WO 2022/069853 PCT/GB2021/052284

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Method for making copper-containing catalysts

This invention relates to methods of manufacture of copper-containing catalysts, in particular copper-containing catalysts suitable for the water-gas shift reaction and methanol synthesis.

5 The copper-containing catalysts for such reactions are generally produced by forming into pellets small discrete particles of an intimate mixture of copper oxide and one or more oxidic materials, generally including zinc oxide, that are not substantially reduced under the conversion reaction process conditions. The intimate mixture is generally made by precipitation of copper compounds and compounds convertible to the other oxidic materials, and/or precipitation of the copper compounds in the presence of the other oxidic materials or compounds convertible thereto, followed by calcination to convert the precipitated copper compounds, and other components as necessary, to the oxides.

In some cases, the copper-containing catalyst has been modified with silica.

15

US6048820 and US9314774 disclose silica-modified methanol synthesis catalysts produced using a single precipitation step employing aluminium nitrate. We have found that materials prepared using this method have relatively low activities.

20 CN101306369 discloses a catalyst preparation method comprising: (1), an acidic solution of Al is precipitated by reaction with a sodium carbonate solution which also contains sodium silicate; (2) Cu and Zn compounds are co-precipitated by reaction with an alkali metal carbonate; and (3) the two obtained co-precipitates are mixed, aged, then filtered, washed, dried and calcined. We have found catalysts prepared by this route using acidic aluminium

25 solutions have relatively low initial activity and poor stability. This may be due in part to a high level of retained alkali in materials prepared via this method.

CN110935478 discloses a catalyst preparation method comprising: (1) carrying out a parallel flow gelling reaction on a mixed solution A and a sodium meta-aluminate solution to obtain a first slurry; (2) adding a mixed solution B and a sodium carbonate solution into the first slurry in a dropwise and parallel flow manner, carrying out a gelling reaction to obtain a second slurry; and (3) carrying out solid-liquid separation on the material obtained in the step (2), and drying, calcining and pelleting the solid phase to obtain the catalyst, wherein the mixed solution A is an aqueous solution containing a soluble copper salt, a soluble zinc salt and a compound

35 containing an element A, the mixed solution B is an aqueous solution containing a soluble copper salt, a soluble aluminium salt and a compound containing an element A, and the element A is one or a plurality of materials selected from boron, phosphorus and silicon. We have found that precipitating the majority of the copper and zinc against alkali metal aluminate in this way produces catalysts with relatively low activities. P101107

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We have found an alternative, simpler, preparation method that provides improved catalyst performance.

Accordingly the invention provides a method for preparing a copper-containing catalyst

5 comprising the steps of: (a) combining an acidic copper-containing solution with a basic precipitant solution in a first precipitation step to form a first precipitate, (b) combining an alkali metal aluminate solution with an acidic solution in a second precipitation step to form a second precipitate, (c) contacting the first and second precipitates together in a further precipitate mixing step to form a catalyst precursor, and (d) washing, drying and calcining the catalyst precursor to form the copper-containing catalyst, wherein at least 70% by weight of the copper in the catalyst is present in the first precipitate and a silica precursor is included in the first precipitation step, the second precipitation step or the precipitate mixing step, to provide a catalyst with a silica content, expressed as SiC>2, in the range of 0.1 to 5.0 wt%.

15 The invention further includes a catalyst obtainable by the method and a process selected from methanol synthesis, methanol steam reforming and water-gas shift using the catalyst.

Key aspects of the present method are the formation of a copper hydroxycarbonate phase and a separately precipitated alumina-containing support phase using a basic alumina source, to

20 produce well dispersed and well supported copper crystallites, combined with the addition of a relatively low level of silica, which has a stabilising effect on the active catalyst components. Unlike CN110935478, the present method requires the majority of the copper to be precipitated against the basic precipitant and included separately from the aluminium source. In this way smaller copper crystallites with higher surface area and having a higher initial activity are

25 produced.

The present method provides catalysts having both high initial activity and excellent stability.

The method includes (a) combining an acidic copper-containing solution with a basic precipitant solution in a first precipitation step to form a first precipitate. The solutions are both preferably aqueous. The acidic copper containing solution may be formed by dissolving copper or copper oxide in a suitable acid, such as nitric acid, or by dissolving one or more soluble copper compounds in water and adding acid if necessary. The one or more copper compounds may be selected from copper (II) nitrate, copper (II) acetate or other water-soluble copper

35 compounds or salts. Copper (II) nitrate is preferred. The acidic copper-containing solution may usefully contain other components suitable for inclusion in copper catalysts. In particular the acidic copper-containing solution may contain one or more soluble zinc compounds. The one or more zinc compounds may be selected from zinc (II) nitrate, zinc (II) acetate or other water-soluble zinc compounds or salts. The acidic copper-containing solution may further P101107

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3 comprise one or more promoter compounds selected from compounds of Mg, Co, Mn, V, Ti, Zr or rare earths. The promoters may stabilise the copper or enhance the properties of the support phase. Magnesium and zirconium compounds are preferred. Suitable magnesium and zirconium compounds are magnesium nitrate and zirconyl nitrate. Suitable promoters for

5 water-gas shift catalysts include potassium and/or caesium. An acid, preferably nitric acid, may be added to the acidic copper-containing solution if desired. Nitrates and nitric acid are preferred because they leave no catalyst poisons in the catalyst upon calcination.

The basic precipitant may be an aqueous solution of an alkali-metal carbonate or bicarbonate, an alkali metal hydroxide or a mixture thereof. Ammonium hydroxide may also be used. The alkaline precipitant in the present method preferably consists of an alkali metal carbonate so that copper hydroxycarbonate materials are precipitated. Potassium or sodium precipitants may be used. Sodium carbonate or potassium carbonate solutions are preferred. The basic precipitant solution may further comprise one or more of the above promoter metals. The pH of

15 the basic precipitant solution may be in the range 9-13. The acidic copper-containing solution and basic precipitant solutions may be added one to another in a first precipitation vessel but are preferably added simultaneously to the first precipitation vessel such that the pH in the first precipitation vessel is maintained between 6 and 9, preferably between 6 and 7. The precipitation step forms a precipitate, which is desirably mixed to form a slurry. If desired, the

20 co-precipitate slurry may be aged to homogenise the precipitate and ripen crystalline materials. Ageing of the co-precipitate slurry may be carried out in a batch or semi-continuous procedure in a first ageing vessel whereby the aqueous slurry of the precipitated material is held in one or more stirred vessels for a period of time. Suspension of the co-precipitate in the liquid can be by mere stirring, the vigour of stirring depending on the tendency of the particles to settle and

25 the viscosity. Alternatively, the co-precipitate slurry may be aged in a pulse-flow reactor as described in W02008/047166, which is herein incorporated by reference. The precipitation and ageing may be performed at temperatures in the range of 10 to 80°C, but is preferably performed at elevated temperature, i.e. in the range 40 to 80°C, more preferably 50 to 80°C, especially 60 to 80°C, as this has been found to produce small crystallites that, after calcination, provide higher copper surface areas. The conditions can be chosen to produce crystalline compounds, for example of the Manasseite, Rosasite, Aurichalcite or Malachite type. The co-precipitation and ageing are preferably operated to produce malachite [Cu2(CC>3)(OH)2], smithsonite [ZnCOs] and/or zincian malachite [(Cu/Zn)2(CC>3)(OH)2] phases, which may be determined by XRD. However, in the present method, the first precipitate need not be aged.

35

In CN110935478, the copper is divided between solution A used in step (1) and the addition in step (2) to the slurry formed in step (1). The copper content in the solution A is 40% to 80% of the copper content in the catalyst. Thus 20-60% of the copper is precipitated by reaction with the alkali metal carbonate solution. In contrast in the present method, at least 70% by weight, P101107

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4 preferably at least 80% by weight, more preferably at least 90% by weight and most preferably at least 95% by weight or essentiality all, i.e. 100% by weight, of the copper in the catalyst is present in the first precipitate. We have found that maximising the copper in the first precipitate allows better control of the overall copper crystallite size compared to the method of

5 CN110935478.

The method further requires a step (b) of combining an alkali metal aluminate solution with an acidic solution in a second precipitation step to form a second precipitate. The alkali metal aluminate is suitably sodium aluminate or potassium aluminate. Sodium aluminate is preferred. The acidic solution may be formed using a suitable acid, such as nitric acid. The pH of the acidic solution may be in the range 0.5-4. The acidic solution may contain one or more copper compounds, one or more zinc compounds and/ or one or more promoter metal compounds as discussed above. If desired, one or more acidic aluminium compounds may also be included. Preferably the second precipitation step consists of combining the alkali metal aluminate

15 solution, such as sodium aluminate solution, with an acidic solution, especially a nitric acid solution, optionally containing one or more promoter compounds, such as magnesium nitrate and/or zirconyl nitrate. The acidic solution and alkali metal aluminate solution may be added one to another in a second precipitation vessel. The final precipitation pH is preferably between 3 and 9, more preferably between 3 and 8. Alternatively, the acidic solution and alkali

20 metal aluminate solution may be added simultaneously to the second precipitation vessel such that the pH in the second precipitation vessel is maintained between 3 and 9, preferably between 3 and 8. Ageing of the precipitate slurry may, if desired, be carried out using the methods described above for the first precipitate. The second precipitation step is also preferably mixed or agitated thereby forming a slurry of the precipitate. The precipitation and

25 ageing may be performed at temperatures in the range of 10 to 80°C but is preferably performed in the range 20 to 70°C, as this has been found to produce suitable support phases with very high surface areas.

Copper compounds need not be included in the second precipitation step. Where copper compounds are included in both the first precipitation step and the second precipitation step, it is preferred that the amount of copper in the second precipitation step is in the range of 0.5 to 20% of the total copper added, more preferably in the range of 0.5 to 10% of the total copper added. Zinc compounds need not be included in the second precipitation step Where zinc compounds are included in both the first precipitation step and the second precipitation step, it

35 is preferred that the amount of zinc in the second precipitation step is in the range of 0.5 to 50% of the total zinc added, more preferably in the range of 0.5 to 40% of the total zinc added, most preferably in the range of 0.5 to 30% of the total zinc added. Where promoter compounds, such as magnesium or zirconium compounds, are included in the catalyst, the P101107

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5 amount added in the first precipitation may be in the range 0-100% of the total, with the balance being added to the second precipitation.

It will be understood that step (a) and step (b) above may be performed in any order, i.e. step

5 (a) may be performed before or after step (b), or step (a) and step (b) may be performed simultaneously. The steps conveniently may be performed in separate precipitation vessels.

The method further requires a step (c) of contacting the first and second precipitates together in a further precipitate mixing step to form a catalyst precursor. This step may be performed by recovering the precipitates from the first and second precipitation steps, for example by filtration or centrifuge, and then combining the recovered precipitates in a slurry of water or other suitable solvent. It is more convenient, however, to combine the slurries of the first and second precipitates together in a mixing vessel. It is preferred that neither of the precipitates is separated and washed prior to the combining step (c).

15

The second precipitate may be added to the first precipitate or vice versa, or the two slurries may be combined simultaneously at a controlled rate. Either precipitate may be subjected to an ageing step prior to mixing with the other precipitate or may be added without previously being aged. Preferably the second precipitate is aged prior to mixing with the unaged first

20 precipitate, after which the mixed precipitate slurry is subjected in step (c) to a final ageing step. This ageing step may be carried out using the methods described above for the first precipitate.

The simple admixture of the precipitate slurries may be performed with stirring or agitation and

25 the resulting mixture held at elevated temperature in the mixing vessel to allow suitable mixing between the precipitates to occur. The resulting mixture may be allowed to mix for a period of 0.1 to 24 hours, at temperature in the range 40 to 80°C, more preferably 50 to 80°C, especially 60 to 80°C. After the mixing and ageing process has taken place for a sufficient time to allow for any necessary physical and/or chemical transformations to take place, the resulting catalyst precursor may conveniently be recovered by filtration, decanting or centrifuging.

In some embodiments, step (c) may be performed at the same time as step (a) or step (b), i.e. the solutions from step (a) may be added to the precipitate of step (b) or the solutions of step

(b) may be added to the precipitate of step (a). In one arrangement, the first precipitation step

35 (a) and the precipitation contacting step (c) occur simultaneously in the same vessel.

In the present method, a silica precursor is included in the first precipitation step, the second precipitation step and/or the further precipitate mixing step, to provide a catalyst with a silica content, expressed as SiC>2, of 0.1 to 5.0 wt%. We have found that lower levels of silica are P101107

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6 surprisingly superior in terms of stability. Hence in preferred embodiments the silica content of the calcined catalyst, expressed as SiC>2, is in the range 0.1 to 3% by weight, 0.1 to 2% by weight and especially 0.2 to 1 .0% by weight.

5 The silica precursor may suitably be a colloidal silica or silica sol and/or a water-soluble silicon compound, such as an alkali metal silicate, e.g. potassium silicate. Organo-silicates, including alkyl-silicates such as tetramethyl-orthosilicate and tetraethyl-orthosilicate may also be used. The silica stabilises the copper during use and thereby improves the long-term activity of the catalyst compared to catalysts without silica.

If an acidic silica sol is used, it may be added in the first precipitation step to the acidic copper- containing solution and/or added to the first precipitation vessel and/or the first ageing vessel, if present. Similarly, a silica sol may be added in the second precipitation step to the acidic solution and/or added to the second precipitation vessel and/or the second ageing vessel, if

15 present. A silica sol may also be added to the mixture of precipitates in the precipitate mixing step (c). Particularly suitable silica sols comprise aqueous dispersions of colloidally dispersed silica having a particle size in the range of 10-20 nm. The pH of the dispersion may be < 7, preferably in the range 2 to 4. The silica concentration in the sol may be 100-400 g/litre. Such sols are available commercially as, for example, Nissan Chemicals Snowtex-O and Grace

20 Ludox HSA.

If a water-soluble silicate, such as an alkali metal silicate, or a basic silica sol is used, it may be added in the first precipitation step to the basic precipitant solution and/or to the first precipitation vessel and/or the first ageing vessel, if present. Similarly, an alkali metal silicate

25 or basic silica sol may be added in the second precipitation step to the alkali metal aluminate solution and/or to the second precipitation vessel and/or the second ageing vessel, if present. An alkali metal silicate or basic silica sol may also be added to the mixture of precipitates in the precipitate mixing step (c). Suitable alkali metal silicates are sodium silicates and potassium silicates. Such alkali silicates are commercially available, for example, as PQ Corporation Kasil 1 , PQ Corporation Kasolv 16 or Zaclon LLC Zacsil 18. The amount of silicon, expressed as SiO2, in the alkali metal silicate solution may be in the range 5-40% wt% preferably 15-30 wt%. Where an alkali metal silicate is used, the alkali metal in the alkali metal silicate may match the alkali metal in the basic precipitant solution or alkali metal aluminate.

35 If an organo-silicate, such as an alkyl-silicate of formula Si(OR)4 where R = C1-C4 alkyl, is used, because it will hydrolyse when contacted with water, it is preferably added to the first and/or second precipitation vessels, the first and/or second ageing vessels, or to the mixed precipitates in the precipitate mixing step (c). P101107

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Unlike CN110935478, it is not necessary in the present method to divide the silica precursor between the precipitation and reaction steps. Accordingly, the silica precursor may be included only in the first precipitation step, only the second precipitation step or only the reaction step.

5 In step (d) the recovered catalyst precursor is washed to remove residual soluble salts that might act as poisons or contaminants during use of the catalysts. Washing of the catalyst precursor may be performed using conventional equipment such as plate-and-frame filter presses, centrifuges or other suitable washing equipment, for example by re-slurrying the catalyst precursor one or more times in salt-free water, or by dynamic cross-flow filtration using an Artisan thickener or Shriver thickener before recovery. For methanol synthesis catalysts, the alkali metal content of the dried catalyst precursor should desirably be reduced to below 0.2% wt, preferably below 0.1% wt, calculated as the respective alkali metal oxide on the dried material on a loss-free basis.

15 The method further requires in step (d) the drying and calcining the catalyst precursor to form the copper-containing catalyst. The drying may comprise heating the damp mixture in discrete stages or continuously over an extended period until the maximum temperature is reached. The drying step may be performed at temperatures in the range of 90 to 150°C, preferably 90 to 130°C under air or an inert gas using conventional drying equipment such as in an oven,

20 rotary drier, spray drier or similar equipment.

The dried composition is typically in the form of a powder. The average particle size (as determined by sieve fractions, i.e. the weight-average particle size) may be in the range of 10- 1000|j.m or 10-300 |j.m (microns). The dried composition may comprise one or more

25 hydroxycarbonates of copper and zinc, as well as alumina and silica or their compounds

The dried composition is calcined and desirably shaped to form the catalyst. The dried composition may be calcined, i.e. heated, to convert the copper and any zinc compounds, and any promoter compounds, to their respective oxides prior to shaping or, less preferably, the dried composition may be formed into shaped units before calcination. This latter method is less preferred because the calcination of shaped units generally reduces their strength and makes it more difficult to control pellet density. The calcination may be performed at temperatures in the range of 250 to 500°C preferably 280 to 450°C, more preferably 280 to 350°C. Lower temperatures provide lower pellet stabilities, whereas higher temperatures

35 significantly reduce the initial activity created by the high copper dispersion. Calcination may be performed under air or an inert gas such as nitrogen, but air or another oxygen-containing gas is preferred. The calcined product is typically in the form of a powder. P101107

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The catalyst is preferably pelleted. The dried or calcined powder may therefore be subjected to pelleting, optionally after pre-compacting the powder, which can improve the pelleting process. The pellet may suitably be a cylindrical pellet. Cylindrical pellets for carbon oxide conversion processes suitably have a diameter in the range of 2.5 to 10 mm, preferably 3-10 mm and an

5 aspect ratio (i.e. length / diameter) in the range of 0.5 to 2.0. Alternatively, the shaped unit may be in the form of rings. In one embodiment, the shaped unit is in the form of a cylinder having two or more, preferably 3 to 7 grooves running along its length. Suitable domed cylindrical shapes having one or more flutes are described in our WO2010/029325 and WO2017/072480, herein incorporated by reference.

Pellets, particularly cylindrical pellets with flat or domed ends as described above, are desirably made with pellet densities in the range of 1.8 to 2.5 g/cm ³ , preferably 1 .9 to 2.4 g/cm ³ . The pellet density may readily be determined by calculating the volume from the pellet dimensions and measuring its weight. As the density is increased, the interstitial volume in the shaped

15 units is reduced, which in turn reduces the permeability of reacting gases. Therefore, for densities > 2.4 g/cm ³ the reactivity of the catalyst may be less than optimal, despite the high volumetric copper content. For densities < 1.8 g/cm ³ the crush strengths may be insufficient for long-term use in modern carbon-oxide conversion processes.

20 The relative amounts of copper-containing solution, zinc-containing solution, alkali metal aluminate solution, promoter solution or solutions and silica precursor may be adjusted to produce compositions suitable for use as catalysts. The copper oxide content of the calcined catalyst (expressed as CuO) may be in the range of 30 to 70% by weight. Within this range a copper oxide content in the range of 50 to 70% by weight, preferably 60 to 70% by weight, is of

25 general application for methanol synthesis, whereas for the water-gas shift reaction, the copper oxide content may be lower, particularly in the range of 30 to 60% by weight. Suitably, the copper (II) oxide content of the calcined catalyst is in the range 50 to 68% by weight. As stated above, zinc is preferably included in the first precipitation step. The weight ratio of Cu:Zn (expressed as CuO:ZnO) in the calcined catalyst may be 1 :1 or higher but is preferably in the range of 2:1 to 3.5:1 , especially 2.5:1 to 2.75:1 for methanol synthesis catalysts and in the range of 1 .4:1 to 2.0:1 for water-gas shift catalysts. In the methanol synthesis catalysts, the calcined catalyst preferably contains 15 to 50% by weight, preferably 20-30% by weight zinc oxide, expressed as ZnO

35 The calcined catalyst contains alumina, which may be present in an amount in the range of 5 to 40% by weight preferably 6 to 20% by weight. The alumina may be present as a boehmite AIOOH, and/or as a transition alumina, such as gamma alumina, and/or as a metal aluminate, such as zinc aluminate P101107

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The calcined catalyst contains silica and may have a Si: Al atomic ratio in the range of 0.004 to 0.2:1 . The amount of silica in the catalyst appears to be optimal when the Si:AI atomic ratio is in the range of 0.03 to 0.09:1 . The amount of silica in the catalyst is therefore relatively low, and may be present in the calcined catalyst in an amount in the range of 0.1 to 5.0% by weight,

5 preferably 0.1 to 2.0% by weight, more preferably 0.2 to 1 .0% by weight. Higher amounts of silica reduce the activity of the catalyst and may generate acidic sites that reduce selectivity in methanol production.

If a promoter is included in the first and/or second precipitation steps, the calcined catalyst may contain promoter oxide, e.g. magnesium oxide and/or zirconium oxide, in an amount in the range of 0.5 to 5% by weight.

Preferred methanol synthesis catalysts consist essentially of oxides of copper, zinc, aluminium, magnesium and silicon.

15

The dried catalyst made by the method may have a malachite (e.g. zincian malachite) crystal size of less than 9 nm, preferably below 8 nm, more preferably below 7 nm. The crystal size may be greater than 3 nm. The malachite crystal size may be determined using X-ray Diffraction (XRD).

20

The catalyst desirably has a copper surface area > 45m ² /g catalyst, preferably > 50m ² /g catalyst, more preferably > 55m ² /g catalyst, most preferably > 60m ² /g catalyst. Copper surface areas up to about 70m ² /g catalyst may be achieved. These surface areas are suitably determined on a sample of crushed catalyst pellets. The copper surface area may be readily

25 established by using reactive frontal chromatography as described in EP-A-0202824.

The BET surface area of the shaped catalyst, as determined by nitrogen physisorption (according to ASTM Method D 3663-03), may be > 95m ² /g, and is preferably > 100m ² /g, more preferably > 110m ² /g, most preferably > 115m ² /g. BET surface areas up to about 130m ² /g may be achieved. The BET surface areas are suitably determined on a sample of crushed catalyst pellets.

In the catalyst, the zinc oxide, alumina, silica, and promoter oxides if present, are not substantially reduced to metal under the carbon oxide conversion process conditions and are

35 generally present as the oxides in the catalyst. In contrast, the copper oxide is more readily reduced to the active elemental form. The copper may be reduced either ex-situ or in-situ to form catalytically active copper metal crystallites before use. P101107

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The catalysts prepared by the method may be used in any carbon oxides conversion process, comprising reacting a carbon oxide containing process gas containing at least one of carbon monoxide and carbon dioxide and additionally containing hydrogen and/or steam, in the presence of the catalyst. The term “carbon oxides” herein includes at least one of carbon

5 monoxide and carbon dioxide. The catalysts are of particular utility in methanol synthesis, methanol steam reforming and in the water-gas shift reaction.

The catalyst may be pre-activated in-situ by exposing it to a reducing gas stream, preferably comprising hydrogen, to convert the copper oxide into elemental copper. Thus, the method may further comprise the steps of (i) activating the catalyst by contacting it with a reducing gas stream and (ii) reacting a carbon oxide containing process gas containing at least one of carbon monoxide and carbon dioxide and additionally containing hydrogen and/or steam, in the presence of a catalyst to form a product stream. Activation may be performed using a hydrogen containing gas, including synthesis gas comprising hydrogen and carbon oxides, at

15 temperatures above 80°C and at pressures in the range of 1-50 bar g. The maximum reduction temperature is desirably 150 to 300°C.

The invention includes processes using the catalyst, in particular:

A. Methanol synthesis in which a gas mixture containing one or both carbon oxides (i.e. carbon

20 monoxide and/or carbon dioxide) and hydrogen is passed over the catalyst at a temperature in the range of 200-320°C, a pressure in the range of 20-250, especially 30-120, bar abs and a space velocity in the range of 500-20000 h ^-1 . The process can be on a once-through, or a recycle, basis and can involve cooling by indirect heat exchange surfaces in contact with the reacting gas, or by subdividing the catalyst bed and cooling the gas between the beds by

25 injection of cooler gas or by indirect heat exchange. For this process, the catalyst preferably contains copper, zinc oxide and optionally magnesia, with alumina and silica. The catalysts may be used in methanol synthesis processes in which natural gas is steam reformed or autothermally reformed with oxygen to produce a synthesis gas containing carbon monoxide, carbon dioxide and hydrogen, or in processes where the synthesis gas is richer in carbon monoxide and is derived by the gasification of coal or biomass. The catalyst may be of particular use in methanol synthesis processes where a synthesis gas is formed essentially from hydrogen and carbon dioxide, especially where the hydrogen and/or carbon dioxide are recovered only from renewable sources, such as from the electrolysis of water for hydrogen and CC>2-recovery from waste gases, such as combustion gas or landfill gas.

35

B. Modified methanol synthesis in which the catalyst contains also free alumina of surface area 50-300 m ² g ^-1 , or another acidic catalyst, so that the synthesis product is relatively rich in dimethyl ether. Temperatures, pressures and space velocities are similar to those for methanol synthesis but the synthesis gas may contain hydrogen and carbon monoxide in a molar ratio of P101107

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11 less than 2.

C. Low temperature shift reaction in which a gas containing carbon monoxide (preferably under 4% v/v on a dry basis) and steam (steam to total dry gas molar ratio typically in range of 0.3 to

5 1 .5) is passed over the catalyst in an adiabatic fixed bed at an outlet temperature in the range of 200 to 300°C at a pressure in the range of 15-50 bar abs. Usually the inlet gas is the product of "high temperature shift" in which the carbon monoxide content has been decreased by reaction over a high temperature shift catalyst, such as an iron or zinc aluminate catalyst, at an outlet temperature in the range of 400 to 500 °C, followed by cooling by indirect heat exchange. The outlet carbon monoxide content from the low temperature shift step is typically in the range of 0.1 to 1 .0%, especially under 0.5% v/v on a dry basis.

D. Medium temperature shift in which the gas containing carbon monoxide and steam is fed at a pressure in the range of 15-50 bar abs to the catalyst at an inlet temperature typically in the

15 range of 200 to 240°C although the inlet temperature may be as high as 280°C, and the outlet temperature is typically up to 300°C but may be as high as 360°C. These conditions are more severe than in B, such that the new catalyst is expected to be especially advantageous.

E. Low-medium temperature shift with heat exchange (also termed isothermal shift), in which

20 the reaction in the catalyst bed occurs in contact with heat exchange surfaces. The coolant conveniently is water under such a pressure such that partial, or complete, boiling takes place. A suitable pressure is 15 to 50 bar abs and the resulting steam can be used, for example, to drive a turbine or to provide process steam for shift, or for an upstream stage in which the shift feed gas is generated. The water can be in tubes surrounded by catalyst or vice versa.

25

F. Methanol reforming in which a gaseous methanol stream is combined with steam and/or carbon dioxide and subjected to reaction, typically at temperatures in the range of 250 to 360°C and at pressures typically in the range of 10 to 30 bar abs, over the catalyst to generate a gas mixture containing hydrogen and carbon oxides. The hydrogen may be recovered from the gas mixture using conventional separation methods such as pressure-swing adsorption or hydrogen-permeable membranes.

The invention is now further described by reference to the following Examples.

35 In the Examples, unless otherwise stated, first precipitates were prepared at a 2-6 litre scale by simultaneous addition of an aqueous mixed metal nitrate solution and an aqueous sodium carbonate solution to a stirred precipitation vessel held at 65 to 70 °C. The first precipitates were unaged. Second precipitates were prepared at a 0.5-4 litre scale by addition of an aqueous nitric acid solution, optionally containing dissolved salts of a metal or metals, to an P101107

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12 aqueous sodium aluminate solution in a stirred precipitation vessel held at 65 to 70 °C. Ageing of the slurries of the second precipitates was performed in a stirred vessel for up to 1 hour, again at 65 to 70 °C. The first and second slurries were combined and mixed in an 3-8 litre vessel for up to 2 hours. The silica precursor was added by various means at different points in

5 the preparation process. The mixed precipitate slurries were filtered and washed with demineralised water. Drying and calcination of the washed precipitate was, unless otherwise stated, carried out at 110 °C and 300 °C respectively. The resulting powders were compacted into a shaped unit, which was subsequently crushed into grit particles suitable for testing. The silica sol used throughout was Snowtex-O (Nissan Chemicals). Sodium silicate used was sodium metasilicate nonahydrate (Sigma Aldrich). Unless otherwise stated, the weight percentages of the metal oxides in the catalyst are determined on a loss-free basis. A particularly suitable method for determining the metal oxide content on a loss-free basis is to heat the catalyst to 900°C for 2 hours in air to remove volatiles before measuring the metal oxide contents. The heat-treated catalyst may be stored under anhydrous conditions. The

15 metal oxide content of the catalysts may be determined using any suitable elemental analysis technique, such as X-ray fluorescence spectroscopy (XRF) using known techniques. Copper surface areas were determined using reverse frontal chromatography as follows: catalyst pellets were crushed and sieved to a particle size of 0.6 to 1 .00mm. About 2.0 g of the crushed material was weighed into a stainless steel tube and heated to 68°C and purged with helium for

20 2 minutes. Then, the catalyst was reduced by heating it in a flow of 5%vol H2 in helium, at 4°C I min up to 230°C and holding at this temperature for 30 minutes until fully reduced. The reduced catalyst was cooled to 68°C under helium. The reduced catalyst then had a 2.5%vol N2O in helium gas mixture passed over the catalyst. The evolved gases were passed through a gas chromatograph and the N2 evolution was measured. The discharged catalyst was

25 weighed and from this, the copper surface area per gram of discharged catalyst was calculated.

BET surface areas were determined on the crushed pellet grit, after drying, by nitrogen physisorption using a Micromeritics 2420 ASAP physisorption analyser in accordance with ASTM Method D 3663-03; Standard Test for Surface Area. Nitrogen was used as the adsorbate and the measurements carried out at liquid nitrogen temperature (77K). The cross- sectional area of a nitrogen molecule was taken as 16.2 A ² . Samples were outgassed prior to analysis by purging with dry nitrogen gas for a minimum of 1 hour at an optimal temperature. Five relative pressure/volume data pairs were obtained over the relative pressure region of

35 0.05 to 0.20 P/Po inclusive. The equilibration time for each point was 10 seconds. Malachite crystal sizes of dried intermediates were determined from powder XRD patterns. These were collected on a Bruker D8 diffractometer equipped with a Gbbel mirror, Lynxeye detector and a copper x-ray tube. Phase identification was completed using the Bruker EVA v5.1 .0.5 software. Crystallite size values were estimated using Bruker Topas v6. In the Rietveld method the usual P101107

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13 parameters (sample displacement, scale factors, background coefficients, unit cell parameters and peak shape) were refined. Atomic positions were fixed and not refined. Reported crystallite size values were obtained from an integral breadth based LVol calculation using Lorentzian and Gaussian type component convolutions.

5

Example 1

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 6.1 : 2.3: 1 .0: 0.04 and a copper oxide content of 67.1 wt.% was prepared. In a first precipitation step a mixed metal solution comprising nitrates of copper and zinc was co-precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C to form a first slurry. In a second precipitation step a nitric acid solution, which additionally contained a silica sol, was added to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes to form a second slurry. The precipitate slurries were combined and further aged with stirring for up to 1 .5 hours at 65-70 °C, then dewatered,

15 washed with demineralised water, dried and calcined in air at 300 °C for 6 hours.

Example 2

An oxidic catalyst with the molar ratio Cu: Zn: Al: Mg: Si of 5.6: 2.1 : 1 .0: 0.2: 0.04 and a copper oxide content of 65.8 wt.% was prepared. In a first precipitation step, a mixed metal solution

20 comprising nitrates of copper, zinc and magnesium was co-precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C. In a second precipitation step, a nitric acid solution was added to a solution of sodium aluminate which additionally contained sodium silicate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. The remaining steps were as described in

25 Example 1 .

Example 3

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 5.1 : 1 .9: 1 .0: 0.08 and a copper oxide content of 65.8 wt.% was prepared using the method of Example 1 .

Example 4

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 6.0: 2.2: 1 .0: 0.04 and a copper oxide content of 66.9 wt.% was prepared. In a first precipitation step, a mixed metal solution comprising nitrates of copper and zinc, and additionally containing a silica sol, was co¬

35 precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C. In a second precipitation step, a nitric acid solution was added to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. The remaining steps were as described in Example 1 . P101107

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14

Example 5

An oxidic catalyst with the molar ratio Cu: Zn: Al: Mg: Si of 5.6: 2.1 : 1 .0: 0.3: 0.03 and a copper oxide content of 65.8 wt.% was prepared. In a first precipitation step, a mixed metal solution comprising nitrates of copper and zinc was co-precipitated with a sodium carbonate solution at

5 a pH of 6.7-6.9 and a temperature of 65-70 °C. In a second precipitation step, a nitric acid solution which additionally contained magnesium nitrate and a silica sol was added to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. The remaining steps were as described in Example 1 .

Example 6

An oxidic catalyst with the molar ratio Cu: Zn: Al: Mg: Si of 5.3: 2.0: 1 .0: 0.2: 0.05 and a copper oxide content of 65.2 wt.% was prepared. In a first precipitation step, a mixed metal solution comprising nitrates of copper, zinc and magnesium was co-precipitated with a sodium

15 carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C. In a second precipitation step, a solution of nitric acid and zinc nitrate was added to a solution of sodium aluminate which additionally contained sodium silicate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. The remaining steps were as described in Example 1 . The amounts of zinc nitrate used in the solutions was such that the

20 first precipitate contained 84% of the Zn and the second precipitate 16% of the Zn in the calcined catalyst.

Example 7

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 4.9: 1 .9: 1 .0: 0.03 and a copper oxide

25 content of 65.6 wt.% was prepared. In a first precipitation step, a mixed metal solution comprising nitrates of copper and zinc was co-precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C. In a second precipitation step, a solution of nitric acid and copper nitrate, which additionally contained a silica sol, was added to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. The remaining steps were as described in Example 1 . The amounts of copper nitrate used in the solutions was such that the first precipitate contained 94% of the Cu and the second precipitate 6% of the Cu in the calcined catalyst.

Example 8

35 An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 5.1 : 1 .9: 1 .0: 0.05 and a copper oxide content of 66.1 wt.% was prepared by addition of a nitric acid solution which additionally contained a silica sol to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. A mixed metal solution comprising nitrates of copper and zinc and a sodium carbonate solution were simultaneously P101107

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15 added to the first precipitate with stirring, while maintaining a pH of 6.7-6.9 and a temperature of 65-70 °C. The final precipitate slurry was aged for 1 hour at 65-70 °C, then dewatered, washed with demineralised water, dried and calcined in air at 300 °C for 6 hours.

5 Example 9

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 5.7: 2.2: 1 .0: 0.03 and a copper oxide content of 66.6 wt.% was prepared. In a first precipitation step a mixed metal solution comprising nitrates of copper and zinc was co-precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C to form a first slurry. In a second precipitation step a nitric acid solution, which additionally contained a silica sol, was added to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 3.5-4.5 and a temperature of 65-70 °C for at least 30 minutes to form a second slurry. The remaining steps were as described in Example 1 .

15 Example 10

An oxidic catalyst with the molar ratio Cu: Zn: Al: Mg: Si of 4.6: 1 .8: 1 .0: 0.2: 0.04 and a copper oxide content of 63.6 wt.% was prepared. In a first precipitation step, a mixed metal solution comprising nitrates of copper, zinc and magnesium was co-precipitated with a sodium carbonate solution, which additionally contained sodium silicate, at a pH of 6.6-6.8 and a

20 temperature of 63-68 °C. In a second precipitation step, a nitric acid solution was added to a solution of sodium aluminate to form a precipitate, which was aged at a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. The remaining steps were as described in Example 1 .

25 Comparative Example 1

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 3.8: 2.2: 1 .0: 0.04 and a copper oxide content of 56.6 wt.% was prepared following the procedure outlined in US6048820 Example 2. A mixed metal solution containing nitrates of copper, zinc and aluminium and a silica sol, and a solution of sodium carbonate were added simultaneously to demineralised water in a stirred vessel at room temperature. The resulting precipitate was aged at room temperature for 24 hours, dewatered, washed with demineralised water, dried and calcined in air at 600 °C for 2 hours.

Comparative Example 2

35 An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 4.4: 1.6: 1.0: 0.05 and a copper oxide content of 65.8 wt.% was prepared following the method described in CN110935478. A mixed metal solution containing nitrates of copper and zinc and sodium silicate, a sodium aluminate solution and a sodium hydroxide solution were added simultaneously to demineralised water in a stirred vessel at 55 °C and at a pH of 6-7. The addition of sodium hydroxide was necessary in P101107

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16 order to achieve the required precipitation pH and final composition. The resulting precipitate was aged at 65 °C and a pH of 6.5 for 30 minutes. This precipitate contained 40 wt.% of the total copper oxide content and 50 wt.% of the total silica content. A mixed metal solution containing nitrates of copper and aluminium and sodium silicate and a solution of sodium

5 carbonate were simultaneously combined with the precipitate at 65 °C and a pH of 8-9 with stirring. The resulting slurry was aged at 65 °C and a pH of 8.5 for 2 hours before being dewatered, washed with demineralised water, dried and calcined in air at 300 °C for 6 hours.

Comparative Example 3

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 3.3: 1 .5: 1 .0: 0.01 and a copper oxide content of 60.1 wt.% was prepared following the procedure outlined in CN101306369 Example 5, by co-precipitating a mixed metal solution comprising nitrates of copper and zinc with a sodium carbonate solution at a pH of 7.0-7.2 and a temperature between 65-70 °C to form a first precipitate. Separately, a second precipitate was formed by mixing an aluminium nitrate

15 solution with a solution of sodium carbonate and sodium silicate at a pH of 7-7.2 and a temperature of 80 °C then ageing at 65 °C for 40 minutes. The first and second precipitates were combined in a 1 :7 ratio by volume, and the mixture was aged at 70 °C with stirring for 2 hours. The slurry was dewatered, washed with demineralised water, then dried and calcined in air at 340 °C for 4 hours.

20

Comparative Example 4

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 5.4: 2.0: 1 .0: 0.16 and a copper oxide content of 65.7 wt.% was prepared by addition of a nitric acid solution which additionally contained a silica sol to a solution of sodium aluminate to form a precipitate, which was aged at

25 a pH of 6.2-7.0 and a temperature of 65-70 °C for at least 30 minutes. Separately a mixed metal solution comprising nitrates of copper and zinc was co-precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70 °C. The two precipitates were combined and further aged with stirring for up to 1 .5 hours at 65-70 °C, then dewatered, washed with demineralised water, dried and calcined in air at 300 °C for 6 hours.

Comparative Example 5

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 4.3: 1 .6: 1 .0: 0.03 and a copper oxide content of 64.6 wt.% was prepared by co-precipitation of a mixed metal nitrate solution comprising nitrates of copper and zinc, which additionally contained a silica sol, with a sodium

35 aluminate solution and a sodium carbonate solution at a pH of 6.3-6.9 and a temperature between 65-70 °C. The resulting precipitate was aged for up to 1 .5 hours at 65-70 °C, then dewatered, washed with demineralised water, dried and calcined in air at 300 °C for 6 hours. P101107

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Comparative Example 6

An oxidic catalyst with the molar ratio Cu: Zn: Al: Si of 4.0: 1 .7: 1 .0: 0.04 and a copper oxide content of 62.5 wt.% was prepared. In a first precipitation step, a solution of copper nitrate was co-precipitated with a sodium carbonate solution at a pH of 6.7-6.9 and a temperature of 65-70

5 °C. In a second precipitation step, a solution of zinc nitrate, which additionally contained a silica sol, was added to a solution of sodium aluminate to form a precipitate. A solution of sodium hydroxide was added to the precipitate to adjust the pH, and the resulting slurry was aged at a pH of 6.5-7.0 and a temperature of 65-70 °C for at least 30 minutes. The two precipitates were combined and further aged with stirring for 45 minutes at 65-70 °C, then dewatered, washed

10 with demineralised water, dried and calcined in air at 300 °C for 6 hours.

The catalyst properties were as follows: P101107

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Microreactor Testing

Each of the catalyst samples were crushed and sieved to a particle size fraction of 0.6 -1 .0 mm. The experiments used a conventional micro-reactor. The crushed catalyst samples were fully reduced with a gas mixture of 2 % v/v hydrogen in nitrogen at 225°C. A process gas mixture

5 with a gas composition of 6 % v/v CO, 6 % v/v CO2, 9 % v/v N2 and 79 % v/v H2 was then introduced over the catalyst samples. This process gas mixture is representative of a synthesis gas produced by reforming of natural gas. The reduced catalyst samples were exposed to the process gas mixture at 225 °C, 40,000 L/hr/kg, 50 barg at the start of life. After a period, catalyst samples were exposed to deactivating conditions over 300°C to simulate harsh

10 operating conditions and accelerate the deactivation effects. Analysis flow scans of product gases were performed at the start of life and after the catalyst had been held at deactivation conditions. Analysis flow scans were performed by varying the mass velocity at 225 °C, 50 barg. An infra-red analyser was used to determine the % v/v concentration of the exit gas streams from the reactors. The analysis flow scan data was used to calculate the relative

15 activity of the test material against a reference catalyst, selected in these experiments to be Comparative Example 1 . The relative activities are calculated from the ratio of the flow rates through each catalyst at constant conversion relative to the flow rate through the standard catalyst. The results are set out in the following table: P101107

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19

The testing results show that catalysts made via methods of the invention possess both higher initial activity and higher retained activity, following a period of high temperature deactivation under methanol synthesis conditions, than catalyst made via prior methods (comparative

5 examples 1 , 2 and 3).

Comparative example 4 shows that higher silica loadings can be detrimental to long-term catalyst performance. Comparative example 5 exemplifies a single-step process using sodium aluminate which has poor activity compared to the two-step method. Comparative example 6 demonstrates that when no zinc is present with the copper in the first precipitation step, the activity of the catalyst is severely impacted.

In addition to the above tests carried out with a conventional synthesis gas, further microreactor tests were also carried out on the catalyst of Example 2 to evaluate performance under

15 conditions appropriate for CO2 hydrogenation. In this case, following reduction as above, the samples were exposed to a process gas mixture with a composition of 16 % v/v CO2, 2 % v/v CO, 10 % v/v N2 and 72 % v/v H2, initially at 225 °C, 70,000 L/hr/kg and 50 barg. After a period, the samples were exposed to deactivation conditions above 265 °C to simulate harsh operation and accelerate deactivation. As in the previous testing, flow scans were periodically carried out throughout the run at the milder conditions in order to monitor the remnant activity of the samples. The results obtained are shown in the following table, again with the Comparative example 1 as the reference catalyst:

25 These results again show that catalysts made via methods of the invention possess both higher initial activity and higher retained activity, following a period of high temperature deactivation under CO2 hydrogenation to methanol conditions, than catalyst made via prior methods.