AU658241B2 - Alkanol decomposition catalyst - Google Patents

Description

OPI DATE 15/06/93 APPLN. ID 29218/92 Il 11 l1111111111111 I |ll illll AOJP DATE 19/08/93 PCT NUMBER PCT/AU92/00613 i lllll 111111i lili li11 AU9229218 IN ItKNAIIUNAL ArtLILA lluI f rUbinri.U UINutrn int. r-irt.ii 04 Lr rt Ii 1\L-r. t (PCT) (51) International Patent Classification 5 (11) International Publication Number: WO 93/09870 B01J 23/72, 23/74, 23/78 Al (43) International Publication Date: 27 May 1993 (27.05.93) (21) International Application Number: PCT/AU92/00613 (81) Designated States: AT, AU, BB, BG, BR, CA, CH. CS, DE, DK, ES, FI, GB, HU, JP, KP, KR, LK, LU, MG, (22) International Filing Date: 13 November 1992 (13.11.92) MN, MW, NL, NO, PL, RO. RU, SD, SE, UA, US, European patent (AT, BE, CH, DE. DK. ES, FR. GB, GR, IE, IT, LU, MC, NL, SE), OAPI patent (BF, BJ, CF, Priority data: CG, CI, CM, GA, GN, ML, MR. SN, TD, TG).

PK 9491 15 November 1991 (15.11.91) AU Published (71) Applicant (for all designated States except US): THE BRO- With international search report.

KEN HILL PROPRIETARY COMPANY LIMITED [AU/AU]; 600 Bourke Street, Melbourne, VIC 3000

(AU).

(72) Inventor; and Inventor/Applicant (for US only) PERCIVAL, Gordon [AU/AU]; Unit 2, 1310 Dandenong Road, Hughesdale, VIC 3166 (AU).

(74) Agent: GRIFFITH HACK CO.; 3rd Floor, 509 St. Kilda Road, Melbourne, VIC 3004 (AU).

(54) Title: CATALYST AND PROCESS (57) Abstract The specification describes an alkanol decomposition catalyst comprising copper and nickel supported on a suitable carrier. Suitable carriers include silica, magnesia and silica/magnesia. The catalyst may be promoted with an element selected from Groups I to VIII of the Periodic Table. The specification also discloses a process for decomposing an alkanol. The process comprises heating an alkanol to an elevated temperature and contacting the heated alkanol with the alkanol decomposition catalyst.

A method of improving the energy efficiency of methanol when used as a fuel in an internal combustion engine is also disclosed.

The method involves contacting heated methanol with the alkanol decomposition catalyst and combusting the decomposition products in the internal combustion engine.

WO 9Q 3/09870 PCT/ALU92/00613 1 CATALYST AND PROCESS The present invention relates to a catalyst and a process for decomposing an alkanol.

Methanol can be catalytically decomposed to form carbon monoxide and hydrogen, mixtures of which are known as synthesis gas. The catalytic decomposition of methanol can be represented as follows: CHOH CO 2H, However the catalytic decomposition of methanol can result in the production of a number of by-products. The formation of these by-products can be represented by the following equations: CO 3H 2 CH, H 2 0 CO H, 2 CO, H, 2CHO30H -4 CH,OCH3 1120 Methanol has become a widely traded commodity for use primarily in the production of formaldehyde. However it has also found application as a fuel or fuel additive in the transport industry as well as a source of synthesis gas. Synthesis gas derived from methanol has been used in the past as a means \of peak shaving Ln the gas distribution industry. Methanol has also been proposed as a substitute for other fuels used in firing gas turbines. Methanol can be readily manufactured through a series of thermal and catalytic steps from low cost coal, natural gas or biomass.

It can also be easily transported and stored.

One disadvantage of using methanol as a fuel is that it has a lower heat of combustion than gasoline or natural gas and therefore a larger volume of methanol is required for equivalent energy production. Similarly methanol has a 'WO 93/09870 PC/AL92/00613 2 lower heat of combustion than its decomposition products carbon monoxide and hydrogen. Hence the catalytic decomposition of methanol to carbon monoxide and hydrogen could provide a more efficient means of using methanol as a fuel especially in motor vehicles. Table 1 contains enthalpies of reaction for several methanol decomposition reactions and for the combustion reactions of methanol, synthesis gas, dimethyl ether and methane. The data contained in Table 1 demonstrate that the energy output of methanol can be improved by catalytically decomposing the methanol into synthesis gas, combusting the synthesis gas, using the energy of combustion to do useful work and recovering waste heat for use in the catalytic decomposition of the methanol.

TABLE 1: REACTION ENTHALPIES FOR DECOMPOSITION AND COMBUSTION REACTIONS Enthalpy AH, (kcal) 400 0 K 800 0

K

Decomposition Reactions 2CH,OH 2CO 4H, 45.26 49.58 2CH 3 OH CH 3

OCH

3 H,0 -5.34 -4.63 2CHOH 2CHO 2H, 41.68 43.74 Combustion Reactions 2CHOH 30, 2C00, 4H,0 -322.40 -321.46 4H, 30, -4 2CO, 4H,0 -367.66 -371.04 CHOCH3 30, -4 2C00 3H,0 -317.06 -316.83 2CH 40, 2C02 4H,0 -364.96 -341.40 PCr/AU 9 2 0 0 6 13 RECEIVED 03 JUN 1993 3 The decomposition of methanol into carbon monoxide and hydrogen over metal catalysts or metal supported catalysts has been demonstrated in the past.

Normally Group VIII metals and/or metals from Groups I to VII of the Periodic Table of Elements alone or supported on carbon or oxide supports have been disclosed as catalysts.

Many patents and publications describe the decomposition of, and catalysts that decompose, methanol to carbon monoxide and hydrogen. However, the present invention compared with, other compositions shows a catalyst of higher activity or methanol decomposition capacity and a higher selectivity to carbon monoxide and hydrogen without making by-products such as methane, carbon dioxide, dimethyl ether and water except in negligible quantities.

The catalyst described herein is stable, easily controlled in the reactor system, easily regenerated and easily and inexpensively prepared.

It is an object of the invention to provide a catalyst and a process for decomposing alkanols.

Accordingly in a first aspect the present invention provides a catalyst for decomposing an alkanol which catalyst comprises active metals supported on a suitable carrier wherein the active metals are copper and nickel and the carrier is magnesia or a mixture of silica and magnesia.

In a second aspect the present invention provides a process for decomposing an alkanol wheja process comprises heating an alkanol to an elevated temperature and contacting the heated alkanol with a catalyst comprising active metals supported on a suitable carrier wherein te active metals are copper and nickel and the carrier is miagnesia or a mixture of silica and magnesia.

IPEA/SUBSTITUTE SHEET SPcr/AU9 0 00 6 13 RECEIVED 0 3 JUN 1993 4 In a third aspect the present invention provides a method of improving the energy efficiency of methanol when used as a fuel which method comprises heating methanol to an elevated temperature using waste heat, contacting the heated methanol with a catalyst to form decomposition products, combusting the decomposition products with oxygen in the internal combustion engine to form combustion products, using these combustion products to perform useful work and recovering waste heat for heating the methanol wherein the catalyst comprises active metals supported on a suitable carrier, the active metals being copper and nickel and the carrier being magnesia or a mixture of silica and magnesia. The catalyst of the present invention also improves cold start capability due to its high activity thus reducing the auxiliary energy required to heat the methanol prior to starting.

The catalyst and process of the present invention are particularly suited to the decomposition of methanol.

However other alcohols such as ethanol and propanol may be decomposed to form a hydrocarbon and hydrogen.

The copper content of the catalyst may lie in the range from 5 to 95 wt% of the catalyst and the nickel content from 2 to 80 wt9. However preferably the copper content lies in the range from 10 to 80 wt% and the nickel content in the range from 2 to 60 wt%.

The carrier may comprise magnesia or silica/magnesia. The selection of the carrier material has an impact on the activity and selectivity of the catalyst.

Preferably the catalyst is a basic (non-acidic) catalyst which comprises from 10 to 90 wt% of silica and from 0.1 to wt% of magnesia. In particular I IPEA/SUBSTITUTE SHEET WO 93/09870 PCT/A U92/00613 the preferred catalysts have silica comprising 20 to 80 wt% of the catalyst and magnesia comprising 0.1 to 40% by weight of the catalysts.

The catalyst of the invention may be prepared by depositing copper and nickel compounds onto the carrier by kneading and/or precipitation and/or impregnating.

Precipitation or impregnation may be of organic and/or inorganic compounds from aqueous and/or non-aqueous solutions. The carrier material itself may also be prepared by kneading, precipitation and/or impregnation of inorganic and/or organic compounds (for example the silica may be derived from tetramethoxysilane) from aqueous and/or non-aqueous solutions.

The catalyst may contain a promoter or promoters such as an element or elements from Groups I to VIII of the Periodic Table of Elements. Such a promoter may be added by mixing, precipitation and/or impregnation from an aqueous and/or non-aqueous solution. The promoter may comprise from 0.01 to 10 wt% of the catalyst. If alkali metal hydroxide, carbonates or hydrogen carbonates are used during the preparation of the catalyst to precipitate the active metals, the catalyst may contain minor amounts of the alkali metal within the catalyst. These minor amounts may comprise from 0.001 to 10 wt% of the catalyst and may act as a promoter.

The catalyst may be combined, dispersed or otherwise intimately mixed with an inorganic oxide matrix or matrices in proportions that result in a product containing 10 wt% to 100 wt% of the catalyst. Matrices which impart desirable properties to the catalyst such as increased strength, attrition resistance and/or thermal WO 93/09870 PC]'/AL'2/00613 6 stability are preferred. Oxides of aluminium, zirconium, titanium, chromium are examples of such inorganic oxides.

Normally it is desirable to calcine the catalyst in air or dilute air before use. However a reduction period in a hydrogen or a dilute hydrogen atmosphere may activate the catalyst.

The decomposition process can be performed in a fixed or fluidised bed of catalyst. The process conditions preferred are temperatures up to 1000 0 C, more preferably 200 to 700 0 C, a pressure in the range from 0.1 to atmospheres, a methanol mass hourly space velocity (MHSV) in the range from 0.1 to 100 more preferably 0.1 to 50 hr" and any other gas or liquid comprising 0 to volume percent of the feed stream.

The following examples illustrate methods for producing the catalysts of the invention (ii) the process of the invention (iii) the performance of the catalysts of the invention and (iv) the performance of comparative catalysts.

Examples 1 to 6 illustrate methods for producing catalysts of the invention and examples 7 to 16 illustrate the preparation of comparative catalysts.

Example 1 73.2g of magnesium carbonate (MgCO) were dissolved in a minimum amount of dilute nitric acid To this was added 40.3g of nickel nitrate (Ni(NO,) 2 6H 2 0) and 119.2g of copper nitrate 2.5H,0) dissolved in a minimum amount of water. 110g of Ludox" SiO,) were added and the solution well stirred at 'WO 93/09870 93CT/AL'92/00613 7 0 o. Ammonium hydrogen carbonate (NH 4 HCO,) was then added until a pH of 7 was attained. The mixture was heated to 0 C and maintained at that temperature as precipitation occurred.

The precipitate was separated, washed twice with 500 zl of water, was dried overnight at 100 0 C and was calcined at 550 0 C. The calcined material was crushed to 500 pm and then pelleted.

Examples 2, 3 and 4 The preparation of these examples of the catalyst is similar to Example 1 except the amount of copper nitrate was 90g, 67.1g and 29.8g respectively.

Example 73.2g of magnesium carbonate (MgC03) were dissolved in a minimum amount of dilute nitric acid wt 9 To this was added 40.3g of nickel nitrate 6H,0) and 119.2g of copper nitrate (Cu(N0 3 3H,0) dissolved in a minimum amount of water. 1lOg of Ludox" (40% Sio 2 were added and the solution well stirred at 400C. Ammonium hydrogen carbonate (NH 4 HCO,) was then Added until a pH of 7 was attained. The mixture was evaporated down with stirring until a firm paste was obtained and this was then dried at 110 0 C and calcined at 550oC.

Example 6 102.2g of MgCO, were dissolved in a minimum amount of dilute nitric acid (20 To this was added 40.3g of Ni(N0 3 2 6H 2 0 and 69.7g of Cu(N0 3 2 3H,0 dissolved in 400g of H,0. 77.3g of Ludox (40% SiO 2 were added and the solution stirred at 40 0 C. Ammonium hydrogen carbonate was then added until a pH of 7 was attained. The mixture SUBSTITUTE SHEET WO 93/09870 PCT/AL'92/00613 8 was aged for 30 minutes and tl i the temperature was increased to 80°C. This was maintained with continuous stirring until a thick paste remained. The paste was dried at 110 0 C and finally calcined at 550 0 C for 5 hours.

Catalyst Trials The catalysts according to the invention were used in a number of experiments for the decomposition or dissociation of methanol to hydrogen and carbon monoxide.

The experiments were carried out in reactors containing a fixed catalyst bed of particles 300-600 micron size. The conditions used to carry out these experiments and the results of these experiments are given below in Table 2.

It is noted that methanol conversion near 100% can be achieved at high mass hourly space velocities in a small diameter reactor and that the selectivity to hydrogen and carbon monoxide is high. (The stoichiometric ratio of hydrogen to carbon monoxide of 2:1 is nearly achieved).

Very small amounts of by-product, water, methane, carbon dioxide and dimethyl ether) are made over the catalysts prepared according to the invention.

TABLE 2 TRIALS FOR METHANOL DECOMPOSITION CATALYSTS Tnzd Number 1141192/2 -R4/190/2 -Rd/ 194/4 R41207/4 1141200/5 R4/16/4 MD3-3 ::Mf6-1 IvW6-2 NMtD15-2 MD 15-3 Calalyor Example I Example I Example I Example 2 Example 3 -Example 4 Example 5 -Example 6 Example 6 -Example 6 Example 6 Example 6 Cornpostion 1%) S.o1 48 6 55.0 59.8 75.9 34 7 29 0 NIO049 0.59 0.44 0.17 28 4 402 CUO 43 0 37,4 294 16.9 224 222 N-0 7 63 65 93 6.91 9.32 8.58 1 Vfc-ulc trnioslirne atmosphenciatmosphenc atnibsphec a tmospheric ltni osphe iphric atmosphen atmosphc nc atopccatmosplieric I O0kPa Reactor Set 'remperirure C Reactor Temperature

MH-SV

2 Methanol Converston (176) Product Gas (Vow%)

H

2 Co C02 ll1/C( ratio 360 292 0.5 95,6 66 5 33 4 0 1 04 0 (13 1 99 307 66.2 32 4 03 2 04 400 269 2.0 64,9 66.5 33 5 0 1 0 0 0 5 1 99 380 267 1I9 71.2 66.1 33.8 0 1 0 0 04 I 96 440 286 2.0 73.6 67.6 32.3 0)1 0 0 0 7 2109 285 2.0 70.3 67.7 32.3 0 0 0 04 2.10 65 1 34.7 0 02 0 0 3 1.88 294 5.2 99 1 66,0 33 7 0 0 3 0 0 1 1 96 600 288 10.2 88.6 04 04 1 98 425 284 5.1 98.5 67.5 32.2 0 03 0 0 2 10 92.7 67.3 32 4 0 03 0 0 2 08 2 07 diameter quariz reactor-4 15mm dtameter quanz I reactor 4- 4mm diamteter stainless steel reactor

I.

I Dry wetght I g watcrlg of methanol consumed x 100 2. Mass hourly space velocity. g methanol/hour/g of catalyst 4. Not detected by the gas chromatographic analysis or less than 0 05"131 WO 93/09870 PCT/AU92900613 The following examples describe the preparation procedure of those catalysts which lie outside the invention.

Example 7 An aluminium phosphate support was prepared by dissolving 615 g of aluminium nitrate in 4 litres of hot water and adding slowly 190 g of 85% phosphoric acid, followed by 51 g of urea. The solution was heated to 90 0 C and with vigorous stirring concentrated ammonia solution was added until a pH of 8.3 was obtained. The resultant precipitate was otirred for 3 hours, then collected by filtration, dried at 150 0 C overnight, calcined at 400 0 C for 2 hours and ground to <1.2 mm.

77.3 g of Ni(N0 3 2 6H 2 0 were dissolved in 250 ml of methanol and combined with 140 g of the aluminium phosphate support.

The slurry was mixed until firm, then dried at 120 0

C

overnight, calcined at 500 0 C for 2 hours, ground to <1.2 mm and finally pelleted (3mm diameter pellets).

Example 8 63.9 g of Ce02 and La 2 0 3 "Misch Metal" oxide (sized to <500 were added to a solution consisting of 20.2 g of Ni(NO,) 2 .6H 2 0 dissolved in 120 g of methanol. The mixture was stirred until a paste, dried at 110 0 C, calcined at 530 0 C for 4 hours, ground to <1.2 mm and finally pelleted (3 mm pellets).

Example 9 52.3 g of silica support (Aldrich Silica Gel grade 63, size to -250 +150 pm and calcined at 500 0 C for 5 hours) were impregnated with a 7.6 solution of 8.3% H 2 PtC1 6 .6H 2 0 in methanol. The material was dried at 110 0 C, calcined at VWO 93/098703 PCT/A U92/00613 11 450 0 C and then reduced in a 10% H 2 in N 2 stream at 400 0

C

for 2 hours. It was further impregnated with a solution of 24.4 g of Ni(NO 3 2 .6H 2 0 and 6.35 g of Ce(N0 3 3 .6H 2 0 in methanol and then dried and reduced as previously.

Example On 31.8 g of activated charcoal (BDH, LR, particle size 0.85-1.77 mm, SA 856 m 2 /g)7.92 g of Ni(N0 3 2 .6H 2 0 and 6.08 g of Cu(N0 3 2 .3H 2 0 were impregnated from a methanol solution.

The material was dried at 110 0 C and calcined at 300 0 C for 1 hour.

Example 11 37.5 g of Ludox AS40" (ammonia stablised colloidal silica, DuPont) was mixed with 250 g of methanol and combined with 49.59 g of Ni(N0 3 2 .6H 2 0 dissolved in a minimum amount of methanol. The slurry was stirred until a paste then dried at 110 0 C and calcined overnight at 550 0 C. Finally the catalyst powder was pressed, crushed and sized to -500 p~ 250 Im.

Example 12 31 g of MgCO 3 were dissolve- in a minimum amount of dilute

HNO

3 and added t- 38-02 g of Cu(N0 3 2 .3H 2 0 dissolved in a minimum amount of methanol. The slurry was stirred until a paste then dried at 110 0 C and calcined at 550 0 C. Finally the catalyst powder was pressed, crushed and sized to -500 pm 250 pm.

WO 93/09870 PCT/AU92/00613 12 Example 13 Example 12 was repeated except the Cu(N0 2 .3H 2 0 was replaced with 49.59 g of Ni(N0 3 2 .6H 2 0.

Example 14 Example 11 was repeated except the Ni(N0 3 2 .6H 2 0 was replaced with 38.02 g of Cu(N0 3 2 Example 15.5 g of MgC03 were dissolved in a minimum amount of dilute HN03 and added to 18.75 g of Ludox AS40TM mixed with 125 g of methanol. To this solution was added 49.59 g of Ni(NO 3 ),6H 2 0 dissolved in a minimum amount of methanol.

The slurry was stirred until a paste then dried at 110 0

C

and calcined overnight at 550 0 C. Finally the catalyst powder was pressed, crushed and sized to -500 um 250 m.

Example 16 Example 15 was repeated except the Ni(N0 3 2 .6H 2 0 was replaced with 38.02 g of Cu(N0 3 2 .3H 2 0.

Catalysts made according to examples 7 to 16 as well as commercially available catalysts were tested for their capacity to decompose methanol to provide H 2 and CO. The results are reported in Table 3.

Comparing the results in Table 3 with those in Table 2 it can be seen that for the commercial catalyst and catalysts of examples 7 to 16j that either the methanol conversion was inadequate at the specific mass hourly space velocity WO 93/09870 PCT/AU92/00613 13 tested or that the selectivity to hydrogen and carbon monoxide was poor with by-products such as either methane, carbon dioxide, dimethyl ether, water or formaldehyde being made in substantial quantities.

Table 3: Trials for Methanol Decoiaposition Catalysts (which are outside the scope of the invention) Availablc Catalysts BliPR-ML Preparcd Inal N'umber R4/13913 R4Il14fl 1141140/3 1131103/3 .03/102f.1 R3/12913 R3/1 1013 R411612 catalysi Zinc Chromnite C-)p4r Copper Copper Zinc Chromtile Copper Zinc Nickel on Nickel on Ccn,.

Chromiitc Chromitc Chromitc on Alumina Churmite Aluminium Lanthana Barium Barium Phosphate Promoted Promoted Supplier I 1 1 2 3 4 Exarnplc 7 Examnple 8 Cornpositiono SiO2=8.l A1203=78.9 A110336.4 CnO3=20 3 Cn-203=7 3 CrnO3-43 3 CnO=4 1.4 CnO0=l10,2 Cr2O03=31.1 NiO=-14.2 NiO=7.O ZnO=6l 4 CuO=75 2 CuO=)33 5 CuO--30.3 ZnO=-9,l ZnO--44.5 P2Os-44 9 CeO 2 =40.0 BaO=-7.4 BaO=6.4 CuO=4 11.9 L.aa0=53.O P'ressure Atmospheric Atmospheric Atmospheric Atmospheric Atmospheric Atmospheric Atmosphcric Atmsphecric RcaIctor Set Ilcmipcrarurc 510 515 520 505 495 410 500 4'10 Reactor retnpcrature C*C) 500 502 502 492 488 395 496 476 N11-iSVot 10 10 1 0 10 VO 10 10 Meithanol Conversion 978 17 4 64 8 636 99.5 34.5 99,7 99.8 Product Gas (Vol%) 112 677 447 67 5 674 71 8 670 576 30.8 CO 292 502 288 I 15.6 31.6 198 CI 14 0) 09 06 05 0.7 04 165 495 C02 29 3 7 29 23 72 09 6.1 137 DM~E 01 0.5 03 0.2 4.6 0.1 0 0 C1120 0(4) 0 0 0 0 0 0 0 wattr Setecrivitytmd% 0 1 14 7 1 I 0.6 03 1.9 72 156 112/CO ratio 232 09W 234 2.27 4.60 2.12 2.91 5.13 mm diameter quartz reactor I Dry Weight 2 Mass hourly space vfelocity. g mctitanol/hour/g of catalyst 3 waitcrlg of methianol con.-umcd x 100 41 Not -cctcd by the ga-s chrlu'ursographic analysis or less titan 0 05 wt%

CI

C

-4

M

Table 3: Trials for Methanol Decomposition Catalysts (which are outside the scope of the invention) I3HPR-NL Prtpaircd Inal NumnbcI MD12-5 MD5-1 MD16-1 MD16-2 MD16 *1 MIM&4 m s6 t.il6 caaytNickcl Cena poppcr. Nickc! Nickcl Coppcr Nickcl COPPxr Nsc~cl C 0ppc I Plaunumn SIhe-' xn CaLrbon on Silic-a on Magncsia on Magnesia oil Silica on Silica on Silica Compo s ic M~jgncsia M-i tncsi.

supplict 'Earplc 9 Exampic 10 Exampic I I Examnple 12 Exarnplc 13 Exzunple 1-1 Etanplc 15 Exam"PI 16 Comiposiucniii AIO,=2 8 SIaD2=8S 4 SiO07=A 7 SiO7=33 4 SQ07=50 1 SiO7= 16 7 SiOI=24 6 NiO=-9 5 C.-A 9 7 MgO=50 7 i,.IgO-50 4 .1-1&027 8 M~gO--2 2 1 CeO2 2 =0 20 CUO-9 1 CuO-49 3 cuO rA9 1 Cu0=52 6 p,=O 51 NjO=9 0 NiO=-46 6 NiQ-49 3 NQ0=55 Pit~surc Aimosphchc Aixnosphcric Atrnosphcnc: Airrnosphcric Aunosphcric ALniosplici Airriosphcnc Aiinosphenc 14cicioi St, I cmprcraiurecC 44~0 500 4-40 4CC0 450 360 4120 -CO Rcacior I cmrpciaiurc CC) 314 391 372 342 389 312 362 291 MHSV,7i 5 4 5 3 56 5 5 5 6 56 5 6 5 6 Mct~hanol Convcrsion% 900 522 69 4 61 7 36 7 57 1 62 6 57 4 Pcoduct Gas (Vol%) H2 58 7 63 4 639 65.3 64.9 71 8 6-43 66 3 CIO 32.0 32,6 34.6 30.6 33.5 195 34 9 27 0 CH4 63 1.5 05 02 03 0 1 02 04 C02 02 0 1 03 20 07 1 r 05 1 6 DMIE 2 8 08 07 06 0.7 0 1 01 02 C420 0 0 0 1 4 0 7 5 0 4 wal cr SclccUvIlYuji(%) 4.7 3 8 4 1 05 4 0 7 1 3 1 1 2 HL/CO rato 1 83 1.95 1 84 2 14 1.93 3 68 1 84 2 1,1 mrn diarretcr siajnlcss aiccl reacior 1.Dry Weight 2 Mass hourly spacc velwity. g rrtianot/houd~g ofT catalyst Ig wtcrlg of niiliancil .onsunicd x 100 *t Not dctcicd by ttc: gas cluomiatograpliic: analysis or less titan 0 05 Wtf

Claims (11)

1. An alkanol decomposition catalyst comprising active metals supported on a suitable carrier whe '-in the active metals are copper and nickel and the carrier is magnesia or a mixture of silica and magnesia.

2. An alkanol decomposition catalyst according to Claim 1 wherein copper comprises from 5 to 95 weight per cent of the active metals and nickel comprises from 2 to weight per cent of the active metals.

3. An alkanol decomposition catalyst according to Claim 1 wherein copper comprises from 10 to 80 weight per cent of the active metals and nickel comprises from 2 to weight per cent of the active metals.

4. An alkanol decomposition catalyst according to Claim 1 wherein silica comprises from 10 to 90 weight per cent of the catalyst and magnesia comprises from 0.1 to weight per cent of the catalyst. An alkanol decomposition catalyst according to Claim 1 wherein the catalyst contains a promoter, the promoter being an element selected from Groups 1 to VIII of the Periodic Table.

6. An alkanol decomposition catalyst according to Claim 5 wherein the promoter comprises from .01 to weight per cent of the catalyst.

7. An alkanol decomposition catalyst according to Claim 6 wherein the promoter is an alkali metal. IPEA/SUBSTITUTE SHEET '0'30JUN 1993 16

8. An alkanol decomposition catalyst according to Claim 1 wherein the catalyst is intimately mixed with an inorganic oxide matrix so that the catalyst comprises from to 100 weight per cent of the mixture.

9. A process for decomposing an alkanol which process comprises heating an alkanol to an elevated temperature and contacting the heated alkanol with an alkanol decomposition catalyst according to any one of claims 1 to 8. A process according to Claim 9 wherein the process is performed in a fixed or fluidised bed of catalyst and the temperature lies in a range up to 1000 0 C.

11. A process according to Claim 10 wherein the temperature lies in a range from 200 to 7000C.

12. A process according to Claim 10 wherein the process is performed at a pressure in the range from 0.1 to atmosphere.

13. A process according to Claim 10 wherein the alkanol is introduced into the fixed or fluidised bed at a mass hourly space velocity in a range from 0.1 to 100 hr 1 IPEA/SUBSTITUTE SHEEi INTERNATIONAL SEARCH REPORT Internaional application No. PCT/AU92/00613 A. CLASSIFICATION OF SUB.ECT MATTER Int. C1. 5 B01J 23/72, 23/74, 23/78 According to International Patent Classification (IPC) or to both national classification and IPC It. I:II)DS SEARCIIEI) Minimum documentation searched (classilication system followed by classification symbols) IPC BO1J 11/22, 11/24, 23/72, 23/74, 23/78 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched AU IPC as above Electronic data base consulted during the international search (name of data base, and where practicable, search terms used) Derwent and JAPIO Copper or Cu and Nickel or Ni and Alkanol or Methanol C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to Claim No. US,A, 5075268 (KURASHIGE et al.) 24 December 1991 (24.12.91) X,P See col 4; table 2 (1-3,7-14) X US.A. 4916104 (ISOGAI et al,) 10 April 1990 (10.04.90) (1-3,7-14) A US.A, 4780300 (YOKOYAMA et al.) 25 October 1988 (25.10.88) US.A, 4431566 (SUZUKI et al.) 14 February 1984 (14.02.84) X Col I lines 49-51 (1,4,11) X Further documents are listed X See patent family annex. In the continuation of Box C. Special categories of cited documents later document published after the international filing date or priority date and not in conflict document definin- the general state of the art which is with the application but cited to understand the not considered tole ol particular relevance principle or theory underlying the invention earlier document but published on or alter the document of particular relevance; the claimed international tiling date invention cannot be considered novel or cannot be document which may throw doubts on priority claim(s) considered to involve an inventive step when the or which is cited to establislh the publication date of ocument is taken alone another citation or other special reason (as specified) document of particular relevance; the claimed document referring to an oral disclosure, use, invention cannot be considered to involve an exhibition or other means inventive step when the document is combined "P1" document published prior to the international filing date with one or more other such documents, such but later than the priority date claimed combination being obvious to a person skilled in the art document member of the same patent family Dale I ofthe actual completion ol the international search Date of mailing of the international search report 7 January 1993 (07.01.93) /14. h1J 3 0 9 N.ai and milling addre.ss ol the ISA;AU Authorized officer AUSTRALIAN PATENT OFFICE PO BOX 200 WODEN ACT 2606 AUSTRALIA G. CARTER Facsimile No. 06 2853929 Telephone No. (06) 2832154 Form PCT/ISA/210 (continuation ol first sheet (2)1 (July 1992) copjne *INTE91NATIONAL SEARCH REPORT international application No. PCT/AU92/00613 C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT Category* x x x x x x Citation of document, with indication, where appropriate of' the relevant passages Relevant to Claim No. US,A. 2010427 (EVERSOLE) 14 January 1933 (14.01,33) PaLge 1, col 2: claims 1-4 Der-went Abstract Accession No. 84-134117/22, Class E17, BE,A, 89/8679 (SOC. CHIM. GRANDE PAROISSE) 2 May 1984 (02.05.84) Derwent Abstract Accession No. 87-254435/36, Class E36, JP,A, 62-176545 (IDEMITSU KOSAN 3 August 1987 (03,08.87) Degwent Abstract Accession No. 89-304168/42, Class E17, JP,A, 1-224046 (AGENCY OF [ND. SCI. TECH.) 7 September 1989 (07.09.89) Derwent Abstract Accession No. 84-026649/05, Class E36, JP,A, 58-216742 (MITSUBISHI HEAVY IND, KXK) 16 December 1983 (16.12.83) Patents Abstracts of Japan, C-907, page 109, JP,A, 3-249943 (MITSUBISHI HEAVY IND. LTD) 7 November 1991 (07.11.91) (1-4,71-1) (1-4,7-16) (1-3,7-14) (1-4,7-8,10-14) (1-4,7-14) Form PCT/ISA/210 (continuation of' second sheet)(July 1992) copjne INTr,!RNATIONAL SEARCH REPORT lriI1olinltiorl on patunt laiiy numbenhI, Intornationtl application No. PCfr/AUJ92/006 13 This Annex lists the known publication level patent family members relating to the patent documents cited in the above-mentioned international search report. The Australian Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent Document Cited in Search Patent Family Member Report us 5075268 JP 4200640 us 4916104 EP 324618 JP 1180250 JP 2119941 us 4780300 AU 46959/85 DE 3531757 JP 61061637 CN 95106645 JP 61232201 us 4431566 .IP 57144031 END OF ANNEX Form PCTfl5A1210(patent family anncx)(July 1992) copjnc