Process for the preparation of solids and use of these solids

Abstract

The present invention relates to a process for the preparation of a solid, the process comprising mixing a compound group comprising at least one Cu2(OH)2CO3 powder, a metal oxide powder selected from the group of metals consisting of copper, zinc, iron, manganese and mixtures thereof and at least one binder, and to the use of the solid prepared by this process.

Description

[0001] This application is a divisional application of patent application No. 201810608806.7, filed on June 13, 2017, with priority date of June 13, 2018, entitled "Method for preparing solids and use of such solids". Technical Field

[0002] This invention relates to a method for preparing copper-based solids, and the uses of these solids, particularly for removing sulfur-containing compounds from gaseous or liquid feedstocks such as natural gas, biogas, syngas, and gaseous or liquid hydrocarbons containing carbon dioxide (CO2).

[0003] The solid prepared according to the present invention can also be used to remove carbon monoxide (CO), mercury-containing compounds, or arsenic-containing compounds from gaseous or liquid feedstocks, and for catalyzing the Dussan reaction (water gas shift reaction, or "water gas shift" according to the English term). Background Technology

[0004] Copper compounds are known in the art to react with sulfur-containing compounds. The use of basic copper carbonate as the active phase is particularly important because its reaction with H₂S appears to be especially rapid.

[0005] Many documents focus on desulfurization in the presence of copper oxide.

[0006] US7837964 describes a desulfurization material that may contain up to 99.8% by weight of copper oxide. This material is prepared by precipitation.

[0007] US4582819 describes a method for desulfurizing liquid hydrocarbons using a solid prepared from basic copper carbonate and alumina. The precursor is not sol-gelled. The solid is heat-treated to partially degrade the basic copper carbonate at temperatures above 260°C to obtain CuO.

[0008] US2013 / 047850 describes a method for purifying syngas (H2, CO) using a CuO-based solid, which is developed based on a method that can prevent or mitigate the reduction of CuO during the industrial processing of syngas. For this purpose, the solid is prepared from basic copper carbonate and a halide additive such as NaCl, and a calcination step at a temperature of 280-500°C (to completely decompose the copper carbonate into CuO).

[0009] Documents US6007706 and EP243052 describe the removal of sulfur-containing compounds using a solid containing at least 70% by weight of a copper compound (carbonate or oxide or otherwise).

[0010] However, none of these documents addressed the issue of the mechanical strength of the prepared materials.

[0011] Document FR2940967 describes the preparation of ZnO-based solids and their use in the desulfurization of liquid or gaseous feedstocks, wherein the solids possess excellent mechanical strength and increased storage capacity. The preparation method includes the steps of mixing ZnO powder, solubilizing, and calcining. According to the document, alkaline solubilization of ZnO allows for partial dissolution of ZnO in an alkaline medium, resulting in a smaller particle size, a denser solid due to better dispersion, and thus increased mechanical strength.

[0012] However, malachite, with the composition Cu2(OH)2CO3, is an alkaline compound that is insoluble in alkaline media but soluble in acidic media. Therefore, as described in FR2940967, alkaline gelation does not have the solubilizing effect that would lead to a reduction in particle size and ultimately an increase in mechanical strength.

[0013] Document WO95 / 24962 describes a trapping material containing at least 75% by weight of copper carbonate, basic copper carbonate, or copper hydroxide. This document relates to obtaining a solid with a loading density of at least 0.9 kg / L, or even 1.2 kg / L, in order to improve the volumetric trapping capacity of the solid (i.e., the amount of sulfur trapped relative to the volume of the solid, not relative to its mass). The document states that the drying / calcination temperature should not exceed 150°C, or even 115°C, so as not to decompose the copper compounds used. This allows for the counting of CO2 and / or water contained in the solid in the form of carbonates and hydroxides, thus contributing to the increased density. Above 150°C, the decomposition of copper carbonate, basic copper carbonate, or copper hydroxide results in a decrease in the loading density of the solid. Furthermore, the document does not describe a gelation step.

[0014] However, solids prepared solely from basic copper carbonate exhibit particularly low mechanical strength properties, even after heat treatment, making them difficult to use, especially prone to wear and the formation of fine particles.

[0015] The method according to the invention can produce a solid that has both increased mechanical strength and a higher effective sulfur capture capacity than that of prior art solids. Summary of the Invention

[0016] Invention Summary

[0017] This invention relates to a method for preparing a solid, comprising the following steps:

[0018] a) A mixture comprising the following compounds: at least one Cu2(OH)2CO3 powder, a metal oxide powder selected from the group consisting of copper, zinc, iron, manganese and mixtures thereof, and at least one binder;

[0019] b) Contact the mixture from step a) with the aqueous solution and mix to obtain the paste;

[0020] c) Extruding the paste mixed in step b) under a pressure of 3 to 25 MPa;

[0021] d) Calcination of the extrudate at a temperature of 140°C to 500°C for 10 minutes to 6 hours under an oxygen-containing gas stream.

[0022] In addition to very good mechanical strength, the obtained adsorbent has optimized density and porosity, thereby maximizing its useful mass capacity while reducing the dispersion front during sulfur capture. Invention Details

[0024] In the following description, the term "solid prepared according to the invention" will also be understood to mean, depending on the intended use of the solid, but not limited to, adsorbents and catalysts or trapping substances.

[0025] In the following description, the terms malachite, basic copper carbonate, and Cu2(OH)2CO3 are used without distinction.

[0026] "Loss on ignition (PAF)" can be understood as the weight loss (wt%) of a solid sample calcined at 550°C for 2 hours.

[0027] "Powder" is understood as a group of particles.

[0028] In the following description, the size distribution of the powder or particles is measured by laser diffraction particle size distribution based on Mie scattering theory (GBJ de Boer, C. de Weerd, D. Thoenes, HWJ Goossens, Part. Character. 4 (1987) 14-19). The particle size distribution of the powder or particles is determined by the median diameter (D). 50 ) indicates that the median diameter (D) 50 A diameter is defined as the diameter of such an equivalent sphere, i.e., 50% by volume of the particles or particles constituting the powder have a size smaller than that diameter.

[0029] In the following text, “specific surface area” may be understood to refer to B.ET. specific surface area, which is determined by nitrogen adsorption according to the ASTM D3663-78 standard, which was established by the BRUNAUER-EMMETT-TELLER method described in “The Journal of American Society, 60, 309, (1938)”.

[0030] Mixing step a)

[0031] According to the present invention, the preparation method includes step a): mixing a compound comprising at least one Cu2(OH)2CO3 powder, a metal oxide powder selected from the group consisting of copper, zinc, iron, manganese and mixtures thereof, and at least one binder.

[0032] In a variation of the method according to the invention, the metal oxide is advantageously copper oxide having the formula CuO. In this variation, the compound group advantageously does not contain zinc oxide.

[0033] In another variation of the method according to the invention, the metal oxide is advantageously zinc oxide (ZnO). In this variation, the compound group advantageously does not contain copper oxide powder.

[0034] According to a preferred variant of the invention, the compound group comprises copper oxide (CuO) powder and zinc oxide (ZnO) powder.

[0035] The compound group is advantageously dry-mixed in step a), i.e., without the addition of liquid. Step a) can be carried out, for example, in a stirrer or any other type of mixer. This step yields a homogeneous mixture of the powder components.

[0036] In a preferred arrangement of the method according to the invention, the compound group comprises CuO powder, which is advantageously obtained by partial decomposition of one or more Cu2(OH)2CO3 powders. This partial decomposition can be carried out, for example, by heat-treating one or more Cu2(OH)2CO3 powders or the compound group of step a) at a temperature of 100-300°C, preferably 150-300°C, preferably 200-300°C, for 1 to 12 hours. This results in a portion of the Cu2(OH)2CO3 powder being converted into CuO powder, the conversion depending on the duration and temperature of the heat treatment.

[0037] In a preferred arrangement of the method according to the invention, the compound group comprises the median diameter (D) of a mixture of CuO powder, Cu2(OH)2CO3 powder, and CuO powder. 50 (less than 45μm)

[0038] The content of metal oxide powder introduced into the mixed compound group in step a), wherein the metal is selected from the group consisting of copper, zinc, iron, manganese, and mixtures thereof, is expressed as the ratio of the mass of metal oxide powder introduced into the mixed compound group in step a) to the total mass of malachite powder and metal oxide powder introduced into the mixed compound group in step a), or in other words, the ratio of (amount of metal oxide powder selected from the group consisting of copper, zinc, iron, manganese, and mixtures thereof introduced into the mixed compound group in step a) to (amount of metal oxide powder selected from the group consisting of copper, zinc, iron, manganese, and mixtures thereof introduced into the mixed compound group in step a) and Cu2(OH)2CO3. This ratio is between 0.01 and 1, preferably between 0.05 and 1, preferably between 0.05 and 0.95, preferably between 0.05 and 0.7, and preferably between 0.1 and 0.6.

[0039] Sources of Cu2(OH)2CO3

[0040] The Cu2(OH)2CO3 powder is from any source known to those skilled in the art. The median diameter (denoted as D) 50 Advantageously, the diameter is between 1-100 μm, preferably between 4-80 μm, and most preferably between 4-50 μm. In a particular arrangement, the compound group comprises only malachite powder, wherein the diameter is between 1-100 μm, preferably between 4-80 μm, and most preferably between 4-50 μm.

[0041] In a particular arrangement, the Cu₂(OH)₂CO₃ powder advantageously exhibits a bimodal distribution. The malachite powder comprises 0.1 to 99.9% by weight, advantageously 2 to 99.9% by weight, preferably 5 to 99.9% by weight, very preferably 5-99% by weight, preferably 5-90% by weight, and very preferably 5-85% by weight of a D₂O₅ having a diameter of 1-15 μm, preferably 1-10 μm, and very preferably 4-9 μm. 50 Malachite particles, and 99.9-0.1 wt%, advantageously 98-0.1 wt%, preferably 95-0.1 wt%, very preferably 95-1 wt%, preferably 95-10 wt%, very preferably 95-15 wt% of a D-type particle with a diameter of 25-100 μm, preferably 25-80 μm, preferably 30-50 μm. 50 Malachite particles, expressed as a weight percentage relative to the total weight of malachite. The bimodal distribution improves the mechanical strength of the resulting final solid.

[0042] Alternatively, the compound group comprises at least two different particle sizes of malachite powder. In this arrangement, the compound group comprises 0.1-99.9% by weight, advantageously 2-99.9% by weight, preferably 5-99.9% by weight, very preferably 5-99% by weight, preferably 5-90% by weight, and very preferably 5-85% by weight of D having a particle size of 1-15 μm, preferably 1-10 μm, and very preferably 4-9 μm. 50 The first type of malachite powder, and 99.9-0.1 wt%, advantageously 98-0.1 wt%, preferably 95 wt%-0.1 wt%, very preferably 95 wt%-1 wt%, preferably 95 wt%-10 wt%, very preferably 95 wt%-15 wt% of a D having a diameter of 25-100 μm, preferably 25-80 μm, preferably 30-50 μm. 50 The second type of malachite powder is expressed as a weight percentage relative to the total weight of the malachite powder.

[0043] Source of CuO

[0044] CuO powder can be derived from any source known to those skilled in the art. It is advantageously derived from precipitation methods or from the calcination of CuO precursors, such as malachite having the formula Cu2(OH)2CO3.

[0045] The copper oxide powder used in the method according to the invention typically has a content of 10-80 μm. 2 .g -1 30-70m is preferred 2 .g -1 Specific surface area.

[0046] The median diameter (D) of the powder 50 Advantageously between 1-50 μm, preferably between 2-35 μm, advantageously between 5-35 μm, and very advantageously between 20-35 μm.

[0047] The combined use of CuO powder and Cu2(OH)2CO3 powder for preparing solids according to the method of the present invention can yield solids with improved mechanical strength and sulfur-containing compound trapping properties.

[0048] Source of ZnO

[0049] ZnO powder is advantageously derived from any source known to those skilled in the art, such as the two main industrial methods known to those skilled in the art for the production of zinc oxide, referred to as the indirect method (the so-called "French method") and the direct method (the so-called "American method"), as described, for example, in FR2940967.

[0050] The zinc oxide powder used in the method according to the invention typically has a content of 10-80 μm.2 .g -1 30-60m is preferred 2 .g -1 Specific surface area.

[0051] ZnO powder has a median diameter (D) 50 Advantageously, the diameter should be less than 60 μm, preferably less than 30 μm, and very preferably less than 10 μm. Most advantageously, the median diameter of the ZnO powder should be between 2 and 5 μm.

[0052] Sources of iron and manganese

[0053] Iron oxide powder and manganese oxide powder are from any source known to those skilled in the art.

[0054] Median diameter (D) of iron oxide powder 50 Advantageously, the diameter should be less than 60 μm, preferably less than 30 μm, and very preferably less than 10 μm. Advantageously, the median diameter of the iron oxide powder should be between 2 and 5 μm.

[0055] Median diameter (D) of manganese oxide powder 50 Advantageously, the diameter should be less than 60 μm, preferably less than 30 μm, and most preferably less than 10 μm. Advantageously, the median diameter of the manganese oxide powder should be between 2 and 5 μm.

[0056] adhesives

[0057] The compound group mixed in step a) includes at least one binder. The binder can shape the adsorbent while providing it with good mechanical strength. The binder is advantageously in powder form.

[0058] Any adhesive known to those skilled in the art can be used. In particular, the adhesive can be advantageously selected from, for example, clays, such as kaolinite-type minerals, palygorskite-type minerals, and montmorillonite-type clay minerals, such as montmorillonite or bentonite. The adhesive can also be selected from alumina, alumina precursors, preferably boehmite, silica, and mixtures thereof. Adhesives of different properties, such as “alumina” type adhesives and “clay” type adhesives, or even adhesives of two different types of clay, can be used in combination. According to a preferred embodiment for preparing the solid according to the invention, the adhesive is a bentonite-type clay.

[0059] The amount of binder used in the preparation method according to the invention is such that the binder accounts for less than 50% by weight of the prepared solid (expressed based on total dry matter, i.e., after burn-off), and depends on the target application.

[0060] Whether for copper compounds, one or more metal oxides, or one or more binders, it is entirely possible to consider mixing multiple sources of each compound.

[0061] When the solid prepared according to the present invention is used for desulfurization of liquid or gaseous feedstock, the binder content of the solid is preferably between 15% and 25% by weight (expressed based on total dry matter, i.e., after burn-off).

[0062] gelation and mixing step b)

[0063] According to the present invention, a method for preparing an adsorbent includes step b) contacting the mixture of step a) with an aqueous solution and mixing the resulting paste.

[0064] This step, which results in the preparation of the paste, disperses the components (i.e., basic copper carbonate, optionally one or more metal oxides, and one or more binders) and partially dissolves the components.

[0065] In the presence of an aqueous solution, the dispersion and dissolution of basic copper carbonate particles, optionally present metal oxide particles, and binder particles that occur during mixing by bringing the different components into contact are preferred. While not wishing to be strictly bound by any particular theory, it can be assumed that better dispersion of basic copper carbonate and optionally one or more metal oxides and one or more binder particles will contribute to improved mechanical strength ultimately obtained by the preparation method.

[0066] The aqueous solution advantageously contains an acidic or basic colloidal solvent.

[0067] The acidic adhesive solvent may be nitric acid, hydrochloric acid, or any other acid known to those skilled in the art, such as inorganic acids like hydrofluoric acid, hydrobromic acid, hydrochloric acid, nitric acid, nitrous acid, sulfonic acid, sulfuric acid, perchloric acid, or even organic mono- or dicarboxylic acids like acetic acid, propionic acid, or butyric acid.

[0068] In one particular arrangement of the method according to the invention, sol-gel is performed using an acidic aqueous solution containing nitric acid. The ratio of HNO3 mass to metal oxide mass is between 0.5-10% by weight, preferably between 0.5-6%, and advantageously between 0.5-3%.

[0069] The mass of the oxide can be calculated using the following formula:

[0070]

[0071] Where m 氧化物 The mass of the oxide initially introduced in step a) in the form of an oxide powder of one or more metals selected from the group consisting of copper, zinc, iron, manganese, and mixtures thereof, m Cu2(OH)2CO3M is the mass of malachite Cu2(OH)2CO3 introduced in step a). CuO M is the molar mass of CuO (=80g / mol). Cu2(OH)2CO3 It is the molar mass of malachite Cu2(OH)2CO3 (=222g / mol).

[0072] The alkaline colloidal solvent can be an inorganic base, such as sodium hydroxide, potassium hydroxide, ammonia, or even an organic base, such as an amine or a quaternary ammonium compound, for example selected from alkyl-ethanolamine or alkyl-ethoxylated amine.

[0073] In a particular arrangement of the method according to the invention, the colloid is performed using an aqueous solution containing an alkaline colloid solvent, preferably selected from sodium hydroxide, potassium hydroxide, ammonia, tetraethylammonium hydroxide (TEAOH), ammonium carbonate, and mixtures thereof. The ratio of the mass of the alkaline colloid solvent to the mass of the metal oxide is 1 to 10% by weight, preferably 2 to 8%, advantageously 2 to 5%. The mass of the oxide is calculated according to the preceding relationship.

[0074] In another specific arrangement of the method according to the invention, sol-gelation is carried out in step b) using an aqueous solution without the addition of acid or alkali. It has been surprisingly observed that sol-gelation with water without the addition of acid or alkali can yield solids with improved adsorption properties, particularly for sulfur-containing compounds. In this specific arrangement, the aqueous solution in step b) is advantageously deionized water, for example, by means of an ion exchange resin.

[0075] The amount of aqueous solution used is adjusted to obtain a non-flowing but no longer too dry paste by means of a peptidation, regardless of the variation implemented, so that it can be extruded in step c) under appropriate pressure conditions known to those skilled in the art and depending on the extrusion equipment used.

[0076] Contact with the reagents (Cu2(OH)2CO3, one or more metal oxides, one or more binders, aqueous solution) is carried out by intermittent or continuous mixing.

[0077] For intermittent mixing, equipment such as a mixer equipped with a Z-arm, roller or cam mixer is known to those skilled in the art, but any other mixing equipment may also be used.

[0078] It is conceivable that adding one or more extrusion additives during the mixing process in step b) can improve the flow of the paste in the die during extrusion. These additives, well known to those skilled in the art, can be selected from, for example, aliphatic monocarboxylic acids, alkylated aromatic compounds, sulfonates, fatty acids, polyvinylpyridine, polyvinylpyrrolidone, polyvinyl alcohol, and cellulose derivatives.

[0079] These additives are typically added at a concentration of 0.1% to 10% by weight, preferably 0.2% to 8% by weight, based on the total mass of the components introduced into the mixer.

[0080] The mixing time is typically between 5 and 60 minutes, preferably between 20 and 50 minutes. The rotation speed of the mixer arm is between 10 and 75 revolutions per minute, preferably between 25 and 50 revolutions per minute.

[0081] Extrusion step c)

[0082] According to the present invention, the method for preparing the adsorbent includes step c) of extruding the paste mixed in step b) under a pressure of 3 to 25 MPa.

[0083] The extrusion step c) can be carried out in any type of extruder, such as a piston, single-screw, or twin-screw extruder. The geometry of the die (the die that shapes the extrudate) can be selected from dies known to those skilled in the art. These dies can be, for example, cylindrical, trilobal, tetralobal, grooved, or have slits.

[0084] The diameter of the mold is given based on the diameter of the desired solid obtained from the calcination step.

[0085] The contacting and mixing in step b) and the extrusion in step c) can be advantageously combined in the same equipment. In one example of this embodiment, the mixed paste can be extruded directly from the end of a twin-screw continuous agitator. In another example of this embodiment, one or more intermittent agitators are connected to the extruder.

[0086] Prior to calcination in step d), the extrudate obtained from step c) is advantageously dried at a temperature of 70 to 160°C for 1 to 24 hours. This drying can advantageously be carried out in air or more preferably in humid air. The advantage of drying is that it removes some of the volatile compounds present in a gentle manner, as direct calcination of the solid may lead to the formation of microcracks. Drying in humid air allows the volatile compounds to evaporate more slowly than drying in air.

[0087] Calcination step d)

[0088] According to the present invention, the method for preparing the adsorbent includes step d) of calcining the extrudate at a temperature between 140°C and 500°C under an oxygen-containing gas stream for 10 minutes to 6 hours.

[0089] The calcination step d) is carried out under an oxygen-containing gas stream. The gas stream may advantageously be air or a mixture of an inert gas (e.g., nitrogen) and oxygen. The gas stream preferably contains at least 5% by volume, more preferably at least 10% by volume, of oxygen. The gas stream also advantageously contains water, and preferably at most 3% by volume.

[0090] The calcination step d) is carried out at a temperature between 140°C and 500°C, preferably between 200°C and 500°C, and preferably between 200°C and 350°C for 10 minutes to 6 hours, preferably 10 minutes to 4 hours, preferably 10 minutes to 3 hours, very preferably 10 minutes to 2 hours, and very preferably 15 minutes to 1 hour.

[0091] The calcination process is particularly effective in converting a portion of malachite into copper oxide.

[0092] Due to the calcination step d), the extrudate has a diameter of 1 to 10 mm, preferably 1 to 5 mm, and very preferably 1.5 to 3.5 mm.

[0093] The solid obtained by extrusion according to the invention has a shape similar to a cylindrical rod. These rods can be introduced into a device that can make their surfaces circular (e.g., a ball rolling machine) or any other device that can be used to spherize them.

[0094] The mass percentage of oxides contained in the solid after burn-off (the content of oxides + CuO, where CuO comes from the decomposition of malachite) can be determined as follows:

[0095]

[0096] Where m 氧化物 The mass, m, of the oxide initially introduced in step a) in the form of an oxide powder of one or more metals selected from copper, zinc, iron, manganese, and mixtures thereof. 粘合剂 It is the mass of the adhesive introduced in step a), m Cu2(OH)2CO3 M is the mass of malachite Cu2(OH)2CO3 introduced in step a). CuO M is the molar mass of CuO (=80g / mol). Cu2(OH)2CO3 It is the molar mass of malachite Cu2(OH)2CO3 (=222g / mol).

[0097] The solid prepared according to the present invention comprises at least:

[0098] - 50-99% by weight, preferably 60-95% by weight, more preferably 75-85% by weight of CuO oxide + optionally present metal oxide, measured after burning at 550°C for 2 hours, the content of which is determined according to the preceding relationship;

[0099] -1 to 50% by weight, preferably 5 to 40% by weight, more preferably 15 to 25% by weight of the binder, the mass percentage being measured after burn-off.

[0100] These contents, expressed as % by weight, are relative to the total mass of the solid prepared by the method according to the invention, and are measured after the precursor has been decomposed at 550°C for 2 hours.

[0101] Properties of solids obtained by the method according to the invention

[0102] Mechanical properties were determined using the pellet breakage test (EGG) as described in ASTM D 6175-3. This involves measuring the breaking strength of each particle in a representative sample containing at least 50 particles. The results are weighted by the length of the extrudate. The EGG value is the average breaking strength (in daN.mm) measured for all sample particles and defined to a unit length of that extrudate. -1 express).

[0103] In the case of the solid prepared according to the present invention, the EGG value is greater than 0.7 daN·mm. -1 (Extrusion length in 10 Newtons / mm), preferably greater than 0.9 daN.mm -1 And regardless of the amount of basic copper carbonate used.

[0104] Furthermore, the resulting solid used as an adsorbent exhibits improved desulfurization performance in treating gases and liquids containing sulfur-containing compounds (especially hydrogen sulfide, thiols, COS, and CS2).

[0105] The present invention also relates to the use of solids prepared by the method according to the invention.

[0106] The solid prepared according to the present invention can be used to purify gaseous feedstocks, such as gaseous hydrocarbons, for example natural gas, biogas, gases containing carbon dioxide (CO2), or syngas, for example in waste heat power generation units, in chemical synthesis units, such as those used in methanol synthesis units or Fischer-Tropsch synthesis units, or liquids, such as hydrocarbons used as feedstocks in catalytic reforming, isomerization, or hydrogenation units.

[0107] The solid prepared according to the invention is advantageously used for purifying any gaseous or liquid feedstock, especially those containing sulfur-containing compounds (e.g., H2S, COS and / or CS2, and / or thiols), at pressures of 0.1-25 MPa, preferably 0.1-15 MPa, and at temperatures of 0-450°C, preferably 15-300°C, and preferably 15-250°C.

[0108] In particular, the solid prepared according to the invention can be advantageously used to purify the raw materials of the Fischer-Tropsch synthesis unit by using it in a reactor operating at a pressure of 0.1 to 15 MPa, preferably 1.5 to 5.0 MPa, and at a temperature of 0 to 400°C, preferably 0 to 220°C, preferably 15 to 180°C.

[0109] The solid prepared according to the invention can also be used to remove some impurities present in liquid or gaseous effluents, such as phosphorus or its compounds, such as phosphine PH3 and / or chlorine, particularly in the form of HCl, preferably at a pressure between 0.1-25 MPa, more preferably between 1-15 MPa, and at a temperature between 0-200°C.

[0110] The solid prepared according to the invention can also be used to remove heavy metals, such as mercury and / or arsenic or its compounds, such as arsine (AsH3), present in liquid or gaseous effluents, preferably at a pressure of 0.1 to 25 MPa, more preferably 1 to 15 MPa, and at a temperature of 0 to 200°C.

[0111] In fact, if the raw material to be purified contains mercury in addition to sulfur-containing compounds, the solid prepared by the method of the present invention can also remove the mercury present in the raw material to be treated.

[0112] If the raw material to be treated does not contain sulfur compounds, the solid prepared according to the invention can advantageously undergo a sulfidation step prior to its industrial implementation in a method for capturing mercury.

[0113] The solid prepared according to the present invention can also be used to remove carbon monoxide (CO) present in liquid or gaseous effluents at temperatures of 0 to 200°C and pressures of 0.1 to 25 MPa.

[0114] The solid prepared according to the invention is used by contacting the gaseous or liquid feedstock to be treated with the solid in a reactor, which may be a fixed-bed reactor, a radial reactor, or even a fluidized-bed reactor.

[0115] The solid prepared according to the present invention can also be reduced with syngas in a reducing atmosphere, such as a hydrogen flow, and then used as a catalyst for the Dussan or water-gas shift reaction, or as a catalyst for the synthesis of methanol from syngas.

[0116] Typical operating conditions for this solid as a catalyst for methanol synthesis are a temperature of 100-500°C, preferably 150-300°C, even more preferably 220-280°C, and a pressure of 0.1 to 25 MPa, preferably 1 to 15 MPa, even more preferably 5 to 10 MPa.

[0117] Typical conditions for using this solid as a catalyst for the Dussan reaction are a temperature of 100-500°C, preferably 150-300°C, even more preferably 180-250°C, and a pressure of 0.1 to 25 MPa, preferably 1 to 15 MPa, even more preferably 1.5 to 10 MPa. Attached Figure Description

[0118] Figure 1 The breakthrough curve can be obtained according to the scheme described below for measuring the ability of a solid to trap impurities. A schematic diagram. In Figure 1 In the middle, t p It is time travel, t f It is the end point that transcends time. Detailed Implementation

[0119] Example

[0120] A scheme for measuring the ability of the prepared solid to trap impurities.

[0121] Use penetration test (test de) The ability of a solid prepared by the method according to the invention to capture impurities is measured.

[0122] For the test used to determine H2S capture capacity, the test was conducted at a temperature of 50°C, a pressure of 0.3 MPa, and for 1530 hours. -1 The test was conducted using hourly volumetric velocity (HVV). "Hourly volumetric velocity" can be understood as the ratio of the gas volumetric flow rate measured at 0°C and 1 atmosphere to the volume of the solid being tested. The gas used for the test contained 0.9 vol% H₂S in nitrogen. The H₂S content present in the outlet gas from the reactor containing the solid was determined by gas chromatography.

[0123] For the test to determine the ability to capture methanethiol (CH3SH), the test was conducted at a temperature of 50°C and a pressure of 0.3 MPa for 1530 h. -1The test was conducted at an hourly volumetric velocity (HVV). "Hourly volumetric velocity" can be understood as the ratio of the gas volumetric flow rate measured at 0°C and 1 atm to the volume of the solid being tested. The gas used for testing contained 0.2% by volume CH3SH in nitrogen. The CH3SH content present in the effluent gas from the reactor containing the solid was determined by gas chromatography.

[0124] For the test to determine the ability to capture ethanethiol (C2H5SH), the test was conducted at a temperature of 50°C and a pressure of 0.3 MPa for 1530 h. -1 The test was conducted at an hourly volumetric velocity (HVV). "Hourly volumetric velocity" can be understood as the ratio of the gas volumetric flow rate measured at 0°C and 1 atm to the volume of the solid being tested. The gas used for testing contained 0.9 vol% C₂H₅SH in nitrogen. The C₂H₅SH content present in the effluent gas from the reactor containing the solid was determined by gas chromatography.

[0125] For the test to determine the ability to capture carbon monoxide (CO), the test was conducted at a temperature of 200°C and a pressure of 0.1 MPa for 2600 h. -1 The test was conducted at an hourly volumetric velocity (HVV). "Hourly volumetric velocity" can be understood as the ratio of the gas volumetric flow rate measured at 0°C and 1 atm to the volume of the solid being tested. The gas used for testing contained 1.8% CO by volume. The CO content present in the outlet gas of the reactor containing the solid was determined by gas chromatography.

[0126] The ability of the solid prepared according to the method of the present invention to trap substance i is determined by implementing a mass balance. As defined in the present invention, the ability to trap substance i corresponds to the amount of substance i accumulated by the solid prior to penetration (i.e., in the schematic representation of the penetration curve). Figure 1 The time t indicated in the middle p (location), which is calculated using the following formula:

[0127]

[0128] in:

[0129] q i : is the mass (in grams) of substance i captured by the solid.

[0130] D i E : is the inflow rate of substance i (mol·min) -1 ),

[0131] Mi: is the molar mass (g·mol⁻¹) of substance i. -1 ),

[0132] C i E : is the content of substance i in the flowing gas.

[0133] C i S : refers to the content of substance i at the reactor outlet.

[0134] t p : is the time (in minutes) required for substance i to penetrate, such as in Figure 1 As shown in the image.

[0135] exist Figure 1 In the middle, t p It is time travel, and t f It is the end point that transcends time.

[0136] The ability of the tested solid to capture substance i is provided by the following relationship:

[0137]

[0138] Where m is the mass of the adsorbent used in the test.

[0139] Example 1: According to the prior art

[0140] In Example 1, reference solids A1, A2, A3, A4, and A5 were prepared according to the following procedure:

[0141] a) A mixture of compounds containing Cu2(OH)2CO3 powder and a binder;

[0142] b) Contact the mixture from step a) with an aqueous solution (gelatinize), and mix the resulting paste in a mixer equipped with a Z-arm at an arm rotation speed of 25 rpm for 30 minutes.

[0143] c) The paste mixed in step b) is extruded at a diameter of 3 mm and a length of 5 to 10 mm by means of a piston extruder under a pressure that varies depending on the solid.

[0144] d) Calcine the extrudate at a temperature that varies depending on the solid, with calcination carried out under an air stream for 1 hour.

[0145] Bentonite-type clay is used as an adhesive.

[0146] After ignition (550°C, 2 hours), the CuO content or the mass percentage of oxides (CuO from the decomposition of malachite) was 80% by weight for solids A1, A2, A3, and A4, and 60% by weight for solid A5 (supplemented with bentonite-type binder). These contents were determined according to the following relationship:

[0147]

[0148] Where m 粘合剂 It is the mass of the adhesive introduced in step a), m Cu2 (OH) 2CO3 M is the mass of malachite Cu2(OH)2CO3 introduced in step a). CuO M is the molar mass of CuO (=80g / mol). Cu2(OH)2CO3 It is the molar mass of malachite Cu2(OH)2CO3 (=222g / mol).

[0149] For solids A1, A2, and A3, the amount of NaOH base is 4 by weight relative to the total amount of Cu2(OH)2CO3 introduced.

[0150] For solids A4 and A5, deionized water is used as an aqueous solution for mixing step b).

[0151] During the extrusion process, the pressure varies between 50 and 150 bar, depending on the formulation used.

[0152] The formulations for solids A1, A2, A3, A4, and A5 are given in Table 1.

[0153] Table 1

[0154]

[0155] The mechanical strength of the extrudate was determined by particle breakage type mechanical test (EGG) as described above.

[0156] Due to limitations related to industrial use, the mechanical strength of solids A1 to A5 is too low. Measured EGG values ​​are below 0.7 daN·mm⁻¹, regardless of calcination temperature and the presence of sodium hydroxide during the sol-gel process.

[0157] The increase in binder content and the decrease in malachite content in solid A5 result in a slight improvement in mechanical strength (however, it is insufficient), which impairs its sulfur capture capacity. In the latter case, its sulfur capacity is weakened compared to the solid according to the invention.

[0158] Example 2: According to the present invention

[0159] In Example 2, the solids, referred to as B1 to B4 according to the present invention, were prepared by mixing and extrusion in the following manner:

[0160] a) A mixture of compounds comprising Cu2(OH)2CO3 powder, CuO powder and binder;

[0161] b) Contact the mixture from step a) with an aqueous solution (gelation), and mix the resulting paste in a mixer equipped with a Z-arm at an arm rotation speed of 25 rpm for 30 minutes.

[0162] c) The paste mixed in step b) is extruded at a diameter of 3 mm and a length of 5 to 10 mm by means of a piston extruder under a pressure that varies depending on the solid.

[0163] d) The extrudate is calcined at a variable temperature according to the embodiment described, and the calcination is carried out under an air stream for 1 hour.

[0164] Bentonite-type clay is used as an adhesive.

[0165] After ignition (550°C, 2 hours), the CuO content or the mass percentage of oxides (oxides + CuO content, from the decomposition of malachite) for solids B1 to B4 is 80% by weight. This content is determined according to the following equation:

[0166]

[0167] Where m CuO The mass of CuO initially introduced in CuO powder form in step a) is m. 粘合剂 It is the mass of the adhesive introduced in step a), m Cu2(OH)2CO3 M is the mass of malachite Cu2(OH)2CO3 introduced in step a). CuO M is the molar mass of CuO (=80g / mol). Cu2(OH)2CO3 It is the molar mass of malachite Cu2(OH)2CO3 (=222g / mol).

[0168] For solid B1, the amount of NaOH base is 4 by weight relative to the total amount of Cu2(OH)2CO3 and CuO introduced.

[0169] For solids B2, B3 and B4, deionized water is used as the aqueous solution for mixing step b).

[0170] During extrusion, the pressure varies between 50 and 200 bar, depending on the formulation used.

[0171] The formulations for the solids are given in Table 2.

[0172] Table 2

[0173]

[0174] The combination of CuO and Cu2(OH)2CO3 in the preparation method according to the present invention yields a product with satisfactory mechanical properties (EGG > 0.7 daN / mm).-1 The solid contains sulfur. Furthermore, the solid exhibits satisfactory vulcanization ability, exceeding 0.15 g sulfur / g solid under the test conditions described in this document.

[0175] Example 3: According to the present invention

[0176] In Example 3, the solids referred to as C1 and C2 according to the present invention were prepared by mixing and extrusion in the following manner:

[0177] a) A mixture of compounds comprising Cu2(OH)2CO3 powder, ZnO powder and binder;

[0178] b) Contact the mixture from step a) with an aqueous solution (gelation), and mix the resulting paste in a mixer equipped with a Z-arm at an arm rotation speed of 25 rpm for 30 minutes.

[0179] c) The paste mixed in step b) is extruded at a diameter of 3 mm and a length of 5 to 10 mm by means of a piston extruder under a pressure that varies depending on the solid.

[0180] d) Calcine the extrudate at a variable temperature according to the embodiment for 1 hour under an air stream.

[0181] Bentonite-type clay is used as an adhesive.

[0182] After ignition (550°C, 2 hours), the CuO+ZnO content or the mass percentage of oxides (oxides + CuO content, from the decomposition of malachite) is 80% by weight for solids C1 and C2. This content is determined according to the following relationship:

[0183]

[0184] Where m ZnO The mass of ZnO initially introduced in the form of ZnO powder in step a) is m. 粘合剂 It is the mass of the adhesive introduced in step a), m Cu2(OH)2CO3 M is the mass of malachite Cu2(OH)2CO3 introduced in step a). CuO M is the molar mass of CuO (=80g / mol). Cu2(OH)2CO3 It is the molar mass of malachite Cu2(OH)2CO3 (=222g / mol).

[0185] For solids C1 and C2, the amount of NaOH base is 4% by weight relative to the total amount of Cu2(OH)2CO3 and CuO introduced.

[0186] During the extrusion process, the pressure varies between 50 and 150 bar, depending on the formulation used.

[0187] Table 3 gives the formulations for the solids.

[0188] Table 3

[0189]

[0190] The combination of ZnO and Cu2(OH)2CO3 in the preparation method according to the present invention yields a solid with satisfactory mechanical properties (EGG > 0.7 daN / mm). -1 Furthermore, the solid exhibits satisfactory vulcanization capacity, exceeding 0.15 g sulfur / g solid under the test conditions described in this document.

[0191] Example 4: According to the present invention

[0192] Example 4 demonstrates the capture properties of solid B3 according to the invention, the preparation of which is described in Example 2.

[0193] The performance in capturing different impurities was determined according to the scheme described above for measuring the ability of the prepared solid to capture impurities.

[0194] The ability to capture the following sulfur-containing compounds H2S, CH3SH, C2H5SH, and carbon monoxide CO has been evaluated under the test conditions described in this protocol.

[0195] The test results are listed in Table 4.

[0196] Table 4

[0197]

[0198] The results show that, under the test conditions, solid B3 obtained by the method according to the present invention can penetrate before (at t p Previously, sulfur was chelated onto solid B3 to remove sulfur-containing compounds H2S, CH3SH, and C2H5SH from gases, as shown in Table 4.

[0199] Because before carbon monoxide was first observed at the reactor outlet (i.e., during breakthrough t) p Previously, under the measured conditions, 0.23 g CO / g solid was captured, and solid B3 was also able to purify gases containing carbon monoxide.

Claims

1. A process for the preparation of a solid, comprising the following steps: a) mixing a group of compounds comprising: malachite Cu2(OH)2CO3 powder, a metal oxide powder selected from the group of metals consisting of copper, zinc and mixtures thereof, the metal oxide powder being present in an amount comprised between 0.05 and 0.7, wherein the amount of said metal oxide powder is expressed as the mass of the metal oxide powder to the total mass of malachite Cu2(OH)2CO3 powder and metal oxide powder introduced in the group of compounds to be mixed in step a), and at least one binder, the amount of said binder being comprised between 15 and 25% by weight, expressed on the total dry matter after loss on ignition; b) contacting the mixture of step a) with an aqueous solution and mixing, thereby obtaining a paste; c) extruding the paste mixed in step b) at a pressure comprised between 3 and 25 MPa; d) calcining the extrudate under a gas flow comprising oxygen at a temperature comprised between 140 °C and 500 °C for a duration comprised between 10 minutes and 6 hours; wherein the solid obtained by said process has a mechanical strength EGG greater than 0.7 daN.mm -1 and the solid has a sulfur capturing capacity greater than 0.15 grams of sulfur per gram of solid.

2. The process according to claim 1, wherein the extrudate obtained from step c) is dried at a temperature comprised between 70 and 160 °C for a duration comprised between 1 and 24 hours before calcination in step d).

3. The process according to any one of claims 1-2, wherein the Cu2(OH)2CO3 powder has a bimodal distribution.

4. The method according to claim 3, wherein the Cu2(OH)2CO3 powder comprises 0.1 to 99.9 wt% of its D 50 1-15 pm malachite particles, and 99.9 to 0.1 wt% of its D 50 between 25-100 pm malachite particles, the weight percentages being expressed relative to the total weight of malachite.

5. The process according to any one of claims 1-2, wherein the metal oxide comprised in the group of compounds of step a) is copper oxide, the group of compounds being free of zinc oxide.

6. The process according to any one of claims 1-2, wherein the aqueous solution of step b) contains an acidic or basic peptizing agent.

7. The process according to claim 6, wherein the aqueous solution contains nitric acid, HNO3, in a mass / metal oxide mass ratio comprised between 0.5 and 10% by weight.

8. The process according to claim 6, wherein the basic peptizing agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, aqueous ammonia, tetraethylammonium hydroxide (TEAOH), ammonium carbonate and mixtures thereof, the basic peptizing agent being present in a mass / metal oxide mass ratio comprised between 1 and 10% by weight.

9. The process according to any one of claims 1 to 2, wherein the aqueous solution of step b) is deionized water.

10. The process according to any one of claims 1 to 2, wherein the calcination step d) is performed at a temperature comprised between 200 °C and 500 °C.

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