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    A good notes on ammonia process

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    A good notes on ammonia process

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    Block FLow Diagram

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    A good notes on ammonia process

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    cu») United States US 20160368843 2) Patent Application Publication co) Pub. No.: US 2016/0368848 A1 Axelrod et al. (54) PROCESS FOR MANUFACTURING METHYL TERTIARY-BUTYL ETHER (MTBE) AND OTHER HYDROCARBON: (71) Applicant: Lyondell Chemical Technology, LP. Houston, TX (US) (72) Inventors: Michael G. Axelrod, Newtown Square, PA (US): Steven T. Coleman, Houston, TX US) (73) Assignee: Lyondell Chemical Technology, L Houston, TX (US) (21) Appl. Now 18/173,042 (22) Filed: Jum, 3, 2016 Related US. Application Data (60) Provisional aplication No, 62/183,014, filed on Jun. 22, 2015, Publication Classitieation (1) Inc core 1106 (2006.01) core 42 (2005.01) (2005.01) (2005.01) (43) Pub. Date: Dee. 22, 2016 core 2950 200501) core $327 (2006.01), core 236 (200501), 2) US. ¢ ce CO7C 41706 (2013.01); COTE $327 (201301): Cu7C 4702 (2013.01), CUTE 2736 (2013.01); €07€ $/257S (2013.01); CU7C 2980 (2013.01); CO7C 256 (2013.01): COTE 2531/14 2013.01); CO7C 2531/24 (2013.01) COPC 2531/02 2013.01) on ABSTRACT A process for manufieturing methyl t-butyl ether (MTBE) ‘including (A) an optional fist step including cracking raw ‘material made from or containing ethane and/or propane, t0 form ethylene and recovering the residual uneracked raw ‘material, (B) a second step including dimerizing eylene to form n-butylene, (C) a third step including isomerizing the butylene to form isobutylene, (D) an optional foun step ‘including oxidizing methane to form methanol (F) fifth sep inchnding etheriving the isobutylene with methanol t0 form methyl t-butyl ether, and (F) a sixth step including collecting the methyl t-butyl ether is provided, The process can also be used to prepare gasoline alkylate, a higher ‘molecular weight ethylene oligomer, a higher-molecua Weigh-cthylene-oligomerbased melhyl ether, an isom ized higher molecular weight ethylene oligomer, or an ‘somerized-higher molecular-weight-thylene-oligomer: based methyl ether 250° 240 270. Patent Application Publication Dec. 22,2016 Sheet 1 of 2 US 2016/0368848 Al FIG. 1 Patent Application Publication Dec. 22,2016 Sheet 2 of 2 US 2016/0368848 A1 FIG. 2 US 2016/0368848 AI PROCESS FOR MANUFACTURING METHYL TERTIARY-BUTYL ETHER (MIBE) AND. OTHER HYDROCARBONS CROSS-REEERENCE TO RELATED ‘APPLICATIONS. [0001] This application claims beneit of priority wo US. Provisional Application No. 62/183,014 fled on Jun. 22 2015, which is incorporated herein by reference in its ‘entity. FIELD OF THE INVENTION 10002] _In genera, the present disclosure relates the field (of chemistry. More specifically, the present disclosure relates toa process for manufacturing methy teriary-butyl ‘ther (MTBE) and other hydrocarbons. In particulat, the present disclosure relates 19 a process for manufacturing MIBE, other gasoline blend stocks and hydrocarbons from methanol and ethylene BACKGROUND OF THE INVENTION [0003] Methyl butyl ether (MTBE) is a useful additive for gasoline. It isan alternative to lead, has a high octane number, and is miscible with gasoline. MTBE can be ‘manufactired by the etherfiation of isobutylene with methanol, 10004] Alkylates are valued gasoline blend stocks die to their high octane, low vapor pressure and low sulfur content. They may be produced by rescting isobutane with a Cy-C ‘olefin in the presence ofa strong aeid catalyst produce & CC, isoparafinie stream that is often referred to a an alkylate stream, Both of these high value gasotine blend stocks may he produced from a C, olefin feedstock 10005] There is a nood to manufacture MTBE and addi- tional gasoline blend stocks from other feedstocks SUMMARY OF THE INVENTION 10006} The present disclosure relates 10 a process for producing MIBE and gasoline alkylstes wherein olefins suel as ethylene may provide the necessary and cost ellee- live olefinic food component for the production of MTRE and/or gasoline alkylate. In some embodiments, the present disclosure provides a process for manufacturing. methyl {chutyl ether ineluding (A) an optional frst step including () ‘racking. raw-material made from or containing ethane andor propane, to form ethylene and (i) recovering residual luncracked raw material, (B) a second step including () sdimerizing ethylene to form n-butylene, (C) a third step ‘including (i) isomerizing the a-bulylene to form isobutylene, (D)n optional fourth step inchading (i) oxidizing methane to form methanol, (E) a fith step incloding () etheri¥ing the isobutylene with methanol to form methyl t-butyl ether, ‘and (F) sixth step including ()colleeting methyl -huryl ‘ether. In further embodiments, the raw material as prev ‘ously been processed or “cracked” such that a sufi ‘concentration of ethylene is present for being dimerized and forming n-butylene [0007] In some embodiments, the present disclosure pro- Vides a process for manufacturing methyl t-butyl ether ‘wherein the second step further includes ji) recovering unconverted ethylene, (i) alkylating n-burylene with sobu- tane to form gatoline alkylte, and (v) rocavering gasoline alkylate. Dee. 22, 2016 [0008] In addtional embodiments, the present disclosure Provides process for manlacturing methyl butyl ether ‘wherein the second step further includes (i) recovering ‘unconverted ethylene, (¥) dimerizing combinations of at Ieast three ethylene molecules to form a higher molecular ‘weight ethylene oligomer, and (vi) recovering the higher ‘molecular weight ethylene oligomer. In finher embod ‘mens, the present disclosare provides a process foe man- ‘acturing methyl t-butyl ethee wherein the fifth step further includes (i) etherlying the higher molecular weight ethy]- ene oligomer with methanol to form a higher-molecular- Neigh-ethylene-oligomer-bused methyl ether and Gi recovering the higher-molecular-veighi-ethylene-oligomer- ‘based methyl ether. 0009} In some embodiments, the present disclosure pro= Vides a process for manufacturing methyl Uburyl ether ‘wherein the thid step furs inclu i) recovering uncon- verte n-butylene, (i) alkylating isobutylene with isobutane to form gasoline alkylaie, and (iv) recovering. gasoline alkylate, [0010] In further embodiments, the present. disclosure provides 1 process for manufacturing. methyl t-butyl ether ‘wherein the third step further inclu (i) recovering ncom- verted butylene, (Vv) isomerizing a higher molecular ‘weight ethylene oligomer, and (vi) recovering the isomer- ized higher molecular weight ethylene oljgomer. In some ‘embodiments, the resent disclosure provides a proces for ‘manufacturing. methyl t-butyl ether wherein the fifth step further includes i) therifying an isomerized higher ‘molecular weight ethylene oligomer with methanol ro form fan isomerized-higher-molecular-weight-ehylene-oligomer- based methyl ether and (i) recovering the isomerized- hipher-molecular-weight-ethylene-oligomer-based methyl ether [011] In some embodiments, the present disclosure pro- Vides a process for manufacturing methyl butyl ether ‘wherein the optional fourth step further includes (i) reov- ring unconverted methane [0012] In general embodiment, the present disclosure Provides process for manvlacturiag methyl butyl ether Jncluding (A) an optional fist step including @) eraeking ‘iw material made from or containing ethane andlor pro- pane, to form ethylene and (i) recovering residual ‘uneraeked raw material, (B) a second step including (j) imerizing ethylene to form n-butylene, (i) recovering ‘unconverted ethylene (i) alkylating n-butylene wih isobu- tane 10 form gasoline alkylate, (iv) recovering. gasoline alkylate,(¥) dimerizing combinations of at east three eth- ylene molecules to form a higher molecular weight ethylene oligomer, and (vi) recovering the higher molecular weight ethylene oligomer, (C) third step ineluding ()isomerizing the n-butylene to form isobutylene, (i) recovering uncon- verted n-butylene, (i) alkylating isobutylene with isobutane {o form gasoline alkylate, (iv) recovering gasoline alkyl (6) isomerizing a higher molecular weight ethylene ol omer, and (vi) recovering the isomerized higher molecular ‘eight ethylene oligomer, (D) an optional fourth st including () oxidizing methane to form methanol and ( recovering unconverted methane, (F) a fifh step including (@esherifying the isobutylene with methanol ro form methyl trhutyl ether, (i) ethorfying a higher molecular weight ethylene oligomer with methanol to form a higher-molecu- larweight-cthylene-oligomerbased methyl ther, (i recovering the higher-molecularveight-ethlene-oligomer- US 2016/0368848 AI dhyl ether, (iv) etherifying an isomerized higher ‘Weight ethylene oligomer with methanol to forma ‘an isomerizes-higher-molecular-weightethylene-oligomer- bused methyl ether, and (v) recovering the isomerized- higher molecular-weightethylene-oligomer-based methyl ether, and (P) a sixth step including () collecting methyl tcbutyl ether 10013] In a general embodiment, the present disclosure provides for the production of methyl t-butyl ether prepared by a process inluding (A) an optional frst stp including () ‘racking raw material made from or containing ethane ‘and/or propane, io form elylene and (i) recovering residual luneracked raw material, (B) a second step including (i ‘dimerizng ethylene to form a-butylene, (C) a third step ‘including () isomerizing the n-butylene to form isobutylene, (D)an optional fourth step including @) oxidizing methane to fom methanol, (E) a fith step ineloding () ethertying the isobutylene with methanol to Torm methyl t-butyl ether, and (F) a sixth step including () collecting methyl t-butyl clher. 10014) In particular embodiments, the present disclosure provides a method for preparing methyl -butyl ether, gaso- Fine alate, a higher molecular weight ethylene oligomer, ‘a higher-moiecular-weightethylene-oligomer-based methyl ‘ther, an isomerized higher molecular weight ethylene ol omer or an isomerized-igher-molecular-weipht-ethylene- ‘ligomer-based methyl eter. [0015] In some embodiments, the present disclosure pro- vides a method for the preparation of gasoline alkylate ‘racking raw material comprising etn or propane to Form ‘ethylene; dimerizing ethylene 10 fom n-butylene; isomer- ing the n-butylene to form isobutylene; alkylating n-bu- tylene with isobstane to form gasoline alkylte, and recov ‘ering gasoline alkylate. In farther embodiments, the method lor preparing gasoline alkylate cracking raw material com- prises recovering residual uneracked raw material that may be, in certain embodiments, further processed (© produce cetiylene for the production of gasoline alkylate andor MIBE. [0016] In some embodiments, the present disclosure relates to 4 process for manufieturing methyl butyl ether ‘comprising:a frst step comprising dimerizing ethylene 10 Jom n-butylene; a second step comprising isomerizing the s-butylene to form isobutylene using an isomerization eac- ‘or, and a third step comprising etherfying the isobutylene ith methanol to form mith t-butyl ether and recycling the “unreacted normal butenes to the isomerization reactor, [0017] While multiple embodiments are disclosed, still ‘ther embodiments will become apparent o those skilled in the art from the following detailed description. As will be ‘apparent, certain embodiments, as disclosed herein, ane ‘capable of medications in various obvious aspects, ll, ‘without departing from the spirit and scope of the claims as presented herein. Accordingly, the drawings and detailed ‘description are to be regarded a istrative in nature and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS [0018] The following figures illustrate preferred embot- ments of the subject matier disclosed herein, The claimed subject matter may be understood by reference to the following description taken in conjunction with the accom- panying figures, in which like rlerence mimerls identify Tike elements, and in whic: Dee. 22, 2016 [0019] FIG. 1 provides a block flow digaram depicting the ‘manufacture of methyl t-butyl ether from ethylene and ‘methanol [0020] FIG. 2 provides an expanded block flow diagram Sepicting the manufacture of methyl butyl ether and other celhers from ethane and methane. DETAILED DESCRIPTION OF THE INVENTION [0021] The preseat technology is described more fully hoereinalter. However, this technology ean be embodied in ‘many differen forms and should not be construed 25 limited to the embodiments set forth herein; rather, these embed rmenis are provided 30 that this disclosure will satisfy Applicable legal requirements. As such, it will be apparent 9 ‘those skilled inthe art that dhe embodiments can incorporate ‘changes and modifications without departing from the gen- eral scope. Is intended to include all the modifications and alterations in $0 far as the modifications and alterations fcome within the seope of the appended claims or the ‘equivalents thereot [0022] As used Singular forms "a ‘unless the context this specification and the claims, the “an,” and “tho” include plural referents larly dictates otherwise [0023] As used in this specification and the claims, the {erms “comprising,” "containing." or “including” mean that at least the named compound, clement, material, patile, oF nethod step ec. is present in the composition, the article, for the method, but does not exclude the presence of other ‘compounds, elements, materials, particles, or method steps, cc. even ifthe other such compounds, elements, materials particles, or method steps, ete, have the same funetion as that which is named, unless expressly excluded in the claims, Is also to be understood thatthe mention of one oF ‘more method steps does not preclude the presence of addi- ‘ional method steps before or after the combined recited steps oF intervening method steps between those steps expressly identified. [0024] Moreover, itis also to be understood that the lettering of process steps or ingredients is meaas for identifying diserete activities or ingredients and the recited Jettering can be arranged in ay sequence, unless expressly indicated, [0025] For the purpose of the present description and of | the claims which follows, except where otherwise indicated ‘numbers expressing amounts, quantities, percentages, and so forth, are to be understood as being modified by the term about" Also, ranges inelude any combination of the ma ‘mum and minimum points disclosed and include any inter ‘mediate ranges therein, which may or may not be speci cally enumerated herein, [0026] Definitions [0027] In the presen description, the terms “alkyl “alkylation” refers to the transfer ofan alkyl group from one molecule to another, such asthe combining of C,-C, olefins ‘with isobutane in the presence ofa steong. acid catalyst [0028] In the present description, the term “eracking” refers to the breaking dowa of hydrocarbons into smaller alkanes and alkenes by using heat, pressure, catalyst, oF ‘combinations thereof, [0029] In the present description, the toms “dimerizing” ‘or “dimerization” refer 10 the bonding of two identical ‘molec subunit to form a single dimer. The bonding may be covalent or intemolecular, ep. hydrogen bonding US 2016/0368848 AI 10030] In the present description, the terms “etherlying” ‘or “ellrification’” refer tothe conversion of an aleobol to ‘ether in the presence ofan acid, an etherifcation catalyst oF Via the Williamson elher synthesis, 10031) In the present description, the term “firs refers to the order in which a particular step is presented and does not nocestrily indicate that a "sccond” step will he presented. For example, “fst step” refers to the first of a leat one process sep. The tenn doesnot reflect priority, importance ‘or significance in any other way. Similar terms used that ean be used herein include “Sevond,” “third,” “fourth,” ete 0032] In the present description, the term “gasoline alky- late” refers o-a combination of olefin which are formed by alkylation of n-butylene oF iso-hutylene with isobutane. 10033] In the present description, the tem “higher molecular weight ethylene oligomer” refers to 4 combina tion of olefins having @ molecular weight greater than butylene (eg, hexene, octene, ete), which are formed by dimerization of three or more etkylene molecules. 10034) In the present description, the term “isomerizing” refers to the chemical process under which a compound is teansformed into any ofits isomeric forms, (i.e. eompounds with the same chemical composition but with different structures or configurations). 10035] In the present description, the term “n-butylene” refers to all forms of n-butylene, for example, I-butene and 2-butene, trans-2-butene or eis-2-butene, and mixtures thereof, 10036] In a general embodiment, the present disclosure provides» process for manufacturing methyl tury! ethee including a first step including cracking rw material made from or containing ethane andor propane, to form ethylene, ‘and recovering the residual uneracked raw material see ‘ond step including dimerizing ethylene to form n-butylene (and higher molecular weight eliylene oligomers); 10037] third step including isomerizing the n-burylene 10 orm isobutylene: aa optional fourth stp including oxidiz- Jing methane to form methanol fith step ineluding ether- fying the isobutylene with methanol to form methyl t-butyl ether; and a sixth step including collecting methyl Cbuyl ‘ether 10038] The optional first step includes () cracking raw material made from or containing ethane andor propane to ‘orm ethylene and (ji) recovering the residual uncrackes aw material. Steam cracking of hydrocarbon feedstocks pro- ‘duees ethylene, propylene, butenes (I-butene, isobutene, ‘eis-2-butene, and trans-2-butene and mixtures thereof), butadiene, isoprene, aromatics, gasfine components, ete, 1nd combinations thereof. The relative proportions af eth- ylene and propylene produced in steam cracking operat ‘can be modulated by changing the nature of the feedstock ‘and by modifying the operating conditions of the eracking process 10039] In an olefin plant, a hydrocarbon feedstock such as naphtha, pas ol, or other factions of whole exude oil may be mixed with steam, This mixture, afer preheating, i ote subjected to severe thermal cracking at elevated tempers- tures in a pyrolysis furnace. The eracked efllent from the pyrolysis furnace contains variable, gaseous hydrocarbons (fiom 1 35 carbon atoms per molecule). This eluent ‘contains hydrocarbons that are aliphatic, aromatic, saturated, ‘and unsaturated, and may contain significant amounts of molecular bydmgen, The emcked product of a pyralysis fumace is then further processed in the olefin plant t© Dee. 22, 2016 produce various individual product steams such as hydeo- en, ethylene, propylene, mixed hydrocarbons having four Or five earbon atoms per molecule, and pyrolysis gasoline [0040] In some embodiments, the second step of the process inchide () dimerizng eylene to form acbutylene ‘The dimerization catalyst ean be a homogeneous catalyst oF a hetergencous catalyst. Examples of suitable homoge- ‘neous catalysts are taught ia US. Pat, Nos. 3321,546; 4.242.531; 4.476.341; 5,260,499 and 514.178; the tee ings of which are herein incorporated by reference [0041] In certain embodiments, the dimerization catalyst comprises a nickel compound and an organo alin compound, Stitable nickel compounds include nickel salts ‘fa mono-or dicarboxylic acid, such as nickel oleae nickel odecanoate, and nickel octanoate. Other nickel compounds include coordination complexes of onganic phosphines with nickel sals. Examples of such complexes are nickel bis (iethylphosphine) chloride [Ni(EtsP),Clg} nickel bist- phenylphosphine) ostanonte, nickel biseiburylphosphine) Chloride, and nickel bisrieyclohexylphosphine) chloride. [0042] Suitable omano aluminium compounds include those having 1 (02 alkyl groups and 1 10 2 halogen atoms per aluminium atom. In certain embodiements, the alkyl oops have 1 10 5 carbon atoms [0083] One dimerization catalyst is made fom or eoatains Bicks! bis(riphenylphosphine) octanoate and ethyl ahi ium dichloride. The molae ratio Ni: can be, in, oa embodiments, from 09:10 to 1-25, from 00:8 w 1:8, and fom 1:25 to Tk [0044] _ The dimerization rection is typically performed at 4 temperature within a range of from about 10 degrees Celsius to about 100 degrees Cosi (10-100° C), stich a8 from 0-75" C. The dimerization reaction canbe cated out in a liguid or gss phase by contacting ethylene with the catalyst, depending on the ection temperature and pressure temployed. The presure of the dimerization reaction ean be from about 348 KPa to about 13,790 kPa, including from out $00-10,000 KPa, [0048] The dimerization reaction produces a dimerization ‘isto that comprises eiylene, I-butene, and 2-butees ‘Other olefins sel as hexenes and ootenes may be present in the dimerization ‘mixture. In cerain embodiments, the amount of hexenes, octenes, and other higher olefins pro duced can be adjusted, eg. minimized, by selecting an appropriate catalyst and controlling ethylene conversion. Higher butenes selectivities can be achieved by runing at lower ethylene conversions. [0046] The thet step includes ()isomerizing the n-buty- Jene to form isobutylene. Many isomerization catalysts ean be used. Suitable acidic catalysts include acidic ion change resins such a5 sulfonated resins (see, ex, US. Pat No. 3,326,866, the teachings of which are incorporated herein by reference), onganosulfonie acids, phosphor aid carboxylic aids, metal oxides (alumina, Zeon, ulated Yirwonia), mined oxides. (eg. silica-alumina, Zionia- silica, acidic eats, acdc clays (se, e&, U.S. Pat Nos. 6,323,384 and 4992.61, US. Patent Application Publica. tion Nos, 200810249229 and 20060084831, the teachings of which are incorporated herein by reference) [0047] When an acidic catalyst is used, the isomerization can be conduct at temperate from about 40 degrees Cols to about 200 degrees Celis (40-200" C), such as from 100-180° C., and under a pressure of about 345 kPa to about 3450 kPa, ineluding from about $00-10.000 kPa, US 2016/0368848 AI some embodiments, the weight hourly space velocities (WHSV) are maintained at about 0.2 kg feed perky catalyst perhour to about 4 kg feed perky eatalyst pee hour, and from 1k feed per ky of catalyst per hour to about 3 ky feed per kg catalyst per hour [0048] The basic isomerization catalysts can be metal ‘oxides such as magnesium oxide, calcium oxide, barium. ‘oxide, and thin oxide, In certain embodiments, meta ‘oxides supported om a carrier may be used. Examples of ‘carters include silica alumina, titania, silca/alumina, and mixtures drool [0049] The isomerization catalysts can be present as beads, granules, pellets, extrudates, tablets, aglomerates, and combinations theron 10050) In some embodiments, an optional fourth step Includes @ oxidizing methane to form methanol. First, methane gas can be converted into a synthesis gas stream ‘consisting of CO, CO. H,O and hydrogen, by the catalytic reforming of methane gas and steam or by partial oxidation. Next, the synthesis pas is catalytically synthesized into smethano 10051} In further embodiments, the fh step includes () ‘ctherfying the isobutylene with methasol to form methyl tchutpl ether. The methanol and the isobutylene can be reacted in the liquid phase over a solid phase strong acid jon-exchange resin catalyst to prodice methyl t-butyl ether (MIBE. 10082] In certin embodiments, 1 mixture of excess methanol and mothy butyl ether can be withdrawn from the etherfication recor and then distilled Wo give a metha- nol/methy| t-butyl ether azeotrope, which may be recycled to the etherifeation reactor, The methyl cbutyl ether ean be collected and further purified by distillation 10053] In some embodiments, the present disclosure pro- Vides a process for manufacturing methyl Uhuiyl ether ‘wherein (B) the second step further inludes (i) recovering unconverted ethylene i) alkylating n-burylene with sobu- tane to form gasoline alkylte, and (iv) recovering gasoline alkylate. 10054) "The alkylation of n-butylene (or isobutylene) with Jsobutane to form gasoline akylate ean be achieved with an alkylation catalyst. Examples of alkylation catalysts include hydroflvorie aid, sulfuric acid, phosphoric acid and metal halides. Furthermore, the catalyst can contain various addi fives or promoters such as boron tifiride, 10055] The alkylation reaction can be carried out with @ substantial molar excess of isobutane, In some embodi- ments, the system operates at a catalysthydrocarbon volume ratio of Il toil, nd from Fl to 3 10086] |The pressure in the rsetors has 10 be at least high ‘enough to keep the n-butylene in the liquid phase for ‘conducting the alkylation reaction. In some embodiments the miniminm presse is about 600 KPa, and the temperature range is about IS degrees Celsius 10 about 50 degrees Celsius (15-50" C.) and from about 25-40° C. 10057] Alternatively, the alkylation can be achieved by an Joni liquid eatalyzed process, whercin at least one hydro- ‘carbon steam is contacted with an ionic liquid catalyst as ‘described, eg. in US. Pat. No. 7.432.408 and U.S. Patent Application Publication No. 20130066130, the teachings of ‘which are incomporated herein by reference: 10058] In adaitional embodiments, the present disclosure Provides « process for mantifacturing methyl butyl ether, ‘wherein (B} the second step further ineludes (iv) recovering Dee. 22, 2016 unconverted ethylene; () dimesiing combinations of at leat thre eiplene molecules 1o form higher molecular ‘wejht eliylene oligomer, and (v) recovering the higher molecular Weight etivlen oligomer {0089} Ia certain embodiments, the preseat diselosire provides a process for manufacturing methyl t-butyl eter, ‘herein (Eth fit step, farber includes: i) etherving "higher molecular weight ethylene oligomer with methanol to foem a highee-molecula-weight-tbylene-oigomer-based methyl ether. and (i) recovering the highcrmolecular- ‘ejghteibylen-ofigomer based methyl ether {0060} In some embustimens, the present disclosure pro- Vides a process for manufasiuring mebyl tbuyl eer ‘wherein (C) the third step, funher includes (i) recovering unconverted n-burylene: (i) alkylating isobutylene with ‘sobutane to form gasoline alkylt; and (iv) recovering the esoinealkylte {0061} 1a some embestimens, the present dislosurepeo- Vides a process for manufacturing methyl Cbutyl elie ‘wherein (©, the thd step farther inludes ijrcovering Uneonverted n-butylene (0) somerzing a higher molecular ‘weight ethylene oligomer, and (vi) recovering the isomer Jed higher molecular sight cthylne oligomer {0062} Ia free embodiments, the present diselosire provides a process for manslaturing methyl t-butyl ether ‘wherein (Ey the th step, farer includes) ethertying higher moiceslar weit ethylene oligomer with ethanol {o form a higher-molevula-weight-ethylene-oigomer-based ‘neti er: (i) recovering the higher-mlectlreweigh cihyleneoligomer-ased methyl ether: (iv) eberiing an Jnomerized higher molecular weight clbyleae oligomer with ‘methanol w form an isomerized-highermolectlr-weight- cthyleneigomer-baod methyl ether and (0) recovering the isomerized -higher-moleculae weight etleneo somer-hosed methyl ether [0063] 1a some embustimens, the present dislosurepeo- Vides a process for manufacturing methyl buy! ether ‘wherein (D), the optional fourth step, further inclodes (3) rpeovering unconverted methane. [0064] In a general embodiment the present disclosure provides a process for manulaeturiag methyl butyl ether Jncluding (A) an optional fist step including @) ening ‘av material made fom o containing tbane andor propane to fom tlene; al i) recovering esi Uneracked ras ‘material (3) second stp inching (i) dimeizing ethylene {© form n-butyene (i) recovering uneonvered eben (Gi) alkylating neburylene with isobutane to foxm gasoline alkslate Gi) recovering gasoline alkylat: (v) dimerzing combinations of at lest three ethylene molocules t form igher molecular Weight eitlene cigomer and (si) weco¥- cing higher molecular eight ethylene oligomer; (C).thind Step inling (i) isomerzing the n-butyene to form isobi- tylene (i) recovering unconverted mbetylene; (i) all dng isobutylene with isobutane to form gasoline alkyote: an Gv) recovering. gasoline alkylte, (0) isomerizing a iipher molecular weight etiylene oligomer and (v) recoy- ering the isomerized higher molecular weight elylene ol omer; (D) an optional four step including (3) oxidizing ethane to form methanol; and (i) recovering unconverted ‘ethane: (E) fifth stop eluding @etherifying the ise fylene with methanol to form methyl t-butyl chen ( iherlying a higher moleclae weight ethylene oligomer ‘ith ethanol to fren bigher-molecularveight-etylene- srbased methyl ether; (i) recovering the higher- US 2016/0368848 AI molecular-weight-thylene-ljgomer-based_methyletbes (iv) etherfying an isomerized higher molecular weight ‘ethylene oligomer with methanol to form an isomerized higher molecular weightethylene-oligomerbased methyl ‘ether; and (v) eeovering the isomerized-higher-molecular- Weightelbylene-oligomerbased methyl ether: and (F) @ sixth step including () collecting meth t-butyl ether 10065] FIG. 1 provides a simplified block flow diagram of ' process for manufacturing methyl butyl ether and other hydrocarbons, including higher molecular weight ethylene ‘oligomers in accordance with the present disclosure somer- ied higher molecular weight ethylene oligomers, and higher-molocular-weightthylene-oligomerhased methyl ‘ethers. The process as depicted involves twa feedstocks: (1) ‘ethylene and (2) methanol 10066] The depicted process exchudes an optional frst step ‘of eracking the aw material. Instead, ethylene is introduced tusing a feed fine 8) into a dimerization unit (100) with @ suitable dimerization catalyst and under appropriate condi- tions. The dimerization nit produces m-butylenes, Any unconverted ethylene is recovered and reeyeled using & recycle line (10) through the dimerization unit 10067] Also, in some embodiments some ethylene units ‘can undergo further dimerization to form higher moleculae ‘weight ethylene oligomers such as hexene and octene. Those higher molecular weight ethylene oligomers can be recov= ‘red or permitted to. prococd through ather steps in the process [0068] Next, the n-butylenes may be introduced using & ood line (120) into an isomerization unit (200) with & suitable isomerization catalyst and under appropriate con- ditions, or removed from the feed line (120) using an ‘extraction Tine (115) for the collection of, e.g high molecu lar weight ethylene oligomer (HIMWEO). The isomerization unit produces isobutylene, which is removed from the unit via an extraction! feed line (220). Any unconverted n-buty- Tene is recovered and reeycled using a reeyele Tine (210) through the isomerization unit (200), 10069] Any higher molecular weight ethylene oligomers that were contained inthe n-hutylene steam can he isomer ined to form isomerized higher molecular weight ethylene ‘oligomer in the isomerization unit (200) ane fed into a feed Tine (230), In turn, the isomerized higher molecular weight ‘ethylene oligomers can be recovered from the process using ‘a recovery line (240), 10070] The depicted process further illustrates the optional our step of oxidizing methane to methanol via intodue- tion of methano! using fee line (260) into an etherifeation unit 300) further comprising 2 suitable etherification eata- Ist. Under appropriate conditions, the etherification unit produces a mixture of excess methanol and methyl t-butyl ‘ether The mixture ean be disiled to give methanol/methyl t-butyl ether azeotrope, and the MTBE may be collected. 10071] Any higher molecular weight ethylene oligomers that Were contsined inthe isobutylene stream can be intro- ‘duced into an etherifieation unit (300) with methanol and a suitable etherification catalyst using the food line (260). Under appropriate conditions, the etherifcation unit pro= duces higher molecular-weight-cthylenc-oligomer-based methyl ether and the higher-moleculat-wegh-ethylene-ol- gomer-based methyl ether may be collected, 10072] FIG. 2 provides an expanded, simplified block flow diagram of a process for manufacturing methyl t-huyl ther ‘and other hydrocarbons in accordance with the present Dee. 22, 2016 disclosure, including higher molecular weight ethylene o ‘gomers, isomerized lecular weight elhslene ol tgomers, and_higher-molecular-veight-ethylene-oligomer- based methyl ethers. The process as depicted invalves (wo feedstocks: (1) ethane and (2) methane, which are respec- tively converted to eiylene and methanol, [0073] ‘The depicted process includes the optional first step ‘of eracking the raw material In this eas, the rw material (ie, feedstock) is ethane. The ethane is introduced into a steam cracker (S00) using a feed line (410) operably con- nected to an ethane source (400). After the ethane is erackod, an etylene-rich stream line (S0) is produced The ethylene ich sircam is introduced into the dimerization unit (100), tnd the process proceeds as described in FIG. 1 0074] As previously-noted, FIG. 2 depicts a process beginning with methane as a feedstock. The methane (ue. alural gis) is introduced into an oxidation processing unit (260) usinga feed line (280), wherein the methane ga is frst converted into a synthesis gas stream and then synthesized fnto methanol, aconrding to the optional fourth step of oxidizing methane to methanol, The resulting methanol is {ntocuced into the etheiication unit (300). [0075] In general embodiment, the present disclosure provides for methyl t-butyl ether prepared by a process Sncluding (A) an optional frst step including (i) cracking ‘aw material made from or containing ethane andor propane to form ethylene; and (i recovering residual uneracked rae ‘material; (B)a second step including (i) dimerizing ethylene to form n-butylene;(C) tied step including () isomerizng the m-butylene to form isobutylene: (D) an optional fours step including () oxidizing methane to form methanol: (E) 4 fith step including (i) ederfying the isobutylene with ‘methanol to form methyl t-butyl ether; and (F) a sith step including (collecting methyl t-butyl ether. 0076] In some embodiments, the present disclosure pro- Vides a method for preparing methy! t-butyl ether, yasoline alkylte higher molecular weight ethylene oligomer, higher molecular-weight-ethylene-ligomer-based methyl ether, isomerized higher molecular weight ethylene oligomer, 0 ‘somerized-higher molecular-weight-

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