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    about chemical reaction

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    © All Rights Reserved
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    3 views7 pages

    Us 20120220804 A 1

    Uploaded by

    hananmaliki
    about chemical reaction

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    © All Rights Reserved
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    US cu») United States c2) Patent Application Publica Mitschke et al. (34) MANUFACTURE OF DIMETHYL ETHER FROM CRUDE METHANOL (75) Inventors: Peter Mitsehke, Maintal (DE) Eckhard Sefdel, Frankfurt am Main (DE); Thomas Renner, Frinktar ‘am Main (DE); Martin Rethaemel Frankl am Main (DE) (73) Assignee: (21) Appl. No. 131509,832 (22). PCT Filed Oct. 25,2010, (86) PCT No. PCTIEPLONGI98 $371 (0M), (2),(4)Dae: May 18,2012 G0) Foreign Application Priority Data Nov. 17,2009 (DB) Nov. 17,2009 (EP) 10 2009 053 357.5 (090143322 20120220804, (10) Pub. No.: US 2012/0220804 Al (43) Pub, Date Aug. 30, 2012 ication Classification 200501) (2006.01) (2006.01), ‘568/698: S880; 422/129 BOL 1900 core 3104 (2) US.CL on ABSTRACT A mettiod of producing dimethyl ether by catalytic dehiydr ‘ion of erude methanol as feedstock in the gas phase includes sroviding the crude methanol from methanol. syathess, ‘where the crude methanol having a total content of earbony ‘compounds of not morethan 100 w-ppm, calculated, as mass ‘equivalents of acetone. The enade methanol is evaporate fand the reaction temperature and reaction presture are adjusted. reactor filled with dehydration catalyst is chargod With the evaporated erude methanol with a defined space velocity. A gaseous produet mixture comprising dimethy] thet, non-reaeted methanol and water is discharged. Cool partial condensation and separation ofthe gaseous prod ‘el mixture ate extried cut so as to provide gaseous dimethy ther, liquid water and methanol as products, andthe metha- polis reineuated, US 2012/0220804 AI MANUFACTURE OF DIMETHYL ETHER FROM CRUDE METHANOL 10001) This application is a U.S. National Phase applic tion under 38 U.S.C. $371 of International Application No. PCT/EP20101006408, fled on Oct. 28,2010, and claimsben- efit European Patent Application No, 09014332. fled on Now. 17, 2009 and Gentin Patent Application No. DE 10 2009 053 3575, fled on November 17, 2009, The Interaa- tional Application was published in German on May 26,2011 ‘88 WO 201 1/060869 Al under PCT Anicle 21 (2) FIELD 0002] ‘This invention relates to the produetion of dimethyl ‘ether from cre methanol. In particular this invention rates toa process for producing dimethyl ether by catalytic deby- «dation of crude methanol inthe pas phase, andto a feedstock. with the use of which a stable long-term operation of the process in eeordance with the invention ean be ensued. This fvention furthermore relates to a plant for performing the process in accordance with the invention, BACKGROUND [0003] The catalytic production of dimethyl ether (OME) from methanol by catalytic debydation is known for many years, The U.S, Pat. No, 2,014,408 for example deseribes @ process for the production and purification of DME. trom methanol on catalysts such as aluminum oxide, titanium ‘oxide and barium oxide, with temperatures of 350 10 400° C, being prefered. 10004} Further information on the conventional practices anon the current practice af the production af dimetbyl ether ‘canbe found in Ullmann’ Encyclopedia of Induseial Chem ‘sty, Sixth Edition, 1998 Electronic Release, keyword “dim- ‘ethyl ether”. In chapter 3 “Production” itis explained in Particular that the catalytic conversion of pure, gascous methanol is performed in a fixed-bed reactor, and after & ‘o-sage condensation the reaction product then i supplied ‘o adisillaton, in which the DME product s separated Irom ‘a methanal-water mixture. The methanol-water mixture then js separatd in a second column, wherein the water is with- drain from the process nd the methanol is again ecrculated into the DME reactor. [0005] Tt should be emphasized thatthe current industrial practice consists in using pure methanol for producing DMF, ‘asitisexplained by Vishwanathan eta, Applied Catalysis ‘General 276 (2008) 281-285. Pure methanol here is under stood to bea purified, largely snbydrous product of methanol synthesis. The direct product of methanol synthesis, om the ‘ther and, is refered to aserude methanol and beside several w1% of water also contains higher alcohols, ethers, esters ketones, aldehydes, hydrocarbons and dissolved synthesis ts constituents each in trace amounts (Ullmana’s Eneyelo- pedis of Industrial Chemisty, Sixth Fition, 1998 Plectronie Release, keyword "Methanol" chapter 4.1.3 “Byproduets") [0006] The production of pure methanol from the direst product ofmethanol synthesis, the erude methanol, generally Js effected by multistage distilation or retfication, wherein inthe first step ina so-called Iow-boiler eokumn the constta- ‘ets witha lover boiling point than methanol are separated. as top prot; also with fear to the removal of dissolved is intermediate product is refered 0 as stabilized Aug. 30, 2012 ede methanol. Occasional, theres als inal effected a Aisillative partial separation of water, wherein the methanol product obtained also is sil refered to a crude methanol bsequenty largely ankydroos pre methanol sobtsned as top pradict in a leost one futher dsilation (Ulimana’s Encjelopedia of lndusteal Chemist, Sinth Eon, 1998 leeuonie Release, keyword “Methanol” chapter $4“Di ‘lation of Crude Metin) [0007] Thepresuctionofpuremetianol ron erademetba- ‘ol involves great expenditure of oth apparatus a ener. Singe in the methanol purfication column lage amounts of the low-boiling methanol must be scpursted fom smaller mounisoltichigh-boiling water Fortheuseo pare mle tol in the succeeding DME production, this represents an cconomic burden since the methanol most agin be evapo ‘ated completely. Therefore the demand exist forquitesame time 1o provide a proteally useful process for producing DMB procesding from erode methanol. The snexemind Geman Patent pplication DE 3817816 AT for example deseribes a process fleyrated in a methanol sya forthe cataste production of DME from methanol by using d= ation elt, which i chargteried in tht the mine merging fom the methanol synthesis reactor ist east partly ‘eovtd ina dehydration reactor on a suiuble caalyt pre exably yA1203, for ecovering DME, witout previous sepa- ‘aon ofthe non-reated symess pas and without pura tion ofthe methanol produced. {0008} ‘The US. Pat No 6,740,783 BI describes process for producing DME from crude methanol. Here, itis cxplined that whea wsing commonly sed alumsins-based dehydration catalysts, the activity ofthe etal impaired bythe water content in the ede mano. Ass solution tis proposed to use a hydrophobic zeolite as dchydration eat Iyst, which i less stongly desetivaed inthe presence of water In ation, the binding of water to strongly Lewis eid enters othe ot catalyst should suppress he cae $onization ofthe catalyst. {0009} A Similar approach is made inthe US. Patent App Eaton US 200910023958 A. Again its te object underly ing the invention to provide a process for the catalytic dehy- dation oferude methanol in the gs pase. According othe inventors isobjectis solved that the erude ethan feed strsam s posse fst overa metal-dopod, hydrophobic zeolite catalyst and subsequently over a catalyst selected fom {-AIOS oF SiO2/A1203, whercin the detydation ection is Performed ia an adibatic reactor According othe iventors, {bis combination of proces features shuld have advantages ‘with respect othe temperature guidance inthe reactor the Jow formation ofbyprouet and the lower catlyst deste tion {0010} Atiogeter it should therefore be note that in vai- ‘us processes or process variants foe producing dimethyl ctor by citalytic dehydration of era methanol in the gas pihse have alteady been proposed, but the proposed pro- esses hive not gained acceptance i the industa! practice. Despite the relevant prior at discussed above, al echnical plants fr prodcing dimethy ther by citalvti debydetion ‘6 methand in the gas phase today stl operate by using pre ethanol as feaistock. Despite the deselbed economic ‘vantages, fundamental disadvanioges therefore seem to exist whea using erode methanol as feedstock, which could bot be overcome to this date SUMMARY, [0011] In an embodiment, the present invention provides ‘method of producing dimethy] ether by catalytic deydration US 2012/0220804 AI ‘oferude methanol as feedstock in the gas phase that includes providing the enide methanol from methanol synthesis, where the erade methanol having a total content of earbony ‘compounds of aot more than 100 wt-ppm, calculated a mass ‘equivalents of acotone. The crude methanol is evaporated and, the reaction temperature and reation pressureare adjusted. A reactor filed with dehydration catalyst is charged with the ‘ceaporated cnide methanol with a defined space velocity. A gaseous product mixture comprising dimethyl ether, non- reacted methanol and water is discharged. Cooling, partial ‘condensation and separation of the gaseous product mixture ‘are carried out sos to provide gaseous dimethyl ether, guid ‘ater and methanol as products and the methanol products recirculated DETAILED DESCRIPTION 10012] An aspect ofthe present invention provides a pro- ‘ess for producing dimethyl ether by catalytic dehydration of ‘rude methanol in the gas pase, which avoids the above mentioned disadvantages and which is suitable for industrial [0013] _Inanembodiment, he presentinvention providesby ‘a process for producing dimethyl ether by eatalytie dehydra- tion oferude methanol inthe gas phase, which comprises the following process steps 10014) (@) providing erode methanol from the methanol synthesis, 10015} (b) evsporating the crude methanol, possibly ater previous stabilization andr after partial separation of water snd adjusting reaction temperature ana reaction presure, [0016] (c) charging a reactor filled With dehydration eata- lyst with the evaporated enude methanol with a defined space velocity, 10017] | (4) discharging a aseous product mixture compris- ing dimethyl ether, non-escted methanol and water, [0018] (e) cooling, partial condensation and separation of the gaseous product mixture, wherein gaseous dimethyl ether ‘swells liquid water and methanol are obtained as products, ‘wherein the methanol is reirculaed to process step I (8), and ‘which is characterized in thatthe eae methanol used as, Teedstock has a total content of carbonyl compounds of aot ‘more than 100 w'-ppm. preferably not more than SO wt-ppm, ‘calculated as mass equivalents of acctone, [0019] Teas found that inthe production of dimethyl ether by catalytic dehydration of erude methanol in the gas phase the content of carbonyl compounds inthe crade methanol has a decisive importance forthe long-term stability ofthe pro- ‘cess, Ths is surprising, since the negative effets of oxyzen- ‘containing tre components on the performance othe pro- ‘duction process or the plant used for this purpose in the production of DMP progseding from erude methanol sofa have not heen discussed or even deni in the prior at. The Interstional Patent Application WO 01/21361. AL for ‘example teaches tht inthe production of short-chain olefins from methanol, which takes place via the intermediate prod- uct DME, the presence of omganic, oxyyen-contaning trace ‘components suc s higher aleaba, aldehydes or other oxy tented compounds only hs an insignificant influeneeon the reaction. By contrast, it has now been find that when ‘excoedinga imit vaeof 100 wt-ppm forthe toal content of ‘carbonyl compounds in the crude methanol feedstock, ealeu- Jated as mass equivalents of acetone, a multitude ofaditional troce components appear in the DME product, which are Undesirable as impurities. This applies in particular forthe Aug. 30, 2012 ‘ase that only the acetone i contained in the crude methanol as earbouyl compound. However, when the ere methanol ‘eedstock also contains higher, potentially more reactive ca- ‘bony! compouids such as methyl ethyl ketone (MEK), fal content of carbonyl compounds in the crude methanol of not ‘more than 50 wt-ppm is preferred, sinew it has been observed that when maintaining this Himit value no unknowa, poten- silly harm trace components appear inthe DME pred. [0020] Te has also heen found that due to condensation or polymerization reaetions these trace components Form said products which lead tothe formation of deposits inside the plant andor on the catalyst, which results in the clogging of plant sections such as heat exchangers the premature deac- tivation ofthe catalyst. Sueh deposits have been observed in corresponding experiments described below. Asan important ingredient ofthe deposits hexametyTbeazene (HMB) coud be identified by means of an analytical determination. The same i obtained ina manner known per se from the reaction ‘of methanol with acetone and duet its high melting point of 165°C. leads othe formation of solid deposit in colder pe sections ant the carbonization of theeatalyst. This reaction is described by Jayamani et l, Indian Journal of Ch Section B: Onganie Chemistry Including Medicinal Chem ‘ey (1985), 24156), 687-9, forthe preparative production of HMB. In the Journal of Catalysis, 119, 288-299 (1980), Ganesan and Pillai also deseribe the resetion of methanol ‘with different ketones and aldehydes on an AI2O3 catalyst to jobiain hexamethylbenzene (HMB), wherein at 350° C. fcetone and MEK are comerted for 100% and HMB is ‘oblained with yields of 87 to 90%, Seen mechanistically, the ‘eacton should always proceed via acetone—independent of the type ofearbonyl compound, so tht aeetone appears to be fn expedient reference component for indicating the foal content of earbonyl compounds This is of particular interest, since enade methanol eotains these compounds and AI03 likewise is used 3s catalyst in the DME production by gas phase processes. Consequently, the undesired condensation ‘reactions fo obtain high-boling compounds such as MBean take place no only with the participation of acetone, but also in the presence of other carbonyl compounds. It should be ‘considered, how ever, that in the experiments described in the paper of Ganesan and Pill avays very high concentrations of the carbonyl compounds of about 16 mol-% were used ‘which les distinctly above the usual concentrations ofthese compounds in the crude methanol, which only amount to some ten to some hundred ppm. [0021] Surprisingly, it was found that list values for tol- ‘mbleamountsof carbonyl compounds in the cade methsnol ‘ean be defined, with the maintenance of which a stable long- tern operation of the DME production plant is possible and 1 impurities are detected in the DME product in disturbing ‘concentrations. It has been Found that fora total content oF tarbony] compounds of not more than 100 wt-ppm, eale- Jatedas mass equivalentof acetone, thesiderevetions proceed to such a subordinate extent that the plant operation and the catalyst are not neyatively influenced. This applies in perticw- Jar forthe case tat only the aeetoneis contained inthe enue ‘methanol. However, when the cae methanol feedstock also contains higher, potentially more reactive carbonyl com- poutds suet as meth] ethyl Ketone (MEK), ftal content of ‘arbory] eompounds inthe cnade methanol of rt more than ‘50 wt-ppm, calculated as mass equivalent of acetone, is pre- ‘ered since it has been observed that when maintaining this Jimit value no unknown, potentially harmful trace compo- US 2012/0220804 AI nents appear in the DME product. Accordingly, correspond- ing limit values can be specified fora enude methanol deter mined a8 feedstock for the DME production, with the ‘maintenance! which an undisturbed operation of the plantis sill possible, and a sulficietly pure DME product is cobained, 10022] In the production of dimethyl ether by catalytic dehydration of pure methanol in the gas phase, said effect, ‘docs not occur, since the total content of carbony/] compounds in the pure methanol is very low, wherein usually only the ‘acetone content is indicated. For example, pure methaol of the purity level “Grate AA” has an acetone content below 20 swe-ppm (Supp, E., How to Produce Methanol from Coal Springer Verlag, Berlin (1989), p. 134), A more recent refer ‘ence specification of the Intemational Methanol Producers and Consumers Association states an acetone limit value of 30 migiky (Janary 2008, biip/hwwwsimpes, be!) 0023) "Te is assumed thatthe problem ofthe presence of ‘oxygen-containing, organi trace components has not been ‘discussed sficently in earlier papers on the catalytic dehy ‘ration of emde methanol in the gas phase fo obtain DME, ‘ine in these papers the attention was directed to the water ‘content ofthe enude methanol. In many ofthe examinations ‘described in the prior art, synthetic enude methanol mixed together from the pure chemicals methanol and water pos bly has been used instead of ere methanol originating Irom echnical plant for methanol synthesis, so tht the above> ‘mentioned problem could not be seen. [0024] |The US. Pat. No. 4,560,807 mentions the possibil- iy of using, beside pure methanol slso 2 non-specified byproduct methanol with a higher content of other oxypen- a8 raw material forthe DMF protion. In this connec tion, the compounds methyl ethyl ether, methyl formate and formal (dimethoxymethane) are mentioned. Hlowever, the indications merely relate to accumulations to be expected of these impurities inthe DME product and not to thir possibly harmful effects on the performance ofthe production process ‘or on the plant itself which is used for this punpose. Inthe ‘merical example contained inthe patent specification only pre methanol again is used, 10025] Inanembodiment ofthe invention, a fxed-bedreve- tor is used as reactor. This type of reactor is characterized by constructive simplicity and has proven quite suecessil ia, the production of DMF proceeding from pune methanol. 10026) An advantagcous aspect af the process ofthe inven- tion provides to use y-A1203 as catalyst. Other acidic solid

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