catalyst separation, recovery and recycling

CA T A LY S T SE P AR P P A R R TION, RECOVE AA R Y R R A ND RE C Y C LIN G C ata ly s i s by Meta l Comp l exes Vo l ume 3 0 E dito r s: Br i an James , U niversity of British Columbia, Vancouver, Canada Pi et W. N. M. van Leeuwen , U niversity of Amsterdam, The Netherland s A d visory Boar d: A lbert S.C. Chan, T he Hon g Kon g Pol y technic Universit y , Hon g Kon g R obert Crabtee, Y ale University, U.S.A. D avid Cole-Hamilton , U niversity of St An d rews, Scotlan d István Horvát h, E otvos Loran d University, Hungar y Kyo k o Noza ki , University o f To k yo, Japan R o b ert Waymout h , S tanford University, U.S.A . T he titles publishe d in this series are liste d at the en d of this volume. A ND RE C Y C LIN G R OBERT P. TOOZE Fi f e, Scotlan d Edited b y Fi f e, Scotlan d an d EaStCHEM, School o f Chemistr y , Universit y o f St. Andrews,S t. Andrews, D AVID J. COLE-HAMILTO N CA T A LY S T SE P AR P P A R R TION, RECOVE AA R Y R R Sasol Technolo gy (UK) Ltd., St. Andrews , Chemistr y and Process Desi g n A C.I.P. Cata l ogue recor d for t hi s b oo k i s ava il a bl e from t h e L ib rary of Congress. I SBN-10 1-4020-4086-5 ( HB ) I SBN-13 978-1-4020-4086-3 ( HB ) I SBN-10 1-4020-4087-3 ( e- b oo k) I SBN-13 978-1-4020-4087-0 (e-book) Pu bli s h e d b y Spr i nger , P .O. Box 17, 3300 AA Dor d rec h t, T h e Net h er l an d s . 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P rint ed in th e N e th e rlan ds. www .springer.com ww © 2006 Sprin g er C HAPTER 1 H O M OG E N E OUS C ATALY S I S – AD V A N TA G E S A N D PR O BLEM S 1 1 .1 C atal y s i s 1 1 .2 C atalyst S tab i l i ty 4 1.2.1 THERMALLY IND UC ED DE CO MP OS ITI O N 4 1.2.2 C HEMI C ALLY IND UC ED DE CO MP OS ITI O N 5 1.2.3 PHY S I CA L L OSS FR O M THE PR OC E SS 6 1 .3 Layout o f the Book 6 1 .4 Re f erences 8 C HAPTER 2 C LA SS I C AL H O M OG E N E OUS C ATALY S T S EPARATI ON TE C H NO L OG Y 9 2 .1.1 Covera g e of Chapter 9 2.2 G eneral Process C onsiderations 9 2 .3 Ever y th i n g i s a Reactor 10 2 .4 Overv i ew o f S eparat i on Technolo gi es 10 2 .4.1 TR A DITI O N A L CO B A LT WITH CA T A LY S T DE CO MP OS ITI O N 10 2 .4.2 UNION CARBIDE-DAVY GAS RECYCLE PROCESS 11 2 .4.3 LI Q UID RE C Y C LE 12 2 .4.4 BIPHASIC SYSTEMS ; WATER-ORGANIC 14 2 .4.5 IND UC ED PHA S E S EPARATI O N 14 2 .4.6 N O N- AQ UE O U S PH AS E S EP A R A TI O N 15 2.4.6.1 NAPS Usin g a Non-Polar Catal y st . 16 2.4.6.2 NAPS Using a Po l ar Cata l yst . 1 7 2.4.6.3 Ligan d Structure an d S olubility Properties . 17 2.5 Hypothetical processes - How Might the Product be Separated from the C atal y st? 18 2 .5.1 PR O PENE HYDR O F O RMYL A TI O N 19 2 .5.2 1- OC TENE HYDR O F O RMYL A TI O N 20 2 .5.3 ALLYL ALCOHOL 20 2 .5.4 METH O XY V INYLN A PHTH A LENE 21 2 .5.5 S EP A R A TI O N TE C HN O L OG Y F O R LE SS S T A BLE CA T A LY S T S 22 2.5.5.1 Mitsu b is h i TPPO / TPP Separation . 22 2.5.5.2 Organic Po l ymer f or Cata l yst Sta b i l ization . 22 2.6 Real-World Com p lications 22 2 .6.1 O R G AN O PH OS PH O R US LI G AND DE G RADATI O N S 23 TABLE OF C ONTENT S 2.6.1.1 Oxidation . 23 2.6.1.2 Alk y ldiar y lphosphine Formation 2 3 2.6.1.3 Ligand Scrambling 24 2.6.1.4 Phosphine Reactions with Con j u g ate d S y stems . 24 2 .6.1.5 Phos p hite Oxi d ation . 24 2 .6.1.6 Simple Phosphite H y drol y sis 2 5 2 .6.1.7 Poisoning P h osp h ite Formation 25 2 .6.1.8 Al d ehy d e Aci d Formation . 2 5 2 .6.1.9 Aci d ity Control . 26 2.6.2 S EPARATIN G BYPR O D UC T S FR O M REA C TANT S O R PR O D UC T S 27 2 .6.2.1 Alkene Hydrogenation 27 2 .6. 2 . 2A lkene I some r i z ation 27 2.6.2.3 Al d ehy d e Dimerization an d Trimerization . 2 7 2.6.2.4 Formation o f Con j u g ate d C arbon y ls 2 8 2.6.3 INTRIN S I C CA T A LY S T DE AC TI VA TI O N 28 2.7 Further S eparat i on C hallenges 29 2.7.1 RECOVERY OF METAL VALUES FROM A SPENT CATALYST 29 2 .7.1.1 Catal y st Containment an d Capture Technolo g ies . 30 2.8 Concludin g Remarks 35 2. 9 Re f erences 36 C HAPTER 3 S UPPORTED C ATALY S T S 39 Immobilisation of Tailor-ma d e Homogeneous Catalysts . 39 3 .1 Introduction 39 3 .2 S hort Historical O verview 4 0 3 .3 Pol y st y rene S upported C atal y sts 41 3 .4 Si l i ca S upported C atal y st 44 3 .5 Catalysis in Interphases 53 3 .6 Ordered Mesoporous S upport 58 3 .7 Non-covalentl y Supported Catal y sts 60 3 .8 S upported Aqueous Phase C atal y s i s 63 3 .9 Process Des ig n [71] 65 3 .10 Concluding Remarks 68 3 .11 References 69 C HAPTER 4 S EPARATI ON BY S IZE-EX C L US I ON FILTRATI ON 73 H omo g eneous Catal y sts Applied in Membrane Reactors . 73 4 .1 Introduction 73 4 . 2 Reactors 7 4 TA BLE O F CO NTENT S v i 4.2.1 DE A D-END FILTR A TI O N RE AC T O R S 75 4.2.2 C R OSS -FL OW FILTR A TI O N RE AC T O R S 7 6 4 . 3 Membranes 78 4.3.1 C LA SS IFI C ATI O N O F FILTRATI O N TYPE S 78 4.4 Dendrimer Supported Catal y sts 80 4.4.1 KH A R ASC H A DDITI O N RE AC TI O N 81 4.4.2 ALLYLIC SUBSTITUTION REACTI O NS 82 4.4.3 HYDROVINYLATION REACTION 86 4 .4. 4 HYDROGENATION REACTION 88 4.4.5 MI C H A EL A DDITI O N R E AC TI O N 89 4. 5 Dendritic Effects 90 4.6 U nmodified or N on-dendritic C atal y sts 94 4.6.1 HYDR OG ENATI O N 95 4.6.2 PH AS E TR A N S FER CA T A LY S I S 97 4.7 S oluble Polymer S upported C atalysts 98 4.8 C onclud i ng Remarks 102 4.9 References 102 C HAPTER 5 BIPHA S I C S Y S TEM S : W ATER – O R G A N I C 105 5 .2.1 GENERAL 106 5 .2.2 BIPH AS I C S Y S TEM S 107 5 .2.3 A Q UEOUS BIPHASIC CATALYSIS 108 5.2.3.2 Aqueous-p h ase Cata ly sis a s a Unit O peration 1 1 0 5 .2.4 EX A MPLE S O F AQ UE O U S BIPH AS I C CA T A LY S I S 114 5 .2.4.1 Hy d roformylation (Ruhrchemie/Rhône-Poulenc[RCH/RP] process) 114 5 .2.4.2 Other In d ustrially Use d A q ueous-bi p hasic Processes 1 16 5 .2.4.3 Sh ort O vervie w of Ot h er Reaction 11 8 5 .2.5 O THER PR O P OSA L S F O R W A TER - BIPH AS I C S Y S TEM S 119 5 .2.6 INTERL U DE - BIPHA S I C S Y S TEM S : O R G ANI C - O R G ANI C 123 5.3 Recycle and Recovery of Aqueous Catalysts 124 5 .3.1 RE C Y C LIN G 126 5 .3.2 RE CO VERY 128 5 .3.3 E CO N O MI CS O F T HE PR OC E SS 132 5 .3.4 ENVIRONMENTAL ASPECTS 132 5.4 Concludin g Remarks 134 5 . 5 References 1 35 C HAPTER 6 FLUOROU S BIPHA S I C C ATALY S I S 145 6 .1 Introduction 145 4 .3.2 MEMBRANE MATERIALS 7 9 5 .1 Introduct i o n . 1 05 5.2.3.1 W ater as a S olvent . 1 08 5 .2 Immob i l i zat i on w i th the Help o f L i qu i d S upports 10 6 TA BLE O F CO NTENT S v i i 6.2 Alkene H y dro g enat i on 148 6.3 Alkene H y dros i lat i on 151 6.4 Alkene Hydroborat i on 151 6.5 Alkene Hydroformylation 152 6.6 Alkene Epoxidation 158 6.7 O ther O xidation Reactions 161 6.8 All y l i c Alk y lat i on 163 6.9 Heck, S t i lle, S uzuk i , S onagash i ra and Related C oupl i ng React i ons 164 6.10 Asymmetr i c Alkylat i on o f A ldehydes 166 6.11 Miscellaneous Catalytic Reactions 169 6.12 Fluorous Catal y sis Without Fluorous Solvents 170 6.13 Continuous Processin g 171 6.14 Process Sy nthes i s f or the Fluorous B i phas i c H y dro f orm y lat i on o f 1 -Octene 1 75 6.15 C onclus i ons 178 6.16 Acknowledgement 179 6 .1 7 Re f erences 1 79 C HAPTER 7 C ATALY S T RE C Y C LIN G U S IN G IONI C LI Q UID S 183 7 .1 Introduction 1 83 7.1.1 INTRODUCTION TO IONIC LI Q UIDS 183 7.1.2 INTR O D UC TI O N T O TR A N S ITI O N MET A L CA T A LY S I S IN I O NI C L I Q UID S 187 7.1.3 MULTIPHASIC CATALYSIS WITH IONIC LI Q UIDS – ENGINEERING AS PE C T S 189 7.2 Liquid-liquid Biphasic, Rh-catalysed Hydroformylation Using Ionic Liq u i ds 192 7.3 Rhod i um C atalysed Hydro f ormylat i on Us i ng S upported Ion i c L i qu i d Phase S ILP ) C atalys i s 201 7.3.1 SUPPORTED IONIC LI Q UIDS BY CHEMICAL BONDS 203 7.3.2 S UPP O RTED I O NI C LI Q UID S BY IMPRE G N A TI O N 204 7.4 C osts And Econom i cs 206 7.5 C onclus i ons 209 7.6 References 210 C HAPTER 8 SU PER C RITI C AL FL U ID S 215 C ompressed Gases as Mobile Phase and Catal y st Support . 2 1 5 8.1 Introduct i on to supercr i t i cal f lu i ds 215 8.2 Appl i cat i ons o f sc C O 2 in Catalyst Immobilisation 217 8 .2.1 CO 2 AS THE O NLY M ASS S EP A R A TIN G AG ENT 217 8 .2.2 BIPHASIC SYSTEMS CONSISTING OF CO 2 A ND LI Q UID PH AS E S 223 8 .2.2.1 Water as the Liquid Phase . 223 8 .2.2.2 Poly(ethyleneglycol) (PEG) as the Liqui d Phase . 225 8 .2.2.3 Ionic Li q ui d s as the Li q ui d Phase . 2 2 5 8 .2.3 BIPHA S I C S Y S TEM S CO N S I S TIN G O F CO 2 A ND SO LID PH AS E S 23 0 8.2.3.2 8 .2.3.1 Inorganic S upports . 230 Organic Polymer Supports 231 T A BLE O F CO NTENT S v ii i 8.4 S ummar y 234 8 . 5 References 2 3 4 C HAPTER 9 AREAS FOR FURTHER RESEARCH 237 9 .1 Introduct i on 237 9 .2 Conventional Se p aration Methods (See Cha p ter 2) 239 9 .3 C atal y sts on Insoluble S upports (C hapter 3 ) 240 9 .4 C atalysts on S oluble S upports (C hapter 4 ) 241 9 .5 Aqueous B i phas i c C atalys i s (C hapter 5 ) 242 9 .6 Fluorous Biphasic Catalysis (Chapter 6) 243 9 .7 React i ons Involv i n g Ion i c L i qu i ds (C haoter 7 ) 244 9 .8 Reactions Usin g Supercritical Fluids (Chapter 8) 245 9 .9 C onclus i ons 247 9 .10 References 247 8 .3 Econom i c Evaluat i on and S ummar y 232 8.3.1 P O TENTI A L F O R SCA LE- U P 232 T A BLE O F CO NTENT S ix C HAPTER 1 H O M OG E N E OUS C ATALY S I S – AD V A N TA G E S A N D PROBLEM S D. J. COLE-HAMILTON a AND R. P. T OO Z E b a EaStCHEM, School of Chemistry, Univesity of St. Andrews, St. Andrews, a F ife, KY19 9ST, Scotland b Sasol Technology UK, Ltd., Purdie Building, North Haugh, St. Andrews, F i f e, KY19 9ST, Scotlan d 1 .1 C atal y s i s Cata l ysts spee d up c h em i ca l react i ons b ut can b e recovere d unc h ange d at t h e en d of t h e reaction. The y can also direct the reaction towards a specific product and allow C h em i str y to b e carr i e d out at l ower temperatures an d pressures w i t h high er se l ect i v i t y towards the desired product. As a result they are used very extensively in the Chemical In d ustry. C h r i s A d ams, wr i t i ng for T h e Nort h Amer i can Cata l ys i s Soc i ety est i mates that “35% of g lobal GDP depends on catal y sis, althou g h this excludes the emer g en t g enet i c b us i ness. Conf i n i n g t h e ana ly s i s to t h e c h em i ca l s i n d ustr y , w i t h gl o b a l sa l es of p erhaps $1.5 x 1 0 1 2 t h e proport i on of processes us i ng cata l ysts i s 80% an d i ncreas i ng. T he catal y st market itself is US $ 10 10 , so that catal y sis costs are much less than 1% of t h e sa l es revenue from t h e pro d ucts w hi c h t h e y h e l p create. Sma ll won d er t h at t h e cata ly st mar k et i s i ncreas i n g at 5% per annum” [1] TABLE 1.1 Comparison of homo g eneous and hetero g eneous catal y sts H etero g eneous H omo g eneous C atalyst form Solid, often metal or metal oxide Metal complex M o d e of use F i xe d b e d or s l urry D i sso l ve d i n react i on me di um So l vent Usua lly not requ i re d Usua lly requ i re d – can b e pro d uct o r by pro d uc t Se l ect i v i ty Usua ll y poor Can b e tune d Sta bili ty Sta bl e to hi g h temperature Often d ecompose < 100 o C R ec y clabilit y Eas y Can be ver y difficult S pecial reactions Haber process, exhaust clean up etc. Hydroformylation of alkenes, methanol c ar b on yl at i on, as y mmetr i c s y nt h es i s etc T h ere are two ki n d s of cata l ysts. Heterogeneous cata l ysts are i nso l u bl e i n t h e me di um in which the reaction is takin g place so that reactions of g aseous or liquid rea g ents o ccur at the surface, whilst homo g eneous catal y sts are dissolved in the reaction m e di um an d h ence a ll cata l yt i c s i tes are ava il a bl e for react i on. Some of t h e propert i es o f catal y sts are collected in Table 1.1, where hetero g eneous and homo g eneous catal y sts a re com p ared. © 2006 Springer. Printe d in the Netherlan d s. 1 1–8 . D . J J J C o C C l e - H a H H m i l t o n a n d R . P . T o T T o z e (eds.), Catalyst Separation, Recovery and Recycling, [...]... for each material in the mixture 9 D J Cole-Hamilton and R P Tooze (eds.), Catalyst Separation, Recovery and Recycling, 9 C H T ( d C ly Se r c g 9–37 © 2006 Springer Printed in the Netherlands 10 D R BRYANT Everything feasible should be recycled so as to minimize waste Pressures should be kept below 35 bar, at least below 100 bar, to minimize costs and because most process design experience is here... are typical polar solvents The catalyst system is modified to have polarity opposite to the product The ligand provides the basis for the desired catalyst separation selectivity 2.4.6.1 NAPS Using a Non-Polar Catalyst An alkene which will give a polar aldehyde product and syn gas are introduced into the reactor containing a non-polar ligand modified rhodium catalyst Catalyst solution exiting the reactor... stability of the ligand and to the stability of the ligand-modified rhodium complex In separation technologies, as in medicine, the first consideration is to do no harm Not only must one separate product from catalyst, one must also separate catalyst from product In addition, one must separate heavy organic byproducts such as aldehyde dimers and trimers, and separate certain ligand decomposition products... hand-in-hand with catalyst design, often in an iterative fashion That is, a catalyst is selected and tested in a continuous unit, with recycle of streams, to discover if there are problems that will necessitate redesign of the catalyst Redesign is more often the fact than the exception The objective of this chapter is to detail considerations that must be addressed in order to successfully marry a catalyst. .. COLE-HAMILTON AND R P TOOZE 2 Heterogeneous catalysts are generally metals or metal oxides and they tend to give rather unselective reactions They are very stable towards heat and pressure, so can be used at high temperature Only the surface atoms are available for reaction Homogeneous catalysts, on the other hand are usually complexes, which consist of a metal centre surrounded by a set of organic ligands... BRYANT 12 reactants, carbon monoxide, hydrogen and propene The entering gas is passed through the catalyst solution and becomes saturated with aldehyde Gas exiting the reactor is chilled to condense butanal, and the reactant gases are compressed and returned to the reactor One advantage of Gas Recycle operation is that the catalyst remains in the reactor and is thus always working This reduces the inventory... propene and syn gas From the degassing column, the catalyst solution passes to column (4) where aldehyde products and condensation byproducts are separated from catalyst solution The catalyst solution is recycled to the reactor, and the product mixture is transferred to column (5) where isolation of the butanal occurs Feed to tails ratio may be defined as the ratio between the liquid fed to column (4) and. .. product separation, the catalyst is dried and then returned to the reactor (Figure 2.4) aldehyde y Reactor water olefin CO/H 2 Induced Phase Separator distilled water Decanter product l catalyst Water Extractor recycled water/NMP y water catalyst recycle y y Catalyst Drying Primary Water/ Catalyst Separation Figure 2.4 Induced Phase Separation Flow Diagram In this process, catalyst solution leaving... hence the problem of separating, recovering and/ or recycling the catalysts must be addressed, perhaps using innovative solutions [5, 6] There are, then, three critical requirements of any catalyst if it is to be exploited on a commercial scale; these are activity, selectivity and stability It has been widely demonstrated and generally accepted that homogeneous catalysts are superior to their heterogeneous... extent by improvements in catalyst or process design, the last is an intrinsic problem for all manufacturing operations and is the subject of this book Catalysts are traditionally designed and optimised based on their performance in the reactor and not for their ability to withstand traditional separation processes However, on taking any system from the laboratory to the pilot plant and beyond, this need . D . J J J C o C C l e - H a H H m i l t o n a n d R . P . T o T T o z e (eds.), Catalyst Separation, Recovery and Recycling, D . J . CO LE-HAMILT O N AND R. P. T OO ZE 2 Heterogeneous cata l ysts. J. COLE-HAMILTON a AND R. P. T OO Z E b a EaStCHEM, School of Chemistry, Univesity of St. Andrews, St. Andrews, a F ife, KY19 9ST, Scotland b Sasol Technology