Water-Gas Shift Catalyst

Abstract

A sintered pelletized catalyst precursor comprising iron oxides, including haematite, and Cr.sub.2O.sub.3 and optionally one or more of Al.sub.2O.sub.3, ZnO, MnO.sub.2, MgO, and/or CuO, the pelletized catalyst precursor having an iron oxide content of 60 wt % to 95 wt %, when expressed as Fe.sub.2O.sub.3, and a Cr(VI) content of less than 0.1 wt %, is physically stable on ignition or when subjected to a reducing gas sufficient to reduce the haematite to magnetite.

Claims

1. A pelletized catalyst precursor in the form of a sintered pellet comprising iron oxides, including haematite, and Cr.sub.2O.sub.3 and optionally one or more of Al.sub.2O.sub.3, ZnO, MnO.sub.2, MgO, and/or CuO, the pelletized catalyst precursor having an iron oxide content of 60 wt % to 95 wt %, when expressed as Fe.sub.2O.sub.3, and a Cr(VI) content of less than 0.1 wt %, both relative to the total weight of the pelletized catalyst precursor and wherein the pelletized catalyst precursor (a) exhibits a loss on ignition of less than 3 wt % and/or (b) when subjected to a step comprising subjecting the pelletized catalyst precursor to a reducing gas sufficient to reduce the haematite to magnetite, exhibits a volume shrinkage of less than 1.5% vol and/or retains at least 40% of its mean horizontal crush strength (MHCS).

2. The pelletized catalyst precursor of claim 1, wherein the Cr.sub.2O.sub.3 or the one or more optional Al.sub.2O.sub.3, ZnO, MnO.sub.2, MgO, or CuO are present in a range of from 1 wt % to 10 wt % relative to the total weight of the pelletized catalyst precursor.

3. The pelletized catalyst precursor of claim 1 that contains CuO in a range of from 1 wt % to 10 wt % relative to the total weight of the pelletized catalyst precursor.

4. The pelletized catalyst precursor of claim 1 that has been pelletized with a pelleting aid or lubricant.

5. The pelletized catalyst precursor of claim 1 wherein essentially all of the iron oxides are present as haematite.

6. The pelletized catalyst precursor of claim 1 comprising acicular haematite.

7. The pelletized catalyst precursor of claim 1 that exhibits a mean horizontal crush strength (MHCS) of 3 kg.sub.F or more when subjected to the reduction step comprising subjecting the pelletized catalyst precursor to the reducing gas sufficient to reduce the haematite to magnetite.

8. The pelletized catalyst precursor of claim 1 consisting of: (a) iron oxide in the form of amorphous or acicular haematite, (b) Cr.sub.2O.sub.3, and optionally one or more of: (c) Al.sub.2O.sub.3, ZnO, MnO.sub.2, MgO, or CuO and/or (d) a pelleting aid or lubricant; the pelletized catalyst precursor having an iron oxide content of 60 wt % to 95 wt % expressed as Fe.sub.2O.sub.3, and a Cr(VI) content of less than 0.1 wt %, both relative to the total weight of the pelletized catalyst precursor and wherein the pelletized catalyst precursor (a) exhibits a loss on ignition of less than 3 wt % and (b) when subjected to a reduction step comprising subjecting the pelletized catalyst precursor to a reducing gas sufficient to reduce the haematite to magnetite, exhibits a volume shrinkage of less than 1.5% vol and/or retains at least 40% of its mean horizontal crush strength (MHCS).

9. The pelletized catalyst precursor of claim 8 that contains CuO in a range of from 1 wt % to 10 wt % relative to the total weight of the pelletized catalyst precursor.

10. The pelletized catalyst precursor of claim 1, wherein the pelletized catalyst precursor is shaped as a cylinder with a length C and a diameter D, the diameter defining a circumference of the cylinder, and has two or more flutes running along its length, and optionally has domed ends of lengths A and B, wherein (A+B+C)/D is in the range of 0.25 to 1.25 and, when one or both of A and B are present, (A+B)/C is in the range of 0.03 to 0.3.

11. The pelletized catalyst precursor according to claim 10, wherein the pelletized catalyst precursor has domed ends of lengths A and B, wherein (A+B+C)/D is in the range of 0.25 to 1.25 and (A+B)/C is in the range of 0.03 to 0.3.

12. The pelletized catalyst precursor of claim 10, wherein (A+B+C)/D is in the range of from 0.50 to 1.00.

13. The pelletized catalyst precursor of claim 10, wherein (A+B)/C is in the range of from 0.05 to 0.25.

14. The pelletized catalyst precursor of claim 10, wherein the pelletized catalyst precursor has 3 to 12 equally spaced flutes running axially along its length.

15. The pelletized catalyst precursor of claim 10, wherein the flutes are semi-circular, elliptical, or U shaped.

16. The pelletized catalyst precursor of claim 10, having 3, 4 or 5 flutes that each have a width d in the range of 0.1D to 0.4D.

17. The pelletized catalyst precursor of claim 10, wherein each of the two or more flutes has a width, which when taken together provide a total flute width that is 35% or less than the circumference of the cylinder.

18. The pelletized catalyst precursor of claim 1 prepared by a method comprising the steps of: (a) combining a solution comprising one or more iron salts and chromium salts with a solution comprising an alkali metal carbonate to form a suspension having a pH in the range of from 2 to 5 to form a suspension comprising precipitated iron and chromium compounds, (b) adding an alkaline compound to the suspension comprising precipitated iron and chromium compounds to raise its pH to at least 7, (c) separating the precipitated iron and chromium compounds from the suspension, (d) washing the separated precipitated iron and chromium compounds to remove residual alkali metal salts, (e) drying the washed precipitated iron and chromium compounds, and either (f)(i) shaping the dried precipitated iron and chromium compounds by pelleting to form a pellet and then calcining the pellet, or, (ii) calcining the dried precipitated iron and chromium compounds and then shaping the calcined material by pelleting to form a pellet, the calcining of step (f)(i) or (f)(ii) being done under inert or non-oxidizing conditions as not to reduce the precipitated iron compounds or oxidize the precipitated chromium compounds.

19. The pelletized catalyst precursor of claim 18, wherein the one or more iron salts comprises iron (II) nitrate, iron (III) nitrate or a mixture thereof.

20. The pelletized catalyst precursor of claim 18, wherein the solution comprising one or more iron salts further comprises a soluble compound of copper, manganese, magnesium, zinc, or aluminum.

21. The pelletized catalyst precursor of claim 18, wherein the combined solution of the iron and chromium salts and the alkali metal carbonate further comprises a particulate metal oxide support material or a particulate metal hydroxide support material.

22. The pelletized catalyst precursor of claim 21, wherein the particulate support material is spherical or comprises support particles having an aspect ratio of at least 2 and an average length within the range of from 500 nm to 1500 nm.

23. The pelletized catalyst precursor of claim 18, wherein the alkali metal carbonate comprises sodium or potassium carbonate, sodium or potassium hydrogen carbonate, or a mixture thereof.

24. The pelletized catalyst precursor of claim 18, wherein the alkaline compound comprises an alkali metal hydroxide.

25. The pelletized catalyst precursor of claim 18, wherein the pH in step (i) is in the range of from 2 to 4.

26. The pelletized catalyst precursor of claim 18, wherein the pH in step (ii) is in the range of from 7 to 10.

27. The pelletized catalyst precursor of claim 18, wherein the washing is performed to reduce the alkali metal content, expressed as alkali metal oxide, of the dried precipitate to 0.25% by weight or less.

28. The pelletized catalyst precursor of claim 18, wherein the drying is performed 150-180 C. in air or non-oxidizing atmosphere so as not to crystallize the precipitated iron compounds.

29. The method according to claim 18, wherein the calcining is performed at a temperature in the range of from 400 C. to 700 C.

30. The method according to claim 18, wherein the non-oxidizing atmosphere is nitrogen or argon, optionally containing 0.1-2% by volume hydrogen.

31. A pelletized water gas shift catalyst prepared by calcining the pelletized catalyst precursor of claim 1 under a reducing atmosphere, so as to reduce at least a portion of the haematite to magnetite, the pelletized water gas shift catalyst containing less than 0.1% by weight of Cr(VI), relative to the total weight of the calcined water gas shift catalyst.

32. The pelletized water gas shift catalyst of claim 31, wherein the reducing atmosphere comprises hydrogen and/or carbon monoxide.

33. The pelletized water gas shift catalyst of claim 31, wherein the reducing atmosphere comprises synthesis gas.

34. The pelletized water gas shift catalyst of claim 31 that exhibits a mean horizontal crush strength (MHCS) of 4 kg.sub.F or more.

35. The pelletized water gas shift catalyst of claim 31, further containing copper, manganese, and/or zinc formed by reduction of the CuO, MnO.sub.2, and/or ZnO in the pelletized catalyst precursor.

36. A process for increasing the hydrogen content of synthesis gas mixture comprising hydrogen, carbon oxides and steam, comprising the step of passing the synthesis gas mixture at an inlet temperature in the range of from 280 C. to 500 C. over the pelletized water-gas shift catalyst according to claim 31 to form a hydrogen-enriched shifted gas mixture.

Description

[0061] The Invention will now be further described by reference to the drawings in which;

[0062] FIG. 1 is a chart depicting the pore size distribution of different catalyst precursors as determined by mercury porosimetry,

[0063] FIG. 2 is a side view, end view and isomeric depiction of a first catalyst pellet having three flutes,

[0064] FIG. 3 is a side view, end view and isomeric depiction of a second catalyst pellet having four flutes,

[0065] FIG. 4 is a side view, end view and isomeric depiction of a third catalyst pellet having five flutes.

[0066] FIGS. 2, 3 and 4 together depict water-gas shift catalyst pellets 10 in the form of solid cylinders 12 having a length C and diameter D, which have three, four or five flutes 14 along its length, equally-spaced around the circumferences of the pellets 10. The cylinders 12 have domed ends 16, 18 of lengths A and B. A and B are the same. The flutes 14 create equally sized lobes 20. The evenly spaced flutes are all semi-circular in cross section.

[0067] The invention is further illustrated by reference to the following Examples.

[0068] Mercury porosomitry was performed using a Micromeritics AutoPore 9520 mercury porosimeter in accordance with ASTM Method D4284-03. Porosimetry Intrusion curves were measured over the pressure range of 0.5 to 60000 psia followed by extrusion down to atmospheric pressure. An equilibration time of 15 seconds was used for each data point on both the intrusion and extrusion curves, the mercury contact angle was taken to be 140 and the mercury surface tension taken as 485 dynes/cm. Samples were dried at 115 C. overnight in an oven prior to analysis. Temperature and pressure effects were compensated for by correction runs on empty penetrometer tubes which were subsequently subtracted from the experimental data.

[0069] Loss on Ignition (LOI) measurements were based on the ASTM D7348 method. 3 g of ground catalyst was weighed and heated from ambient (ca 20 C.) to 900 C. in air for 2 hours. After 2 hours' sample was discharged and allowed to cool before re-weighing, so as to provide a weight loss on ignition (LOI). The LOI value is expressed as a percentage of the dry weight before ignition.

[0070] Crush strength was determined using the average, or mean, horizontal crush strength (MHCS). Horizontal crush strengths were measured by applying force to the sides of the cylindrical pellets as opposed to the domed ends because this provides a better measure of strength in duty. MHCS measurements were carried out using a calibrated CT-6, tonne desktop mechanical strength testing machine on a number of both fresh and discharged pellets (10 to pellets) selected at random. The standard load range was 0 to 500 kg. For more sensitive readings a 50 kg or 5 kg load cell was fitted.

[0071] The pellets were weighed and the diameter and height of the pellets were measured before and after activity testing. From this data the pellet shrinkage and pellet density was calculated. The discharged pellets were first dried overnight at 110 C. to remove any water present before these measurements were taken.

Example 1

[0072] A solution containing iron, chromium, and copper nitrates in the atomic proportions of 90 Fe:8 Cr:2 Cu and having a total metals concentration of about 2M, was added to a near saturated solution of sodium carbonate while continuously stirring and maintaining the temperature at about 60 C. to precipitate a composition comprising iron, chromium, and copper compounds. Acicular iron oxide particles were added to the sodium carbonate solution to form a slurry before addition of the mixed metals nitrates solution. Addition of the metals solution was stopped when the pH was 3.2. While continuing the stirring, the slurry was allowed to de-gas and then the pH adjusted to 7.2 using 47-50% w/w sodium hydroxide solution. The precipitate was filtered and washed until the sodium content (expressed as Na.sub.2O) was below 0.25% by weight. The precipitate was then dried in air at 150 C. to form a dried powder.

[0073] The powder composition was pelleted to either a simple flat-ended cylindrical shape or a domed 5-fluted cylindrical shape as depicted in FIG. 4. The powder composition was doped with a small amount of graphite lubricant to aid pellet ejection from the pelleting die and pelleted to a pellet density of about 2.0 g/cm.sup.3. The dried, cylindrical pellets are referenced in the following as Comparative 1, and the dried domed fluted-cylindrical pellets are referenced in the following as Comparative 2. The pellets had the following dimensions:

TABLE-US-00001 Flute size Example A mm B mm C mm D mm (A + B + C)/D (A + B)/C Width/depth (mm) Comparative 1 4.50 8.50 0.529 Comparative 2 0.25 0.25 4.50 8.50 0.588 0.111 1.8/0.75

[0074] The dried Comparative 1 pellets were subjected to a post pellet calcination in air at 500-550 C. for 0.5 hours. Upon heating, the stresses caused during calcination resulted in fracturing of the pellets.

[0075] The dried Comparative 2 pellets were subjected to a post pellet calcination in either (i) air or (ii) nitrogen, at 500-550 C. for 0.5 hours. In contrast to the cylindrical pellets, the domed, fluted pellets were not fractured by the calcination step. The domed 5-fluted shape was better able to withstand the stresses during calcination than the simple flat ended un-fluted cylinder. The domed fluted catalyst precursor calcined in air is referenced in the following as Example 1 (a). The domed fluted catalyst precursor calcined in nitrogen is referenced in the following as Example 1 (b). The dimensions of the calcined domed fluted pellets were as follows;

TABLE-US-00002 Flute size Example A mm B mm C mm D mm (A + B + C)/D (A + B)/C Width/depth (mm) Example 1(a) 0.25 0.25 4.50 8.30 0.602 0.111 1.8/0.75 Example 1(b) 0.25 0.25 4.50 8.20 0.602 0.111 1.8/0.75

[0076] For comparison, a calcined co-precipitated high temperature shift catalyst composition was prepared as described above except the precipitation was performed so that the addition of the metals solution was stopped when the pH was 1.4-1.7 and the pH was adjusted, after degassing, to 7.6-8.1. The powder composition was pelleted to produce a simple cylindrical shape having the same dimensions as Comparative 1 (length C, 4.50 mm, diameter D, 8.50 mm). The calcined pellet dimensions were length C, 4.50 mm, diameter D, 8.30 mm. This catalyst is referenced in the following as Comparative 3.

[0077] The Physical characteristics of the various catalyst precursors was as follows:

TABLE-US-00003 Catalyst Compar- Compar- Compar- Exam- Exam- Precursor ative 1 ative 2 ative 3 ple 1a ple 1b Loss on Ignition 15.09 14.08 2.05 2.51 2.43 to 900 C. % wt Pellet Density 1.97 1.89 2.18 1.92 2.00 (g/cm.sup.3) Median Pore 365 368 429 960 871 Diameter () Cumulative pore 0.25 0.26 0.21 0.35 0.31 volume (cm.sup.3/g) % Portion of 2 14 6 82 66 pores >60 nm % Portion of 98 85 94 19 35 pores <60 nm % retained crush 11 12 83 45 54 strength Volume 14-15 15-18 1.8 0.2 0.0 Shrinkage on reduction (% vol)

[0078] The pore size distributions as determined by mercury porosimetry are depicted in FIG. 1. FIG. 1 clearly shows the distinct profiles for the calcined catalyst precursors of the present invention (Examples 1 (a) and (b)) compared to the un-calcined catalyst precursors (Comparatives 1 and 2) and the calcined catalyst precursor formed at a different pH (Comparative 3). Whereas the retained crush strength for Comparative 3 is relatively high compared to Examples 1 (a) and (b), it was formed under different pH conditions and so does not have the desired porosity. Moreover, the retained crush strength for the Examples 1 (a) and (b) are superior to the un-calcined precursors. Moreover the volume shrinkage in the Examples 1 (a) and 1 (b) are superior to Comparative 3.

Example 2

[0079] The catalyst precursor were tested for water-gas shift performance in a multi-reactor laboratory test facility. Each reactor contained a 200 mL diluted catalyst bed volume comprising the catalyst precursor (15 ml) thoroughly mixed with fused alpha-alumina chips (3-5 mm).

[0080] The catalyst precursors were reduced in situ using a synthesis gas which was used in the subsequent test procedure. The reduction was performed at a maximum temperature of 460 C. for 4 hours. The same reduction method was used in each case. A catalyst activity was measured by monitoring the CO conversion as the reaction temperature was increased from 350 C.-450 C. All samples were tested under a synthesis gas comprising of 14.0% CO, 6.5% CO.sub.2, 55.5% Hz, 0.5% CH.sub.4 23.5% N.sub.2; at an inlet temperature of 350-450 C., a pressure of 27 barg, and a gas hourly space velocity (GHSV) of 85,000 hr.sup.1. The % molar CO conversion was calculated by using an Emerson X-Stream 4 channel IR spectrometer to measure the CO concentration in the dry inlet and outlet gases and determine the volume of CO consumed during the reaction. The results were as follows;

TABLE-US-00004 CO Conversion (%) Temperature ( C.) 350 375 400 425 450 Comparative 1 12 15 23 28 32 Comparative 2 11 21 28 35 39 Comparative 3 12 18 28 34 37 Example 1(a) 11 15 27 35 42 Example 1(b) 6 17 27 33 38

[0081] The results demonstrate that the shaped calcined catalysts according to the present invention achieve high CO conversions under these conditions, especially at 425-450 C. The domed 5-15 fluted shaped in Comparative 2 and in Example 1 (a) are superior at 425-450 C. to the simple cylindrical shaped catalysts.

Example 3

[0082] The effect of catalyst shape was evaluated. Computer modelling of a series of high temperature shift catalysts catalyst was performed Examples 3a-3c relate to the 3-, 4- and 5-fluted domed cylindrical pellets depicted in FIGS. 2, 3 and 4 respectively. Comparative Example X is a commercially-available high temperature shift catalyst cylindrical pellet currently widely used. The dimensions of the pellets were as follows;

TABLE-US-00005 Flute size Example A mm B mm C mm D mm (A + B + C)/D (A + B)/C Width/depth mm Comparative X 0 0 4.50 8.50 0.529 3a 3 flutes 0.25 0.25 4.50 8.50 0.588 0.111 3.1/1.24 3b 4 flutes 0.25 0.25 4.50 8.50 0.588 0.111 2.3/0.93 3c 5 flutes 0.25 0.25 4.50 8.50 0.588 0.111 1.8/0.75

[0083] Strength analysis: A COMSOL FEM software package produced simulations to assess the relative strengths of the shaped materials. A total of 10 N load was applied vertically along the cross-section of the pellets. The shape was not allowed to be displaced by the applied force and the principle stress was reported along line going through the center of the pellet shape. (The reported values are those along the weakest plane if the shape has two directional planes). The results were normalized to the comparative example.

[0084] Voidage analysis: A DigiPac software package was used to simulate the packing of material in a cylindrical bed. The dimensions of the packed bed were set to 170 mm ID and 240 mm length and the simulated voidage was noted at the center of the bed length to avoid the impacts of the end effects. The resolution used was at 0.2 mm/pixel. The results were normalized to the comparative example.

[0085] Simulation of the pellet strength and flow under the same conditions gave the following;

TABLE-US-00006 Example Relative Crush Strength Relative Voidage X 1.00 1.00 3a 0.70 1.07 3b 1.00 1.07 3c 1.20 1.09

[0086] The results show the fluted catalyst pellets have a higher voidage (and so improved pressure drop) and for 4 and 5 flutes, the same or better crush strength than the commercially available cylindrical catalyst.