be obtained from natural gas or biomass by other conventional processes.
[0004] Available technology to convert methanol and other lower oxygenates to hydrocarbon products utilizes a fixed bed process, such as the processes described in U.S. Pat. Nos. 3,998,899; 3,931,349 and 4,035,430. In the fixed bed process, the methanol is usually first subjected to a dehydrating step, using a catalyst such as gamma-alumina, to form an equilibrium mixture of methanol, DME and water. This mixture is then passed at elevated temperature and pressure over a catalyst for conversion to the hydrocarbon products which are mainly in the range of light gas to gasoline. The fixed bed process uses a recycle gas for temperature control and very large heat transfer to manage low quality heat, which results in high compression costs and a large heat exchange network. Typically, a fixed bed process is a multi-reactor, unsteady state operation, which requires a large bore valving system to control the process.
[0005] In contrast, direct cooling of the reactor in the fluidized bed process eliminates the need for recycle gas for temperature control, which simplifies the heat exchange. Further, the fluidized bed process with continuous catalyst regeneration is a steady state operation with constant product yield. Thus, the fluidized bed process requires lower capital costs and savings on operating expenses compared to the fixed bed process. However, current fluidized bed processes typically have a low product yield. For example, C.sub.5+ gasoline yield from a fluidized bed process ranges from 65 wt % to 75 wt % of hydrocarbons (HC), while the C.sub.5+ gasoline yield from a fixed bed process ranges from 80 wt % to 90 wt % of HC. Thus, an alkylation unit is usually required to increase C.sub.5+ gasoline yield in a fluidized bed process. Therefore, there is a need to provide fluidized bed processes for converting oxygenates to hydrocarbons with increased product yields and further, without the use of an alkylation unit.
SUMMARY OF THE INVENTION
[0006] It has been found that hydrocarbon product yields can be increased without the need for an alkylation unit by providing apparatuses and processes for converting oxygenates in a fluidized reactor bed by staging the reactor, operating the reactor at a higher pressure and lower temperature, and/or providing a recycle stream, such as light olefins.
[0007] Thus, in one aspect, embodiments of the invention provide a process for converting an oxygenate feedstock to a C.sub.5+ gasoline product comprising: feeding the oxygenate feedstock to a fluidized bed reactor under conditions to convert the oxygenate feedstock to a hydrocarbon mixture in a reactor effluent, wherein the fluid bed reactor comprises: (i) a catalyst; and (ii) at least one packing layer; cooling the reactor effluent comprising the hydrocarbon mixture and condensing a portion of the reactor effluent to form a mixed phase effluent; separating the mixed phase effluent into an aqueous liquid phase, a hydrocarbon gas phase and a hydrocarbon liquid phase; separating a C.sub.4- light gas comprising C.sub.2-C.sub.4 olefins and the C.sub.5+ gasoline product from the hydrocarbon gas phase and the hydrocarbon liquid phase.
[0008] In another aspect, embodiments of the invention provide an apparatus for producing a C.sub.5+ gasoline product comprising: a fluidized bed reactor comprising: (i) a fluid inlet for a feedstock; (ii) a catalyst; and (iii) at least one packing layer; a cooler for cooling the reactor effluent and condensing a portion of the reactor effluent to form a mixed phase effluent; a separator for separating the mixed phase effluent into a gas hydrocarbon stream, a water stream, and a liquid hydrocarbon stream; a means for transporting the reactor effluent from the fluid bed reactor to the separator; at least one fractionating column for producing the C.sub.5+ gasoline product; and a means for transporting the liquid hydrocarbon stream and gas hydrocarbon stream to the at least one fractionating column.
[0009] In still another aspect, embodiments of the invention provide a process for converting an oxygenate feedstock to olefins comprising: feeding the oxygenate feedstock to a fluidized bed reactor under conditions to convert the oxygenate feedstock to a hydrocarbon mixture in a reactor effluent, wherein the fluid bed reactor comprises: (i) a catalyst; and (ii) at least one packing layer; cooling the reactor effluent comprising the hydrocarbon mixture and condensing a portion of the reactor effluent to form a mixed phase effluent; separating the mixed phase effluent into an aqueous liquid phase, a hydrocarbon gas phase and a hydrocarbon liquid phase; separating olefins from the hydrocarbon gas phase and the hydrocarbon liquid phase.
[0010] In still another aspect, embodiments of the invention provide a process for converting an oxygenate feedstock to aromatics comprising: feeding the oxygenate feedstock to a fluidized bed reactor under conditions to convert the oxygenate feedstock to a hydrocarbon mixture in a reactor effluent, wherein the fluid bed reactor comprises: (i) a catalyst; and (ii) at least one packing layer; cooling the reactor effluent comprising the hydrocarbon mixture and condensing a portion of the reactor effluent to form a mixed phase effluent; separating the mixed phase effluent into an aqueous liquid phase, a hydrocarbon gas phase and a hydrocarbon liquid phase; separating aromatics from the hydrocarbon gas phase and the hydrocarbon liquid phase.
[0011] Other embodiments, including particular aspects of the embodiments summarized above, will be evident from the detailed description that follows.
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C8-Oxygenates for Clean Diesel Combustion

CATEGORY: OXYGENATES 
C8-Oxygenates for Clean Diesel Combustion

Type	Report
Author	Benedikt Heuser
Author	Thomas Laible
URL	http://papers.sae.org/2014-01-1253/
Place	Warrendale, PA
Date	2014-04-01
Report Type	SAE Technical Paper
Abstract	Reports results of a study of the two possible alternative and biomass-based fuel candidates Di-n-butyl ether (DNBE) and 1-octanol are investigated with regard to their utilization in a diesel-type engine. In order to assess the fuels emission-reduction potential, both were tested in a single cylinder engine (SCE) and a high pressure chamber (HPC) in comparison to conventional EN590 diesel at various load points. Due to its reduced reactivity 1-octanol features a longer ignition delay and thus higher degrees of homogenization at start of combustion. DNBE, on the other hand, ignites rather rapidly in both the HPC and the engine, leading to a predominantly mixing controlled combustion. Thus, both fuels feature completely different combustion characteristics. However, compared to diesel, both fuels contribute to a significant reduction in Filter Smoke Number (FSN) up to a factor of 15. In addition to FSN measurements also size-number-distributions of particulates have been measured by means of an Engine Exhaust Particle Sizer Spectrometer (EEPS™). With the oxygenated fuels a shift in the characteristic particle diameter distribution was observed in the higher engine load points. With DNBE, engine out emissions of unburned hydrocarbons (HC), carbon monoxide (CO) and combustion noise were below standard diesel fuel even without changing any engine hardware or calibration.