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    US9091433B2 - MOnolith Catalyst Sues Thereof - BASF

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    2) United States Patent oy 0s) wy o ey @ (86) 7) (60) on) Mabande et MONOLITH C “ATALYST AND USE THEREOF Inventors: Godwind Tafara Peter Mabande, Limburgeshof (DE Mannheim (DE) Se ‘Soo Yin Chin, joete-Peter 1) Gerald ler, Ludsgshafen( Koermer, Basking Ridge, NJ (US); Dieter Harms, Bad Neandorl (DE); Burkhard Rabe, Husum (DE): Howard Furbeck, Hamilton, NJ (US); Oliver Seel, Nienburg (DE) Assignee: BASF SE (DE) Notice: Subject to any disclaimer, the team ofthis patent is extended or adjusted under 35 us! Appl No PCT Filed PCENa $371 (00), (2.4) Date PCT Pubs No. PCT Pub, Date: Related Provisional spp 20, 2009, Int.Cl. F25C 1308 BOL 1928 Bois 23/40 BOL 2342 BOLs 23/58 BOLI 23/62 BOLs 23/63 BOLL 23/656 B01 2396 BOLI 35/00 Bold 3502 BOLL 35/04 BOL 3700 BOL 3702 Cor $33 core 5393 Bond 21/04 Bors 21/06 Bors 38/10 BOLI 38/12 us.cl. crc C1540) by 192 days. 13821,88 May 18,2010 PCTIEP2010056769 Now. 18, 2011 WO2010/133565 Nov: 28, 2010 Prior Publication Data S 2012/0065443.A1 Mar. 15,2012 Application Data ication No. 61/179.918, filed on May (2006.01) (2006.01) (2006.01) (2006.01) (2005.01), (2006.01) (2005.01), (2006.01) (2005.01), (2006.01) (2006.01) (2008.01) (2005.01), (2006.01) (2005.01), (2006.01) (2005.01) (2006.01) (2006.01) (2006.01) F23C 13/08 2013.01); BOLI 192485 (2013.01); BoLs 21/066 (2013.01); Bots 23/40 (2013.01), Bond 2442 (2013.01), BOLI 258 (2013 01); BOL 24/624 (2013.01), BOLI 2768 'US009091433B2 (10) Patent No.: US 9,091,433 B2 (45) Date of Patent: Jul. 28, 2015 (2013.01), BoLs 28/6567 2013.01), BOLE 24196 (2013.01): BOLJ 38/002 (2013.01): BOLT 3570026 (2013.01), BOLT 35023 (2013.01) ‘BOLT 35/04 (2013.01); BOLI 370036 (2013.01); BOIS 37/0045 (2013.01): BOLT 37205 (2013.01); BOLT 37/0228 (2013.01) ‘BOLT 3770242 (201301); BOLI 37/0248 (2013.01); €07C 5337 2013.01); C07C 5/493 (201301), BOLI 21/04 (2013.01); BOIL 21/06 2013.01): BOLL 38/40 2013.01), BOL! 3842 (2013.01); CO7C 2523/42 (2013.01), Co7C 2528/62 (2013.01); F23C 29009901 (201301) (58) Field of None ‘See application file for complete search history. tassfication Search 66) References Cited US. PATENT DOCUMENTS 3440461 A 611969 Jenkins NeTO4 A ¢ 61972 Dechman etal sasin3 49899 A | S18 Raw eal A * $1988 Ima 85.60 A) ALOR Ima ta A + ‘1005 ‘Spadacin et a caso S| 611956. Chakeaboty a A+ 34908 Durante eta sass A + 122000 Bhaadvaj el S558 S366 BL 42002. Schmit et a Si480370 BL* 112002 Reade sasisss Senso: B2* 82005 Schindler ea. 585.600 (Continsed) FOREIGN PATENT DOCUMENTS tosi2s c 71992 242 AL $2002 (Continued) OTHER PUBLICATIONS "Emmet. Pal H, "Alkylation, omerizaton, Polymerization, Cack- ing and Hydoreforming” Catalysis, vl. 6 (1988), pp. 535-542, Primary Examiner — Walter D Grit Assistant Examiner —Jelitea Perez (74) Attornes, Agent, or Firm — Drinker Biddle & Reath LP 6 ABSTRACT Te invention relates to a catalyst comprising 2 monolith composed of # catalytically inert material with low BET surface area und a catalyst layer which has een applied tothe ‘monolith and comprises, on an oxidic suppor material, at Jeqst one noble metal selected from the group consisting of the noble metals of group VII ofthe Periodic Table of the Elements, optionally tin and/or rheaium, and optionally fur ther metals, wherein the thickness ofthe catalyst layer is 510 500 micrometers, US 9,091,433 B2 Page 2 66) References Cited ee OsTsHs AL ILI 1p Vistas AL '32007 USS. PATENT DOCUMENTS iP TBs AL 102007 2 S61-197012 8911986 2O0ANOLS1 AL* 1/2004 Merenger sssoss IP Sel2oimo A 121986 doogoosoald AL 22004 Schindler » 2008's30034 A 122005, 20040034266 AL Brophy ea » doors? A "82007 Fengetal » oor-stozs0 A 112007 Schindler et a. » 2oos-l1o078 A 52008 Nochi et Wo WO-D420001 A 20o8OITTLIT AL Bendel eal WO WO.D633150 Al WO Wo.633I5t FOREIGN PATENT DOCUMENTS. WO WO.00T8I80 WO Wo.2005036193 od Lame A 32004 wo 102007 DE 1os00 366 C15 1006, wo 02009 DE 19727001 AL 11999 P ONS SH AL 41998 * cited by examiner US 9,091,433 B2 1 MONOLITH CATALYST AND USE THEREOF (CROSS-REPERENCE TO RELATED "APPLICATIONS, ‘This application is a national stage application (under 35, US. $871) of PCTIEP20100056769, fied May 18, 2010, ‘which claims benefit of USS. Provisional Application No. 61/179.918, fled May 20,2009. BACKGROUND OF THE INVENTION ‘The invention relates ta monolith catalyst and tothe use thereat for petrochemical conversions such ws dehydrogens- tions, aromatizations, reforming and combustion. Ta merous petrochemical rections (for example deby- “drogenations, aromatization, reformings and combustion), supported noble metal catalysts are used. The use of suc ‘catalysts is very expensive owing tohigh noble metal costs. In, ‘addition, unfvoruble noble metal distbution and long dif fusion pathways in conventional catalyst lead to low noble metal exploitation, TUS. Pat, No. 4.788.371 describes a process for steam ‘dehydrogenation of dehydrogenatable hydrocarbons in the as phase combined with oxidative reheating ofthe interme- ‘ates, with the same catalyst being used for the selective ‘oxidation of hydrogen and the steam dehydrogenation. Her, hydrogen can be introduced as eo-feed, The catalyst used ‘comprises ible motal of group Vill an alkali metal and a Jurther metal selected from the group consisting ofB, Ga, In, ‘Ge, So and Pb on an inorganic oxide support such as alumi num oxide. The process can be carried out in one o more stages ina fixed or moving bed ‘WO 94/2002] describes a catalyst whieh comprises a sup= port consisting essentially of a mixed oxide of magnesium ‘and aluminum Mg(ADO and also a noble metal of group VII, preferably platinum ametal of group IVA, proferably ti and Possibly an alkali metal, preferably cesium. The catalyst is used inthe dehydrogenation of hydrocarbons, which can be ‘arti ont in the presence of oxygen, TUS. Pt, No. 5,733,518 describes a process for the selec tive oxidation of hydrogen by oxygen in the presence of hydrocarbons such as n-butane overa catalyst comprising & phosphate of germanium, tn, lead, arsenic, antimony or bis- ‘uth, preferably in. The combustion of the hydrogen gener- ates, ina least one reaction zone the heat of reaction neces sary foe the endothermic dehydmgenation, EP-A 838 534 describes a catalyst for the steam-free hydrogenation of alkanes, in particular isobutane in the pres- fence of oxygen. The catalyst used comprises platinum, troup metal applied to @ support comprising tin oxi’ zireo- rium oxide and having a tin content of at least 10%. The ‘oxygen content ofthe feed stream forthe dehydrogenation is ‘calculated so thatthe quantity of heat generated by the com- bustion reaction of hydrogen and oxygen is equal to the _quantty of heat require forthe dehydrogenation "WO 96/3315! deseribes a process forthe dehydrogenation ‘of a C.-C alkane inthe absence of oxygen over a dehydro= nation catalyst eomprising Cr, Mo, Ga, Za ora group VIIT ‘metal with simultaneous oxidation of the resulting hydrogen ‘over a reducible metal oxide, eg, an oxide of i, ln, Sb, Za, ‘T, Ph or Te. The dehydrogenation has to be interrupted at regula intervals in order to reoxidize the reduced oxide hy meansof anoxygen source. US, Pat, No, $490,209 describes ‘corresponding process in which the dehydrogenation step tnd the oxidation step procecs sequentially and the assoc ‘ated catalysis are separated physically from one another 2 Catalysts used for the selective oxidation of hydrogen are ‘oxides of Bi, Sb and Te and also their mixed oxides, Finally, WO 96/33150 describes a pracess in which a C.-Cyalkaneis dehydrogenated overa dehydrogenation cata- Ist ina first stage, the output gas from the dehydrogenation stageis mixed with oxygen and ina second stage, passed over ‘an oxidation catalyst, preferably Bi,Oy, so as (0 selectively ‘oxidize the hydrogen formed to water, and, in a tind stage, the output as from the second stage is again passed over @ {ehydrogenation catalyst. isknown that aromatic hydrocarbons can be obtsine by catalytic. dehydrogenating aromatization of open-shain hydrocarbons (se, for example, Catalysis VI, p. 35-542, ed by P-H. Emmet, Reinhold Publishing Co., New York, 1958) USS. Pat, No, 3449461 describes the dehydrogenating somatization of open-chain C, to Ca parallins to aromatic hydrocarbons including o-xylene with the aid of a sulfur catalyst which comprises a noble metal such as palladium or platinum, TUIS-A 20080044261 describes a process for selectively preparing p-xylene by converting C;, isoalkenes or alkenes ‘over a catalyst which comprises a molecular sieve laden with ‘noble meal of transition group VII DE-A 197 27 O21 describes a process for preparing Cy ‘aromaties from butenes by delydrogenating olefinially ‘unsaturated C, hydrocarbon mixtures obiinable by dimeriz- ing technical C, cuts overaeatalyst which comprises atleast ‘one element of the platinum group on an amphoteric cera suppor. The main reaction product is ethylbenzene; in ade tion, o-ylene is also formed. DETAILED DES CRIPTION OP THE INVENTION Its anobjeet ofthe present vention w provide a process {forthe dehydrogenation of hydrocarbons which ensures igh conversions, space-time yields and selectivities, "The object is achieved by catalyst comprising a monolith ‘composed of a catalytically inert material with low BET surface area anda catalyst layer which has been applied to the ‘monolith and comprises, on an oxidie suppor material, at least one noble mictal selected from the group consisting of the noble metals of group VII ofthe Periodic Table of the Elements, optionally tin and/or rhenium, and optionally fur thee metals, where the thickness ofthe catalyst layer is 50 500 micrometers, ‘The invention provides fixed bed catalysts with signi cantly lowered noble metal requirement and improved per- formance. At the same time, the penetration depth of the catalyst is limited to 5 t0 500 pm, preferably 5 t0 250 ym, more preferably 25 to 250 jm and especially 50 o 250 jm: The peaetration depth ofthe catalyst is Himited by dhe thick ‘ness of the catalyst layer applied 1 the monolith ‘The catalyst layer on the monolith comprises atleast a ceramic oxide as catalyst support and atleast @ noble metal selected from the elements of transition group VII of the Periodic Table ofthe Elements, especially palladium, pat ‘num or rhodium, optionally sheaium and/or tin. The catalyst support are one or more ceramic oxides of elements from the second third and fourth main group and the third and fourth transition group (group IVB) of the elements and of the lan- thanides, expecially MgO, CaO, AL,O,, SiO,, Z20;, TIO,, 1.a,0, and Ce,0;. In 8 particulary preferred embodiment, the catalyst support comprises SiO, and ZrO,, in particular & mixed oxide of SiO, and ZrO Tnaddition to the noble metas of teansition group VIN, itis possible touse further elements: in particular, chentum andlor tin should be understood as additions to the elements of US 9,091,433 B2 3 ‘eanstion group VII. Another constituent isthe addition of or the doping with ether compounds ofthe third min oF ran- sition group (ILA or IIB) or basic compounds such as alkali ‘earths, alkaline earths or rare earths, of their compounds Which can be converted to the comesponding oxides at tem- peratures above XP C. Simultaneous doping witha puraity ‘of the elements mentioned or their eompounds is posible Suitable examples are potassium and lanthanum compounds In adiion, the catalyst may be admixed with sulfur, tella- rium, arsenie, antimony or selenium compounds, which many cases bring about an inerease in the selectivity, presun- ably by paral “poisoning” (moderators) The catalyst layer comprises at east one noble metal fom group VII ofthe Periodic Table of the Elements (Ru, Rh Pi, (0s, IP). The prefered noble metal isplatinum. The catalyst layer may optionally comprise tn and/or rhenium; it prefer ably comprises tn In a prefered embodiment, the catalyst layer comprises platinum and ti In addition, the catalyst xyer may be doped with further metal, Ina prefered embodiment, the catalyst layer eom- prises one or more metals f the third transition group (group IIIB) of the Periodic Table of the Elements including the lanthanides (SY, La, Co, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Br ‘Tm, Yb, Lu), preference being given to cerium and laniha- ‘num, particular preference to lanhsnum. Ina further preferred embodiment, the eatalyst layer com= prises platinum, tn and lanthanum, In addition, the catalyst layer may comprise: metals scleted from the metals of main groups Land Tl of the Peri ‘odie Table of the Flements. In a preferred embodiment, the ‘catalyst layer comprises potassium andor cesium. In a spe cific embodiment, the catalyst layer comprises platinum, in, lanthanum and an alkali metal selected from the group con sisting of potassium and cesium. ‘The catalyst layer comprising the oxidie support material and the at east one noble metal of group VIII ofthe Periodic ‘Table of the Elements, in andor chen snd i appropiate Jurdier meals i applied wo the monolith by washeoating the ‘ataltically setive material, For this purpose iis alterna tively also possible first to apply a catalyst support layer ‘composed of oxidie support material tothe monolith wash- ‘coatiig and to impregnate this layer ina later process step with one or more diferent solutions comprising the metals. “The inventive catalysts are used especially forthe dehy’ “drogenation of alkanes to alkenes, for example of propane 10 propene of of n-butane to butenes (I+ and 2-butene), for LUchydrogenating aromatization and forthe catalytic eombus- tion of hydrogen with oxygen. Monoliths ‘Suitable monolithic structures are either metal or ceramic. Preferably, they consist of single blocks with smal (0-54 ‘mm parallel channels. Preferably monolith pars from either ‘Coming Incorporated or NGK or Denso ae used “The most common material for monolithic strututes is ‘condierte (a ceramic material consisting of magnesia sili, ‘and alumina in the ratio of 2:5:2). Other materials whose ‘monolith structures are commercially available are metals mullite (mixed oxide of silica and alumina, ratio 2:3) and silicon carbide. These materials hove, similar to cordirite, a Jow Brunauer, Frum, and Teller (BET) specific surface area (ex, for eordierite, typically 0.7 m’/g). A low BET surface arcs in the context with his invention sa BET surface aca of 0 o 4 Preferably monolith parts of eordierte are used according to the invention Ceramic monolithic elemeats are avilable with cell den- sitios of 25-1600 epsi (cells per square inch, equal 1 a coll size of $-0.6 mm), By using a higher cell density, the geo- ‘metrical surface area increases and, ths, the catalyst can be sed more effectively. Disadvantages of higher cel densities fare a somewhat more difficult manufacturing process, more ifcult washeoating, and a higher pressure drop over the reactor. However, the pressure drop remains very low for high-cell-density monoliths (ypically a factor of 10 lower) compared 10 @ packed-bed reactor, becamse of the stright ‘monolith channels, Preferably, cell densities of monolithic elements used according tthe presen vention are from 1000 1200 epi, nostprelerably 300 to 600 eps. ‘Ceramie monolithic elements can bepreparedby preparing a mixture of tale, clay, and an alumina-yielding eomponeat And silica, mixing the mixture to form a moldable composi- ‘ion, molding the mixture, deying the preenware, and heating it at a temperature of 1200 t0 100° C. to form a ceramic containing mainly condierte and having alow coeiient oF ‘thermal expansion. Generally speaking. » paste with appeo- priate rheological properties and composition can be extrided into a monolith support. The pase usally consists ofa mixture of ceramie powders of suitable sizes, inorzan andlor organic additives, solvent (water), peptizer (acid) to ‘adjust pH, and a permanent binder (colloidal solution or a sol). The adlitives ean bea plasticizer ora surfactant to adjust the viscosity ofthe pase, oFaremporary binder, which ean be ‘ume off later. Sometimes, glass or carbon fibers are added ‘o enhance the mechanical strength of the monolith. The permanent ine shoo improve teint ofthe eno CCondcrt monoliths can be produced from a batch consis ing of tale, Kaolin, caleined Kaolin, and alumina tha ellee- tively provide a chemical compound of SiO, 4510 $5, ALO, 321040, and MgO 12 to 15 wt 2%, Tale isa material mainly ‘consisting of hydrous magnesium silicate, Mg,Si,0) (OH) Depending on the source and purity ofthe tale, t may also be associated with other minerals sich a tremalite (CaMe, (Si0,).), serpentine (3MgO.2Si0,, 211.0), anthophyllite (Mg,(O4 (Si,0,,),) magnesite (MgCO,), mica, and chlo- sie Extrusion can also be used to produce monoliths of other materials such a8 SIC, B,C, SiNg, BN, AIN, AIO, Z1O,, mullite, Al titanate, ZeB,,'sialon, perovskite, carbon and TO, In extrusion, in addition to the quality ofthe die and the nature and the properties of the materials used to make the smoldable mixture, the additives added, pH, water content and the force used in exteusion are also of importance with respoct to the properties of the monolith products. The add- tives applied in extrusion are, for example, celluloses, CaCl, ethylene alycols, diethylene glycols, alcohols, wax, paraffin, ‘acids and heat-resistant inorganic bers. Resides water, other solvents can also he used such as Ketones, alcohols, and ethers. The ation of aditives may lead to improved prop- erties ofthe monoliths sue as the production of microcracks that enhances the resistance to thermal shock, bettr porosity and absorbability and enhanced meckanieal seagth or alow thermal expansion ‘Washcoating Procedre ‘According to the present invention, the bare monolithic structure is coated with a catalyst support layer comprising ‘ne ormore ceramic oxides or acatalst layer comprising the catalytically ative metals and the optional further (promoter) US 9,091,433 B2 5 ‘elements aleady supported on the ceramic oxide support material, wherein te coating is prodoced by a asheoating procedure “The macroporous siractre of seramie monoliths esl tas the anchoring of the washeoat layer. The manne in ‘which wasboosting fs carid ont can he divided oto ba methods: the macroporous soppot can be (pay) filled with thebigh-sirfacesareawashcoat materia, ora washcost canbe ‘deposited as layer inthe pores onthe ceramic support Pore filling results inthe strongest interaction between sonolith and washecat, 36 most ofthe eva ayer i actualy Hixated inside the pores othe support instead of only being attached tothe extemal surface the monolith channels. Ths type of ‘coating cared out by using a solution (or sob ofthe material tobe depositedorby wsingasolaton containing very Soll colloidal pails. The disadvantage of coating by means of por filing is thatthe anount of eating that ean be ‘posites ite, because alone stage, pores will becom pletely illed andthe washooat wil become inaccessible. Preferably the cays suppor or eau ayer is coated ‘onthemonolithi walls. Coating layeronthemonalith walls has the vantages tht higher loadings are possible an that

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